Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture 1774912015, 9781774912010

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SUSTAINABLE NANOMATERIALS FOR BIOSYSTEMS ENGINEERING Trends in Renewable Energy, Environment, and Agriculture

Innovations in Agricultural and Biological Engineering

SUSTAINABLE NANOMATERIALS FOR BIOSYSTEMS ENGINEERING Trends in Renewable Energy, Environment, and Agriculture

Edited by Junaid Ahmad Malik, PhD Megh R. Goyal, PhD, PE Mohamed Jaffer M. Sadiq, PhD

First edition published 2023 Apple Academic Press Inc. 1265 Goldenrod Circle, NE, Palm Bay, FL 32905 USA 760 Laurentian Drive, Unit 19, Burlington, ON L7N 0A4, CANADA

CRC Press 6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487-2742 USA 4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN UK

© 2023 by Apple Academic Press, Inc. Apple Academic Press exclusively co-publishes with CRC Press, an imprint of Taylor & Francis Group, LLC Reasonable efforts have been made to publish reliable data and information, but the authors, editors, and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors, editors, and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged, please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, access www.copyright.com or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. For works that are not available on CCC please contact [email protected] Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe. Library and Archives Canada Cataloguing in Publication Title: Sustainable nanomaterials for biosystems engineering : trends in renewable energy, environment, and agriculture / edited by Junaid Ahmad Malik, PhD, Megh R. Goyal, PhD, PE, Mohamed Jaffer M. Sadiq, PhD. Names: Malik, Junaid Ahmad, 1987- editor. | Goyal, Megh R., editor. | Sadiq, Mohamed Jaffer M. editor. Series: Innovations in agricultural and biological engineering. Description: First edition. | Series statement: Innovations in agricultural and biological engineering | Includes bibliographical references and index. Identifiers: Canadiana (print) 20220446180 | Canadiana (ebook) 20220446326 | ISBN 9781774912010 (hardcover) | ISBN 9781774912027 (softcover) | ISBN 9781003333517 (ebook) Subjects: LCSH: Nanostructured materials—Environmental aspects. | LCSH: Nanobiotechnology. | LCSH: Biological systems. | LCSH: Bioengineering. Classification: LCC TA418.9.N35 S87 2023 | DDC 620.1/15—dc23 Library of Congress Cataloging-in-Publication Data

CIP data on file with US Library of C ​ ​ongress

ISBN: 978-1-77491-201-0 (hbk) ISBN: 978-1-77491-202-7 (pbk) ISBN: 978-1-00333-351-7 (ebk)

ABOUT THE BOOK SERIES: INNOVATIONS IN AGRICULTURAL AND BIOLOGICAL ENGINEERING Under this book series, Apple Academic Press Inc. is publishing book volumes over a span of 8–10 years in the specialty areas defined by the American Society of Agricultural and Biological Engineers (). Apple Academic Press Inc. aims to be a principal source of books in agricultural and biological engineering. We welcome book proposals from readers in areas of their expertise. The mission of this series is to provide knowledge and techniques for agricultural and biological engineers (ABEs). The book series offers high-quality reference and academic content on agricultural and biological engineering (ABE) that is accessible to academicians, researchers, scientists, university faculty and university-level students, and professionals around the world. Agricultural and biological engineers ensure that the world has the necessities of life, including safe and plentiful food, clean air and water, renewable fuel and energy, safe working conditions, and a healthy environment by employing knowledge and expertise of the sciences, both pure and applied, and engineering principles. Biological engineering applies engineering practices to problems and opportunities presented by living things and the natural environment in agriculture. ABE embraces a variety of the following specialty areas (): aquaculture engineering, biological engineering, energy, farm machinery and power engineering, food, and process engineering, forest engineering, information, and electrical technologies, soil, and water conservation engineering, natural resources engineering, nursery, and greenhouse engineering, safety, and health, and structures and environment. For this book series, we welcome chapters on the following specialty areas (but not limited to): • • • •

Academia to industry to end-user loop in agricultural engineering; Agricultural mechanization; Aquaculture engineering; Biological engineering in agriculture;

vi

About the Book Series

• • • • • • • • • • • • • • • • • • • • • • • • • •

Biotechnology applications in agricultural engineering; Energy source engineering; Farm to fork technologies in agriculture; Food and bioprocess engineering; Forest engineering; GPS and remote sensing potential in agricultural engineering; Hill land agriculture; Human factors in engineering; Impact of global warming and climatic change on agriculture economy; Information and electrical technologies; Irrigation and drainage engineering; Nanotechnology applications in agricultural engineering; Natural resources engineering; Nursery and greenhouse engineering; Potential of phytochemicals from agricultural and wild plants for human health; Power systems and machinery design; Robot engineering and drones in agriculture; Rural electrification; Sanitary engineering; Simulation and computer modeling; Smart engineering applications in agriculture; Soil and water engineering; Micro-irrigation engineering; Structures and environment engineering; Waste management and recycling; Any other focus areas.

For more information on this series, readers may contact: Megh R. Goyal, PhD, PE Book Series Senior Editor-in-Chief: Innovations in Agricultural and Biological Engineering E-mail: [email protected]

OTHER BOOKS ON AGRICULTURAL AND BIOLOGICAL ENGINEERING BY APPLE ACADEMIC PRESS, INC. Management of Drip/Trickle or Micro Irrigation Megh R. Goyal, PhD, PE, Senior Editor-in-Chief Evapotranspiration: Principles and Applications for Water Management Megh R. Goyal, PhD, PE and Eric W. Harmsen, PhD Editors Book Series: Research Advances in Sustainable Micro Irrigation Senior Editor-in-Chief: Megh R. Goyal, PhD, PE • Volume 1: Sustainable Micro Irrigation: Principles and Practices • Volume 2: Sustainable Practices in Surface and Subsurface Micro Irrigation • Volume 3: Sustainable Micro Irrigation Management for Trees and Vines • Volume 4: Management, Performance, and Applications of Micro Irrigation Systems • Volume 5: Applications of Furrow and Micro Irrigation in Arid and Semi-Arid Regions • Volume 6: Best Management Practices for Drip Irrigated Crops • Volume 7: Closed Circuit Micro Irrigation Design: Theory and Applications • Volume 8: Wastewater Management for Irrigation: Principles and Practices • Volume 9: Water and Fertigation Management in Micro Irrigation • Volume 10: Innovation in Micro Irrigation Technology Book Series: Innovations and Challenges in Micro Irrigation Senior Editor-in-Chief: Megh R. Goyal, PhD, PE • Engineering Interventions in Sustainable Trickle Irrigation: Water Requirements, Uniformity, Fertigation, and Crop Performance • Management Strategies for Water Use Efficiency and Micro Irrigated Crops: Principles, Practices, and Performance

viii

Other Books on Agricultural and Biological Engineering

• Micro-Irrigation Engineering for Horticultural Crops: Policy Options, Scheduling, and Design • Micro-Irrigation Management: Technological Advances and Their Applications • Micro-Irrigation Scheduling and Practices • Performance Evaluation of Micro-Irrigation Management: Principles and Practices • Potential of Solar Energy and Emerging Technologies in Sustainable Micro-Irrigation • Principles and Management of Clogging in Micro-Irrigation • Sustainable Micro-Irrigation Design Systems for Agricultural Crops: Methods and Practices Book Series: Innovations in Agricultural and Biological Engineering Senior Editor-in-Chief: Megh R. Goyal, PhD, PE • Advanced Research Methods in Food Processing Technologies • Advances in Food Process Engineering: Novel Processing, Preservation and Decontamination of Foods • Advances in Green and Sustainable Nanomaterials: Applications in Energy, Biomedicine, Agriculture, and Environmental Science • Advances in Sustainable Food Packaging Technology • Analytical Methods for Milk and Milk Products, 2-volume set: o Volume 1: Sampling Methods, Chemical and Compositional Analysis o Volume 2: Physicochemical Analysis of Concentrated, Coagulated and Fermented Products • Biological and Chemical Hazards in Food and Food Products: Prevention, Practices, and Management • Bioremediation and Phytoremediation Technologies in Sustainable Soil Management, 4-volume set: o Volume 1: Fundamental Aspects and Contaminated Sites o Volume 2: Microbial Approaches and Recent Trends o Volume 3: Inventive Techniques, Research Methods, and Case Studies o Volume 4: Degradation of Pesticides and Polychlorinated Biphenyls • Dairy Engineering: Advanced Technologies and Their Applications • Developing Technologies in Food Science: Status, Applications, and Challenges

Other Books on Agricultural and Biological Engineering ix

• • • • • • • • • • • • • • •

• • •

Emerging Technologies in Agricultural Engineering Engineering Interventions in Agricultural Processing Engineering Interventions in Foods and Plants Engineering Practices for Agricultural Production and Water Conservation: An Interdisciplinary Approach Engineering Practices for Management of Soil Salinity: Agricultural, Physiological, and Adaptive Approaches Engineering Practices for Milk Products: Dairyceuticals, Novel Technologies, and Quality Enzyme Inactivation in Food Processing: Technologies, Materials, and Applications Field Practices for Wastewater Use in Agriculture: Future Trends and Use of Biological Systems Flood Assessment: Modeling and Parameterization Food Engineering: Emerging Issues, Modeling, and Applications Food Process Engineering: Emerging Trends in Research and Their Applications Food Processing and Preservation Technology: Advances, Methods, and Applications Food Technology: Applied Research and Production Techniques Functional Dairy Ingredients and Nutraceuticals: Physicochemical, Technological, and Therapeutic Aspects Handbook of Research on Food Processing and Preservation Technologies, 5-volume set: o Volume 1: Nonthermal and Innovative Food Processing Methods o Volume 2: Nonthermal Food Preservation and Novel Processing Strategies o Volume 3: Computer-Aided Food Processing and Quality Evaluation Techniques o Volume 4: Design and Development of Specific Foods, Packaging Systems, and Food Safety o Volume 5: Emerging Techniques for Food Processing, Quality, and Safety Assurance Modeling Methods and Practices in Soil and Water Engineering Nanotechnology and Nanomaterial Applications in Food, Health, and Biomedical Sciences Nanotechnology Applications in Agricultural and Bioprocess Engineering: Farm to Table

x

Other Books on Agricultural and Biological Engineering

• Nanotechnology Applications in Dairy Science: Packaging, Processing, and Preservation • Nanotechnology Horizons in Food Process Engineering, 3-volume set: o Volume 1: Food Preservation, Food Packaging and Sustainable Agriculture o Volume 2: Scope, Biomaterials, and Human Health o Volume 3: Trends, Nanomaterials, and Food Delivery • Novel and Alternative Methods in Food Processing: Biotechnological, Physicochemical, and Mathematical Approaches • Novel Dairy Processing Technologies: Techniques, Management, and Energy Conservation • Novel Processing Methods for Plant-Based Health Foods: Extraction, Encapsulation and Health Benefits of Bioactive Compounds • Novel Strategies to Improve Shelf-Life and Quality of Foods: Quality, Safety, and Health Aspects • Phytochemicals and Medicinal Plants in Food Design: Strategies and Technologies for Improved Healthcare • Processing of Fruits and Vegetables: From Farm to Fork • Processing Technologies for Milk and Milk Products: Methods, Applications, and Energy Usage • Quality Control in Fruit and Vegetable Processing: Methods and Strategies • Scientific and Technical Terms in Bioengineering and Biological Engineering • Soil and Water Engineering: Principles and Applications of Modeling • Soil Salinity Management in Agriculture: Technological Advances and Applications • State-of-the-Art Technologies in Food Science: Human Health, Emerging Issues and Specialty Topics • Sustainable and Functional Foods from Plants • Sustainable Biological Systems for Agriculture: Emerging Issues in Nanotechnology, Biofertilizers, Wastewater, and Farm Machines • Sustainable Nanomaterials for Biomedical Engineering: Impacts, Challenges, and Future Prospects • Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture • Technological Interventions in Dairy Science: Innovative Approaches in Processing, Preservation, and Analysis of Milk Products

Other Books on Agricultural and Biological Engineering xi

• Technological Interventions in Management of Irrigated Agriculture • Technological Interventions in the Processing of Fruits and Vegetables • Technological Processes for Marine Foods, From Water to Fork: Bioactive Compounds, Industrial Applications, and Genomics • The Chemistry of Milk and Milk Products: Physicochemical Properties, Therapeutic Characteristics, and Processing Methods

ABOUT THE EDITORS Junaid Ahmad Malik, PhD Lecturer, Department of Zoology, Government Degree College, Bijbehara, Kashmir, Jammu and Kashmir, India Junaid Ahmad Malik, PhD, is a Lecturer with the Department of Zoology at Government Degree College, Bijbehara, Kashmir (J&K), India, and is actively involved with teaching and research activities. He has more than eight years of research experience. His areas of interest are ecology, soil macrofauna, wildlife biology, conservation biology, etc. Dr. Malik has published over 20 research articles and technical papers in international peer-reviewed journals and has authored and edited books, book chapters, and more than 10 popular editorial articles. He also serves as an editor and reviewer of several journals. He has participated in several state, national, and international conferences, seminars, workshops, and symposia and has more than 20 conference papers to his credit. He is a life member of the Society for Bioinformatics and Biological Sciences. Dr. Malik received a BSc (2008) in Science from the University of Kashmir, Srinagar, J & K; MSc (2010) in Zoology from Barkatullah University, Bhopal, Madhya Pradesh, India; and PhD (2015) in Zoology from the same university. He completed his BEd program in 2017 at the University of Kashmir, Srinagar, J&K.

ABOUT SENIOR-EDITOR-IN-CHIEF Megh R. Goyal, PhD, PE Megh R. Goyal, PhD, PE, is, currently a retired professor of agricultural and biomedical engineering from the General Engineering Department at the College of Engineering at the University of Puerto Rico–Mayaguez Campus (UPRM); and Senior Acquisitions Editor and Senior Technical Editor-in-Chief for Agricultural and Biomedical Engineering for Apple Academic Press Inc. During his long career, Dr. Megh R. Goyal has worked as a Soil Conservation Inspector; Research Assistant at Haryana Agricultural University and Ohio State University; Research Agricultural Engineer/Professor at the Department of Agricultural Engineering of UPRM; and Professor of Agricultural and Biomedical Engineering in the General Engineering Department of UPRM. He spent a one-year sabbatical leave in 2002–2003 at the Biomedical Engineering Department of Florida International University, Miami, USA. Dr. Goyal was the first agricultural engineer to receive the professional license in agricultural engineering from the College of Engineers and Surveyors of Puerto Rico. In 2005, he was proclaimed the “Father of Irrigation Engineering in Puerto Rico for the Twentieth Century” by the American Society of Agricultural and Biological Engineers, Puerto Rico Section, for his pioneering work on micro irrigation, evapotranspiration, agroclimatology, and soil and water engineering. During his professional career of 52 years, he has received many awards, including Scientist of the Year, Membership Grand Prize for the American Society of Agricultural Engineers Campaign, Felix Castro Rodriguez Academic Excellence Award, Man of Drip Irrigation by the Mayor of Municipalities of Mayaguez/Caguas/Ponce and Senate/Secretary of Agriculture of ELA, Puerto Rico, and many others. He has been recognized as one of the experts “who rendered meritorious service for the development of [the] irrigation sector in India” by the Water Technology Centre of Tamil Nadu Agricultural University in Coimbatore, India, and ASABE who bestowed on him the 2018 Netafim Microirrigation Award.

About Senior-Editor-in-Chief xv

Dr. Goyal has authored more than 200 journal articles and edited more than 100 books. AAP has published many of his books, including Management of Drip/Trickle or Micro Irrigation; Evapotranspiration: Principles and Applications for Water Management; ten-volume set on Research Advances in Sustain­able Micro Irrigation. Dr. Goyal has also developed several book series with AAP, including Innovations in Agricultural & Biological Engineering (with over 60 titles in the series to date), Innovations and Challenges in Micro Irrigation; and Innovations in Plant Science for Better Health: From Soil to Fork. Dr. Goyal received his BSc degree in Engineering from Punjab Agricultural University, Ludhiana, India, and his MSc and PhD degrees from the Ohio State University, Columbus, Ohio, USA. He also earned a Master of Divinity degree from the Puerto Rico Evangelical Seminary, Hato Rey, Puerto Rico, USA.

ABOUT THE EDITORS Mohamed Jaffer M. Sadiq, PhD Dr. Mohamed Jaffer Sadiq M., PhD, is working as a Postdoctoral Researcher, School of Chemical Science and Technology, Yunnan University, Kunming, P.R. China Mohamed Jaffer M. Sadiq, PhD, is a Postdoctoral Researcher at the School of Chemical Science and Technology at Yunnan University in Kunming, P.R. China. He started his career as a Chemist at Hindustan Zinc Limited, Rajasthan, India, for 4 years. Dr. Sadiq has published 20 research articles and technical papers in international peerreviewed journals. He is also serving as an editor and reviewer for several journals. He has participated in several state, national, and international conferences, seminars, workshops, and symposia. Dr. Sadiq has more than 10 years of industrial and research experience. His areas of interest are photocatalysis, heterogeneous catalysis, wastewater treatment, biomaterials, bio-nanotechnology, etc. Dr. Sadiq received a BSc (2006) in Chemistry from Bharathiyar University, Coimbatore, Tamil Nadu; MSc (2008) in Applied Chemistry from National Institute of Technology (NIT), Tiruchirappalli, Tamil Nadu; MTech (2014) in Nanotechnology from Karunya University, Coimbatore, Tamil Nadu; and PhD (2017) in Chemistry from National Institute of Technology Karnataka (NITK), Surathkal, Mangalore, Karnataka, India.

CONTENTS

Contributors............................................................................................................ xix Abbreviations......................................................................................................... xxv Preface..................................................................................................................xxxv PART I: Bionanomaterials for Renewable Energy Sources: Trends..................1 1. Usage of Bionanomaterials in Production of Solar Energy..........................3 Md. Jahidul Haque, Zahidul Islam, Ahmed Sidrat Rahman Ayon, Akib Jabed, Zarin Rafa Shaitee, Sanzana Tabassum Proma, Mst. Esmotara Begum, M. Humayan Kabir, M. Mintu Ali, M. Abdul Kaiyum, and M. S. Rahman

2. Scope of Bionanomaterials in Generation of Solar Energy........................27 Ambreen Ashar, Muhammad Zeshan, Muhammad Mohsin, Noshin Afshan, Zeeshan Ahmad Bhutta, and Alina Bari

3. Advanced Electrochemical Bionanomaterials for Energy Conversion and Storage.................................................................................57 Suman Gandi, Saran Srihari Sripada Panda, Saidi Reddy Parne, Nagaraju Pothukanuri, and Gangaraju Gedda

PART II: Nanomaterials for Biosensing Applications........................................89 4. Carbon Nanomaterials for Optical and Electrical Biosensors...................91 Hridoy Jyoti Bora, Gautomi Gogoi, Samiran Upadhyaya, Kangkan Jyoti Goswami, Geeti Kaberi Dutta, and Anamika Kalita

5. Recent Trends in Graphene-Derived Applications for Energy Harvesting and Biosensing.............................................................131 Vedant A. Joshi and Girish M. Joshi

6. Nanomaterials for Biosensing Applications: Concepts and Recent Advancements...................................................................................165 Jnanraj Borah and Anupam Chetia

PART III: Bionanomaterials for Renewable Environmental Trends..............191 7. Advanced Bionanomaterials for Environmental Remediation................193 Jaya Gangwar, Joseph Kadanthottu Sebastian, and Preethy Chandran

xviii

Contents

8. Advanced Bionanomaterials for Environmental Clean Recovery Processes.......................................................................................213 Noshin Afshan and Alina Bari

9. Advanced Bionanomaterials for Heavy Metals and Radioactive Metals Recovery Processes.....................................................241 Gayathri Vijayakumar, Surya Arcot Venkatesan, Suparna Perumal, and Shivani Kumar

10. Advanced Bionanomaterials Used to Recover Pollutants from Wastewater...........................................................................................271 Noshin Afshan, Alina Bari, Ayub Khan, and Yaqoob Shah

11. Role of Nanomaterials in the Treatment of Polluted Cauvery River Water in Tiruchirappalli District (Tamil Nadu)..............................297 R. Arulnangai and Kamal Ahmad Qureshi

12. Potential Nanomaterials for Bioremediation and Biodegradation...........319 Vijaya Geetha Bose, Shreenidhi Krishnamurthy Subramaniyan, Saranya Sri Santhanam, Shreaya Bhaskar, and Sowmia Narayan Sridhar

13. Smart Nanomaterials for Bioremediation and Biodegradation: Laboratory and On-Site Applications and Future Trends........................341 Zeynep Yilmaz-Sercinoglu, Selcen Durmaz-Sam, Fulden Ulucan-Karnak, and Cansu İlke Kuru

PART IV: Nanomaterials for Sustainable Development..................................369 14. Scope of Nanotechnology in Biomedical and Ecological Research..........371 Dwaipayan Sinha and Arpita De

15. Green Nanotechnology: The Novel and Emerging Strategy for Sustainable Development.............................................................................417 Ria Ghosh, Priyanjana Ghosh, Somnath Kar, Suchetana Mukherjee, and Dwaipayan Sinha

16. Sustainable Nanomaterials for the Food Industry: Current Scenario and Perspectives.............................................................447 Vishal Sharma, Abhishek Kumar, Neha Kumari, and Manisha Thakur

Index......................................................................................................................493

CONTRIBUTORS Noshin Afshan

Assistant Professor, Department of Chemistry, Government College Women University, Faisalabad–38000, Pakistan

M. Mintu Ali

Assistant Professor, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

R. Arulnangai

Assistant Professor, Department of Chemistry, Jamal Mohamed College, Kaja Nagar–620020, Tiruchirappalli, Tamil Nadu, India

Ambreen Ashar

Associate Professor, Department of Chemistry, University of Agriculture, Faisalabad–38000, Pakistan,

Ahmed Sidrat Rahman Ayon

BSc Candidate, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Alina Bari

PhD Research Scholar, School of Chemistry and Chemical Engineering, Anhui Normal University, Wuhu–241000, China

Mst. Esmotara Begum

Lecturer, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Shreaya Bhaskar

Undergraduate Student, Department of Biotechnology, Rajalakshmi Engineering College (Autonomous/Affiliated to Anna University), Tamil Nadu–602105, India

Zeeshan Ahmad Bhutta

PhD Research Scholar, Laboratory of Biochemistry and Immunology, College of Veterinary Medicine, Chungbuk National University, Cheongju, Chungbuk–28644, Republic of Korea

Hridoy Jyoti Bora

Project Fellow, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Paschim Boragaon, Guwahati–781035, Assam, India

Jnanraj Borah

PhD Research Scholar, Department of Physics, Gauhati University, Guwahati–781014, Assam, India

xx

Contributors

Vijaya Geetha Bose

Assistant Professor (SS), Department of Biotechnology, Rajalakshmi Engineering College (Autonomous/Affiliated to Anna University), Tamil Nadu–602105, India

Preethy Chandran

Assistant Professor, School of Environmental Studies, Cochin University of Science and Technology, Kochi–682022, Ernakulam, Kerala, India

Anupam Chetia

PhD Research Scholar, Department of Physics, Indian Institute of Technology, Jodhpur–342037, Rajasthan, India

Arpita De

Guest Faculty, Department of Botany, Government Science College (Autonomous), Bangalore–560001, Karnataka, India

Selcen Durmaz-Sam

PhD Research Scholar, Department of Bioengineering, Marmara University, Faculty of Engineering, Göztepe Campus, Kadıköy–34722, İstanbul, Turkey

Geeti Kaberi Dutta

PhD Research Scholar, Department of Chemical Sciences, Tezpur University, Napaam, Tezpur–784028, Assam, India

Suman Gandi

Assistant Professor, Department of Applied Sciences, National Institute of Technology, Ponda–403401, Goa, India

Jaya Gangwar

Research Scholar, Department of Life Sciences, CHRIST (Deemed to be University), Bangalore–560029, Karnataka, India

Gangaraju Gedda

Associate Professor, Department of Basic Science, Vishnu Institute of Technology, Vishnupur, Bhimavaram–534202, Andhra Pradesh, India

Priyanjana Ghosh

Senior Lecturer and Course Architect, Biotecnika Info Labs Pvt. Ltd., Bangalore–560102, Karnataka, India

Ria Ghosh

Research Scholar, Department of Life Sciences, Presidency University, Kolkata–700073, West Bengal, India

Gautomi Gogoi

PhD Research Scholar, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Paschim Boragaon, Guwahati–781035, Assam, India

Kangkan Jyoti Goswami

PhD Research Scholar, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Paschim Boragaon, Guwahati–781035, Assam, India

Contributors xxi

Megh R. Goyal

Senior Editor-in-Chief (Agriculture and Biomedical Engineering) for AAP, Retired Professor in Agricultural and Biomedical Engineering, University of Puerto Rico-Mayaguez, Mayaguez, Puerto Rico

Md. Jahidul Haque

Lecturer, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Zahidul Islam

MSc Candidate, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Akib Jabed

BSc Candidate, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Girish M. Joshi

Associate Professor, Department of Engineering Physics and Engineering Materials, Institute of Chemical Technology, Mumbai Marathwada Campus, Jalna Aurangabad Road, Jalna–431203, Maharashtra, India

Vedant A. Joshi

Undergraduate Student, Department of Engineering Physics and Engineering Materials, Institute of Chemical Technology, Mumbai Marathwada Campus, Jalna, Beej Sheetal Innovations Center Pvt. Ltd. BT-6/7, Biotechnology Park, Additional MIDC Area, Aurangabad Road, Jalna–431203, Maharashtra, India

M. Humayan Kabir

Assistant Professor, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

M. Abdul Kaiyum

Assistant Professor, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Anamika Kalita

DST-INSPIRE Faculty, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Paschim Boragaon, Guwahati–781035, Assam, India

Somnath Kar

Assistant Professor, Department of Botany, Holy Cross College, Agartala–799210, Tripura, India

Ayub Khan

Assistant Professor, Department of Chemistry, University of Education, Jauharabad Campus, Lahore–41200, Pakistan

Abhishek Kumar

Junior Research Fellow, G.B. Pant National Institute of Himalayan Environment, Himachal Regional Center, Mohal, Kullu–175126, Himachal Pradesh, India

xxii

Contributors

Shivani Kumar

Undergraduate Student, Department of Biotechnology, Rajalakshmi Engineering College, Thandalam, Chennai–602105, Tamil Nadu, India

Neha Kumari

PhD Research Scholar, Department of Biotechnology, Dr. Y. S. Parmar University of Horticulture and Forestry, Nauni, Solan–173230, Himachal Pradesh, India

Cansu İlke Kuru

Scientist, Department of Biochemistry, Ege University, Faculty of Science, 35100 and Buca Municipality Kızılçullu Science and Art Center, İzmir–35390, Turkey

Junaid Ahmad Malik

Lecturer, Department of Zoology, Government Degree College, Bijbehara–192124, Kashmir, Jammu and Kashmir, India

Muhammad Mohsin

PhD Research Scholar, Department of Chemistry, University of Agriculture, Faisalabad–38000, Pakistan

Suchetana Mukherjee

Assistant Professor, Department of Botany, Sripat Singh College, Jiagan–742123, Murshidabad, West Bengal, India

Saran Srihari Sripada Panda

PhD Candidate, Department of Applied Sciences, National Institute of Technology, Ponda–403401, Goa, India

Saidi Reddy Parne

Associate Professor, Department of Applied Sciences, National Institute of Technology, Ponda–403401, Goa, India

Suparna Perumal

Undergraduate Student, Department of Biotechnology, Rajalakshmi Engineering College, Thandalam, Chennai–602105, Tamil Nadu, India

Nagaraju Pothukanuri

Associate Professor, Nanosensor Research Laboratory, Department of Physics, CMR Technical Campus, Kandlakoya, Medchal Road, Hyderabad–501401, Telangana, India

Sanzana Tabassum Proma

BSc Candidate, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Kamal Ahmad Qureshi

Lecturer, Department of Pharmaceutics, Unaizah College of Pharmacy, Qassim University, Unaizah–51911, Al-Qassim, Saudi Arabia

M. S. Rahman

Professor Head, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Contributors xxiii

Mohamed Jaffer M. Sadiq

Postdoctoral Research Fellow, School of Chemical Science and Technology, Yunnan University, 2 North Cuihu Road, Kunming–650091, P. R. China

Saranya Sri Santhanam

Undergraduate Student, Department of Biotechnology, Rajalakshmi Engineering College (Autonomous/Affiliated to Anna University), Tamil Nadu–602105, India

Joseph Kadanthottu Sebastian

Assistant Professor, Department of Life Sciences, CHRIST (Deemed to be University), Bangalore–560029, Karnataka, India

Yaqoob Shah

PhD Research Scholar, Department of Applied Sciences, National Textile University, Manawala, Faisalabad–37610, Pakistan

Zarin Rafa Shaitee

BSc Candidate, Department of Glass and Ceramic Engineering, Rajshahi University of Engineering and Technology (RUET), Rajshahi–6204, Bangladesh

Vishal Sharma

Project Associate-I, School of Agricultural Biotechnology, Punjab Agricultural Biotechnology, Ludhiana–141001, Punjab, India

Dwaipayan Sinha

Assistant Professor, Department of Botany, Government General Degree College, Mohanpur–721436, Paschim Medinipur, West Bengal, India

Sowmia Narayan Sridhar

Undergraduate Student, Department of Biotechnology, Rajalakshmi Engineering College (Autonomous/Affiliated to Anna University), Tamil Nadu–602105, India

Shreenidhi Krishnamurthy Subramaniyan

Assistant Professor, Department of Biotechnology, Rajalakshmi Engineering College (Autonomous/Affiliated to Anna University), Tamil Nadu–602105, India

Manisha Thakur

Associate Professor, Department of Biotechnology, Dr. Y. S. Parmar University of Horticulture and Forestry, Nauni, Solan–173230, Himachal Pradesh, India

Fulden Ulucan-Karnak

Scientist, Department of Biochemistry, Ege University, Faculty of Science, 35100 and Buca Municipality Kızılçullu Science and Art Center, İzmir–35390, Turkey

Samiran Upadhyaya

PhD Research Scholar, Physical Sciences Division, Institute of Advanced Study in Science and Technology, Paschim Boragaon, Guwahati–781035, Assam, India

xxiv

Contributors

Surya Arcot Venkatesan

Undergraduate Student, Department of Biotechnology, Rajalakshmi Engineering College, Thandalam, Chennai–602105, Tamil Nadu, India

Gayathri Vijayakumar

Associate Professor, Department of Biotechnology, Rajalakshmi Engineering College (Autonomous), (Affiliated to Anna University), Thandalam, Chennai–602105, Tamil Nadu, India

Zeynep Yilmaz-Sercinoglu

PhD Research Scholar, Department of Bioengineering, Marmara University, Faculty of Engineering, Göztepe Campus, Kadıköy–34722, İstanbul, Turkey

Muhammad Zeshan

PhD Research Scholar, Department of Chemistry, University of Agriculture, Faisalabad–38000, Pakistan

ABBREVIATIONS (NH4)2SO4 ammonium sulfate 2,4-DCP 4-DiChloroPhenol 2-D two dimensional 31 31 PNMR P nuclear magnetic resonance 3-D three-dimensional 4-NQO 4-nitroquinoline N-oxide AA ascorbic acid AC amorphous carbon AChE acetylcholinesterase AFM atomic force microscope Ag silver silver oxide Ag2O AgCl silver chloride AgNO3 silver nitrate Ag-NPs silver nanoparticles Al2O3 aluminum oxide Al3+ aluminum cation AOP advanced oxidation process As arsenic ATP adenosine triphosphate Au NPs gold nanoparticles Au gold AuCl3 gold chloride Au-DR Au-NP + D. radiodurans AuNI 2D-Au nanoislands Aβ β-amyloid BAW bulk acoustic wave BES bioelectrochemical system BET Brunauer–Emmett–Teller BHMS Bushnell Hass mineral salt medium Bi bismuth building-integrated photovoltaics BIPVs BIS Bureau of Indian standards BMIM 1-butyl-3-methylimidazolium

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BMIM-OAc 1-butyl-3-methylimidazolium acetate BNP bionanoparticle bisphenol A BPA BPV biophotovoltaics BR bacterio-rhodopsin BR basket reactor BSA bovine serum albumin BSSCs biomolecule-sensitized solar cells BTEX benzene, toluene, ethylbenzene, xylene C3G cyanidin-3-O-glucoside C4H6N2 methylpyrazolone C60 carbon 60 CAGR compound annual growth rate CaO2 calcium peroxide CaO2-NPs CaO2 nanoparticles CaWO4 calcium tungstate CB conduction band Cd cadmium CD cyclodextrin cadmium (II) ion Cd2+ C-dots carbon dots CE coulombic efficiency CEI cathode/electrolyte interphase CeO cerium oxide CeO2 cerium dioxide CLEAs cross-linked enzyme aggregates CMC carboxymethyl cellulose CMOS complementary metal oxide semiconductor CNC cellulose nanocrystals CNF carbon nanofibers CNM carbon nanomaterials CN-PPVs cyano-substituted PPVs CNT carbon nanotubes COD chemical oxygen demand CoFe2O4 cobalt-based ferrite CoFeNPs cobalt–iron oxide nanoparticles COFs covalent organic frameworks CPT concentrating photovoltaic technology coated onto polyurethane foam CPU

Abbreviations

Abbreviations xxvii

Cr chromium Cr3+ chromium (III) ion CS chitosan CSP concentrating solar thermal power CTS chitosan Cu copper Cu2+ copper (II) ion Cu2O copper (I) oxide CuO cupric oxide CuO-NP-AC copper oxide nanoparticle-loaded activated carbon CV cyclic voltammetry CVD chemical vapor deposition DA dopamine DCF diclofenac DDS drug delivery system DDT dichlorodiphenyltrichloroethane DEHP di(2-ethylhexyl) phthalate DIS differential impedance spectroscopy DMPA dimethyl phosphorothioic acid DMSO dimethyl sulfoxide DNA deoxyribonucleic acid DO dissolved oxygen DSSCs dye-sensitized solar cells DTPA diethylenetriaminepentaacetic acid e– electron E input solar energy EC electrical conductivity EC European Commission ECL enhanced chemiluminescence EDAX or EDX energy dispersive x-ray EDCs endocrine disrupting chemicals EDs endocrine disruptors EDTA ethylenediaminetetraacetic acid EES electrochemical energy storage EESS electrical energy storage systems ELISA enzyme-linked immunosorbent assays Eoc open circuit potential EP epoxide electrochemically reduced carboxyl graphene ERCGr

xxviii

ERCGr-GOD/GCE (ERCGr)-modified glassy carbon electrode ESS energy storage systems electric vehicles EVs EZVI emulsified zero-valent iron Fe/Ag iron/silver Fe/Cu iron/copper Fe/Pd iron/palladium Fe2+ ferrous cation Fe2O3 iron oxide ferric cation Fe3+ Fe3O4 ferrous ferric oxide Fe-Ni/AC iron/nickel activated carbon FeNPs iron NPs FG fish gelatin FNA framework nucleic acid FPU fused into polyurethane foam FRET Forster resonance energy transfer FRR faradic redox reaction FTIR Fourier transform infrared spectroscopy G2/M Gap2/mitotic (Cell cycle) GB glass beads GCE glass carbon electrode GCPEs glassy carbon paste electrodes GHG greenhouse gas GIT gastrointestinal tract GMR giant magnetoresistance GNS graphene nanosheet GO graphene oxide GOS graphene oxide sheet GOx glucose oxidase enzyme Gox graphene oxide GQDs graphene quantum dots GRA graphene h+ hole H2O water H2O2 hydrogen peroxide HAuCl4 chloroauric acid Hb hemoglobin HCs hydrocarbons

Abbreviations

Abbreviations xxix

HF hydrogen fluoride Hg mercury human immunodeficiency viruses HIV HOMO highest occupied molecular orbital high-performance liquid chromatography-fluorescence HPLC-FLD detector HPLC-MS high-performance liquid chromatography-mass spectroscopy HRGO highly-reduced graphene oxide ICC induced cellulose carbon IDT interdigital transducers IEP isoelectric point ISO International Organization for Standardization ITO-PET indium tin oxide coated polyethylene terephthalate film monopotassium phosphate K2HPO4 KIBs K ion batteries KMnO4 potassium permanganate LABs lead-acid batteries LB Langmuir–Blodgett LDPE low-density polyethylene LED light emitting diode LFIA lateral flow immunoassay LIBS Li-ion batteries LOD limit of detection LUMO lowest unoccupied molecular orbital M molar MAB monoclonal antibody MB methylene blue MCF-7 Michigan Cancer Foundation-7 (Cell Line) 2+ magnesium cation Mg MgO magnesium oxide MgO2 magnesium peroxide MIBs Mg-ion batteries MII divalent metal ion MIII trivalent metal ion MIP molecular imprinted MJFs metaplexis japonica fibers mM milli molar MMP matrix metalloproteinase

xxx

MNCs MNER-EM

Abbreviations

magnetic nanocomposites magnetic nanoeffervescent reaction-enhanced microextraction manganese dioxide MnO2 magnetic nanoparticle MNP MnP manganese peroxidase MO metal oxides MOF metal-organic framework MSG magnetic sulfonated graphene MSW municipal solid waste MTB magnetotactic bacteria MTPP maximum tracking of power points MV methyl viologen MWCNT multi walled carbon nanotube NADH nicotinamide adenine dinucleotide NASICON sodium superionic conductor NBR nanobioremediation NC nanocomposite NEMS nanoelectromechanical methods NF nanofiltration NGP nanographene platelets N-GQDs nitrogen-doped GQDs NGS nanogenerators NH2 amine ammonium fluorides NH4F NH4NO3 ammonium nitrate Ni/Fe nickel/iron Ni2+ nickel (II) ion NIBS Na-ion batteries NiFe2O4@COFs magnetic covalent organic framework nanocomposites NiO nickel oxide NIR near infrared NM nanomaterial nm nanometer nM nanomolar NNI national nanotechnology initiative NO3– nitrate NPs nanoparticles NSE neuron-specific enolase

Abbreviations xxxi

NT nanotechnology NTA nitrilotriacetic acid nanoscale zero valent iron nZVI O2 oxygen outer membrane protein A Omp A OpdA organophosphohydrolase Ops organophosphates Ox oxidized p(HEMA-MAAL) poly (2-hydroxyethyl methacrylate-N-methacryloyl-L-alanine) P3Ats (poly(3-alkyl thiophene)s P3BT poly(3-butyl thiophene) P3HT poly-(3-hexylthiophene) PAB polyclonal antibody PAHs polycyclic aromatic hydrocarbons PAMAM-Fc polyamide-amine-ferrocene PANI polyaniline PAP p-aminophenol Pb lead PBBs proton-based batteries PbrD specific recombinant fusion metalloprotein PC polycarbonate PCA photocatalytic activity PCB polychlorinated biphenyl PCE power conversion efficiency PCL polycaprolactone Pd palladium PDI perylene diimide PE polyethylene PEC photoelectrochemical PEDOT poly(3,4-ethylene dioxythiophene) PEDOT-AQ poly(3,4-ethylene dioxythiophene) anthraquinone PEG polyethylene glycol PEI polyethylenimine Pen-G penicillin-G PENG piezoelectric nanogenerator PES polyethersulfone PET polyethylene terephthalate PHA polyhydroxyalkanoates

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Abbreviations

PL photoluminescence spectroscopy PLA polylactic acid polylactic acid, glycolic acid PLGA PLL poly-L-lysine highest power point Pm PM particulate matter PNA peptide nucleic acid PO4 phosphate PO43– phosphate POMs polyoxometalates PRB permeable reactive barrier PS I photosystem I PS II photosystem II PSCs perovskite solar cells Pt platinum Pt-Ag platinum-silver PTCDA 3,4,9,10-perylene tetracarboxylic dianhydride PTCDA/NC/CNT PTCDA/nitrogen-doped carbon/carbon nanotubes PTEC photoelectron transport chain PTNs nitrogen-doped TiO2 NPs PU polyurethane PV photovoltaic PVC polyvinyl chloride PVDF polyvinylidene fluoride PZT PbZrxTi1-xO3 QDs quantum dots QDSSC quantum dot-sensitized solar cells R&D Research and development RDB-GQD rhodamine-B functionalized GQD RFBs redox flow batteries rGO reduced graphene oxide rGOx reduced graphene oxide RhB rhodamin B RHE reversible hydrogen electrode RNA ribonucleic acid ROS reactive oxygen species RS series resistance RSH represent these resistances RT-PCR reverse transcription polymerase chain reaction

Abbreviations xxxiii

Ru ruthenium S synthetic phase surface-area-to-volume ratio SA:V SAED selected area electron diffraction self-assembled monolayers on mesoporous silica, SAMMS dendrimers SARS-CoV-2 serious acute respiratory syndrome coronavirus SAW surface acoustic wave SEI solid electrolyte interphase SELEX systematic evolution of ligands by exponential enrichment SEM scanning electron microscope SEN single nanoparticle enzymes SERS surface-enhanced Raman scattering SG sulfonated graphene S-GQDs sulfur functionalized graphene quantum dots Si silicon SIBs sodium-ion batteries SiO2 silicon dioxide SiRNA small interfering ribonucleic acid SLN solid lipid nanoparticles SNP silver nanoparticle SPE self-powered electronics SPIONs superparamagnetic iron oxide nanoparticles SPM scanning probe microscopy SPR surface plasmon resonance SQUID superconducting quantum interference device SR shunt resistance ssDNA single-stranded DNA ssRNA single-stranded nucleic acids SWCNT single-walled carbon nanotube TCE tri-chloroethane TDS total dissolved solids TEM transmission electron microscope TFSI trifluoromethanesulfonimide TiO2 titanium dioxide TiO2-NPs titanium oxide nanoparticles TNAs TiO2 nanotube arrays TNWs/TNAs TiO2 nanowires on TNAs

xxxiv

Abbreviations

U.S. FDA United States Food and Drug Administration uric acid UA UNEP United Nations Environment Program United States Environmental Protection Agency US EPA USFDA United States Food and Drug Administration UV ultra-violet VB valence band VFBs vanadium flow batteries VIS visible Voc open circuit voltage VP vapor pressure W/O water-in-oil WHO World Health Organization WQI water quality index WRF white rot fungi XNA xeno-nucleic acid XRD x-ray diffraction Zn NPs zinc nanoparticles Zn zinc Zn2+ zinc (II) ion ZnO zinc oxide ZnONPs zinc oxide nanoparticles ZVI zero-valent iron β temperature coefficient

PREFACE Sustainable resources and bionanomaterials are currently the two key concepts facilitating the development of new and emerging sustainable processes. There are a few interdisciplinary methodologies introduced to address future challenges related to the depletion of fossil resources, catalysis, adsorption, electrochemical, photochemical, bioremediation, energy conversion, storage, and environmental issues in the context of the sustainable development of bionanomaterials. These methodologies include the reuse of biomass waste and the proper usage of green technologies. To promote specifically designated nanostructured sustainable development of bionanomaterials, only a few important efforts have been done. Because of this, materials and technologies will need a lot more improvement in the future. The implementation of these strategies results in the predicted impact on the economy of certain countries and reduces unnecessary environmental burdens. The field offers a great deal of potential to solve present human problems, such as reducing the amount of pollutants currently in the system and preventing new contaminants from entering. A combination of technologies and procedures known as sustainable nanotechnology is utilized to advance sustainable development and, consequently, a sustainable environment. This book, Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture, briefly discusses the idea of fundamental bionanomaterials obtained from sustainable resources and the correlation to the degree of competence, practicality, damage, and environmental friendliness. The presented contributions to this book aim to provide an overview of the most current developments, challenges, and uses of bionanomaterials made from renewable resources. The fundamental models presented in this book represent how innovative and emerging green technologies for bionanomaterials configuration can get ready for a prosperous and sustainable society for the advancement of humanity. Based on this, we can genuinely assume that we can encourage new research in the scientific community. The main ideas for understanding sustainable nanomaterials for biosystems engineering—trends in renewable energy, environment, and agriculture—have been explored and communicated, in brief, in this book volume.

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Preface

The present book has been categorized under four subsections: Bionanomaterials for Renewable Energy Source Trends, Nanomaterials for Biosensing Applications, Bionanomaterials for Renewable Environment Trends, and Nanomaterials for Sustainable Development. These four sections comprise of 16 chapters that cover the role of bionanomaterials for solar energy production, energy conversion and storage, environmental remediation, and environmental clean recovery process. Each chapter provides a detailed description of the mechanisms, benefits, and drawbacks of the technologies used. The book emphasizes the use of various bionanomaterials that are used in engineering applications of biosystems. This book brings together various topics, representing the new resource for researchers to solve problems in biosystems engineering. This book is designed for academicians, environmentalists, practitioners, NGOs, and industrialists who are working in the field of biosystems engineering. There is ample information available for all researchers to continue their research on bionanomaterials for biosystems engineering applications and recent advancements in this field based on current and future research. —Editors

PART I BIONANOMATERIALS FOR RENEWABLE ENERGY SOURCES: TRENDS

CHAPTER 1

USAGE OF BIONANOMATERIALS IN PRODUCTION OF SOLAR ENERGY MD. JAHIDUL HAQUE, ZAHIDUL ISLAM, AHMED SIDRAT RAHMAN AYON, AKIB JABED, ZARIN RAFA SHAITEE, SANZANA TABASSUM PROMA, MST. ESMOTARA BEGUM, M. HUMAYAN KABIR, M. MINTU ALI, M. ABDUL KAIYUM, and M. S. RAHMAN

ABSTRACT Even though nanotechnology (NT) has brought tremendous improvements to human lifestyles, one of the most critical questions of the 21st century still arises is that “Will NT can be advanced enough for reducing environmental hazards, unlike other technologies?” Well, lucky for us that we can utilize NT for green purposes and fabricate renewable energy applications. Our chapter will merge two of the most crucial, most critical, and promising technologies of this modern era-renewable solar energy and NT. Bionanomaterials have secured an extensive NT area these days and flourished its incredible influences in mitigating various dangerous short- and long-term challenges. Bionanomaterial has opened a new door for the enhancement of solar energy efficiency. Reasons that make solar energy so feasible are affordability, low maintenance, and energy source reliability. Solar energy dramatically impacts reducing global warming, another reason behind the rapid increase in solar energy use today. To reduce greenhouse gas (GHG) emissions, demand for fossil fuels, and shrink carbon footprint – solar energy is the solution for all of these. Our chapter will emphasize the importance of solar energy production by utilizing nanomaterials (NMs). We will be discussing the properties of these types of materials that make them suitable Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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for such purposes. For example, pure gold nanoparticles (Au NPs) increase the flexibility and stability of solar cells several times. The other significant sections of our chapter will be the synthesis of bionanomaterials, precautionary measures that must not be overlooked, the future possibility of these materials, and the permanent sustainability of this new technology. 1.1 INTRODUCTION Bio-nanomaterials are molecular materials formulated partly or entirely of biomolecules, causing them to form molecular structures with nanoscale dimensions. The fabricated materials have potential in several applications like novel adhesives, energy production or materials binding, fibers, and sensors [41]. In recent years, many projects have been performed using NMs to produce solar energy to find a suitable replacement for non-renewable energy. While projecting these experiments, the aspect of environmental pollution was somehow ignored or avoided [31]. Nowadays, environmental pollution through the widespread use of modern technology is a big concern. For the advancement of the world, we cannot but use these technologies. There might be a possible solution to find a suitable way to move from NMs to bio-nanomaterials [31]. Bio-nanomaterials combined with solar energy may be one of the best alternative sources of non-renewable energy and may regard as a renewable source of green energy. Bio-based NMs have already been used in composite materials to increase the thermal conductivity of composite materials [45]. If we can use these materials to construct solar cells, the electrical conductivity (EC) will grow, reducing thermal energy loss. Carbon nanomaterials (CNMs) attract attention in flexible photovoltaic (PV) devices due to their numerous advantages, such as long-term stability, better transparency, excellent conductivity, and mechanical flexibility [7]. Lead halide-based organicinorganic perovskite solar cells (PSCs) are of broad interest nowadays as they are of less friction cost, have less-temperature solution process, and more incredible energy conversion abilities [34]. Moreover, it can enhance the range of absorption spectra and the steadiness of the PSCs by utilizing rare-earth ion-doped NMs [34]. NMs synthesized through the aqueous system using the genetically engineered M13 virus, such as perovskite NMs, show catalytic and PV performance, extending solar energy conversion applications and the utility of multiferroic perovskite materials [29]. Previously, titanium oxide-based solar cells used to have an efficiency of just around 10%. But coating with Au or silver nanoparticles (Ag-NPs), the

Usage of Bionanomaterials in Production of Solar Energy 5

increment has finally been acquainted [24]. All of this research mentioned above provides evidence that NMs have enriched and decorated our day-today life in the aspect of energy usage. Bio-nanomaterials can open the best possible prospective chance to meet the demand for an enormous amount of energy for civilization and industrial purposes. Since fossil fuels are running out and the query is ongoing whether it will be possible to find a suitable source of backup energy, the solar cell accompanying bio-nanomaterials paves the way for the production of an abundant amount of renewable or green energy known as solar energy [2]. This chapter describes the effectiveness of bionanomaterials in response to solar energy generation and its potential functionality in different solar cells. 1.2  THE CONCEPT OF BIONANOTECHNOLOGY The term ‘NT’ was firstly developed by one of the illustrious scientists of Japan named Norio Taniguchi. He defined it as “NT is composed of handling the segregation, amalgamation, and dislocation of the materials by single atom or single-molecule.” Taniguchi also considered NT as a technological system with nanometer tolerances. Since then, NT has been deemed to prepare such structures in which at least one dimension remains on a nanometer scale [46]. However, the measurement varies between 1 and 100 nm (Usually in the range of a milliard to many tens of milliards of a meter) [1]. To get an idea about how small nanoscales are, we can consider the thickness of a regular paper, approximately 100,000 nanometers. In contrast, a Au atom has a diameter of one-third of a nanometer [12]. Nowadays, NT has been utilized in different disciplines, whereby nanobiotechnology consumes the most fundamentals from NT. Generally, bionanotechnology correlates the phenomenon of biological life science that uses NT’s analytical and experimental tools [35]. Bionanotechnology also illuminates the connection between structural molecular biology and molecular NT. The advancement of the nano-device is performed by considering the structural definition and the function of the living nanomachines that remained in the living cells. According to the latest research of nature, “Nanobiotechnology is regarded as a discipline in which devices are prepared from NT and utilized themselves to analyze biological phenomenon [5]. Mainly, biochemical principles control the properties and usability of the materials that are used in bio-nanodevices. The properties involve mechanical

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(e.g., adhesion, misstatement, breakdown), electrical or electronic (e.g., capacitors, simulation of electromechanical, storage of energy), optical (e.g., assimilation, radiance, photochemistry), thermal (e.g., thermostability, management of thermal), organic or biological (e.g., interaction with cells, biosensing, mechanosensation), etc. [27]. 1.3  THE NEED FOR SOLAR ENERGY Generally, solar energy is feasible worldwide and can provide more than 1,500 times of the atomic or fuel energy to the earth as required per year. It may effectively utilize energy for various purposes, i.e., in PV technology – conversion of solar light directly towards the electric current, in the systems of solar-thermal for solar collectors, in passive solar technology – production of carbohydrates or hydrogen through water splitting, and also in biomass technology – utilization of solar light by different plants for chemical transformations and generation of complex carbohydrates which can further use for the production of electricity, steam or biofuels [39]. Energy experts predict that the world requires 50 TW of energy sources for maintaining economic progress by 2050. However, many scientists believe that solar energy is the best source for solving the energy crisis. In addition, they can drop the usable cost of this energy source to a reasonable level compared with other renewable natural resources [1]. 1.4  MECHANISM BEHIND SOLAR ENERGY UTILIZATION Generation of usable electricity from solar power is accomplished by interacting solar panels with the sunlight. This phenomenon is termed PV transformation. PV cells generate electricity for various purposes like running water pumps, powering homes, or utility-scale electricity generation by different-sized arrays divided from panels or modules [19]. In this segment, we will be looking at how sunlight is converted to usable electric power. 1.4.1  CONVENTIONAL METHOD Power generation from sunlight begins with the installation of solar panels. Generally, a solar panel consists of monocrystalline or polycrystalline silicon embedded on a glass-cased metal panel. The upper surface of the

Usage of Bionanomaterials in Production of Solar Energy 7

solar panel containing a thin silicon layer ejects electrons as sunlight falls on them. The negatively charged electrons are attracted by a part of the silicon cell producing an electrical current absorbed by the panel’s wiring. This mechanism is called the PV effect. Here, the free mobile electrons hit by the sunlight act as the critical factor behind this phenomenon, creating a proportional relationship between sunlight exposure and emitted electrons. Therefore, local clouds and shades prove to be the crucial factors to be dealt with in this solar energy system [38]. 1.4.2  RECENT INVENTED TECHNOLOGY 1.4.2.1  CONCENTRATING SOLAR THERMAL POWER In this technology, sunlight is converted directly into electrical energy without any conversion interface. Therefore, the devices used in this method are designed and have handling efficiency. Moreover, they can deliver more outputs by consuming lower inputs. It is the reason why they have huge applications all over the world. The basis of this system is to excite electrons to higher energy levels by supplying additional energy along with sunlight [11]. This electron excitation creates plenty of free electrons and holes in the semiconductor, which ultimately makes electricity. Concentrating solar thermal power (CSP) and concentrating PV technology (CVT) are also utilized for generating electricity from solar energy along with the PV method. CSP contains a generator, steam condenser, turbine, parabolic troughs, and thermal storage tanks (Figure 1.1). The field of electrical grid system possesses almost 90% capacity of the generation of current from PV. Proper labeling has to be ensured for the indication of the ability and durability of a PV system. Usually, the capacity of such a system ranges from 10–60 MW [15]. 1.4.2.2  PV-SYSTEMS OF ROOF-MOUNTED FOR BUILDING INTEGRATION Building-integrated PVs (BIPVs) has gained massive popularity for households in places with no grid electric access. PV panel arrays are installed on the roof or building walls (Figure 1.2). They can also supply excess solar energy generated from this technique into the system. BIPVs are the most excellent technique for better household electricity consumption when

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it comes to price and prospects. Some researchers researched the capital city of Brazil on the tendency of connecting buildings with the integrated photovoltaic solar energy transformation. In areas where the grid electricity is unavailable, this technique can be beneficial as it effectively generates electricity without almost any emission [36].

FIGURE 1.1  Schematic view of the concentrated solar thermal power.

1.4.2.3  AUTOMATIC SOLAR MICROIRRIGATION SYSTEM The wide range of applications of solar energy has reached areas that do not have any electricity access. Nowadays, this technology is used for irrigating agricultural fields in those areas much more efficiently. Automatic irrigation

Usage of Bionanomaterials in Production of Solar Energy 9

systems at a pre-decided rate turn out to be a very effective irrigation technique powered by solar energy [25]. In drip or sprinkler irrigation systems, water can be utilized efficiently by solar energy with storage energy-based microprocessors containing electric motors. It can do it by Calculating the rate of discharge and the interval of irrigation according to the requirement of water to crop. Based on such demand, MPLAB IDE can program microprocessor-controlled pumps with chosen discharge depending on the irrigation interval and its duration. One of the prime advantages of this system is that it remains in service 24/7 as it is not dependent on an electric grid system for electricity. Figure 1.3 shows the schematic view of an automatic solar microirrigation system. The main parts of this system are the solar PV, storage devices like batteries, processing devices such as a microprocessor, and irrigation system with micro-scale. The microprocessor of the water pump powered by electric motors is used to program the machine according to the soil’s moisture level. As the system is PV system dependent, it is said to be one of the magnificent discoveries of solar energy application in the agriculture sector [19].

FIGURE 1.2  Schematic view of building integrated PV system.

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FIGURE 1.3  Schematic representation of automatic solar microirrigation system.

1.4.2.4  HYBRID SOLAR CELLS In hybrid PV devices, electron-hole pairs(excitons) are formed by the influence of absorbed light in the conjugated polymer. After that, the excitons dissociate to create free carriers. Electrons are then moved to the inorganic acceptor material, whereas the holes remain in the polymer. Charge carriers in the polymers are known as polarons because of the tendency of lattice distortions to accompany the charges in the organic materials. The dissociated electrons and holes can produce photocurrent by moving on to their cathodes or reassembling across the interphase without having any photocurrent. For this reason, electron transfer or recombination at the organic or inorganic

Usage of Bionanomaterials in Production of Solar Energy 11

heterojunction interface holds a crucial influence on the proper functioning of hybrid solar cells [13]. 1.5  POTENTIALITY OF BIONANOMATERIALS The researched journal of physical chemistry introduced something new in solar cells for the last few decades. They emphasized the critical areas of these cells. They gave many essential and fundamental knowledge and kinetic and thermodynamic limitations, details about the mechanism of energy conversion processes, and methods to increase energy conversion efficiency. The advanced uprising techniques in converting energy and storage systems amid the last few periods have delivered numerous significant developments in research. Numerous novel nanostructured designs and molecular assemblies have been developed for future solar cells [14]. Following the advancement in NT, three distinct categories of solar cells have emerged: (a) hybrid organic solar cells, (b) dye-sensitized solar cells (DSSCs), and (c) quantum dot solar cells. Increasing transport efficiency and separating charge carriers from charge separation due to photo induction through the nanoassemblies are still problems. The kinetic criteria and thermodynamic criteria are successfully designed. It will open the door for new research. Several new methods have already been invented in the branch of quantum dot solar cells to utilize nanocrystals’ exclusive optical and electronic characteristics for converting and capturing light energy. Quantum dot sensitized solar cells are less efficient, with efficiency between 1% and 2% compared to DSSC and organic hybrid cells. Either electrolyte or semiconductor plays an important part in influence necessary par transmission and the anodic corrosion of semiconductors. More combined efforts are required for formulating hybrid or functionalized nanostructures to minimize photo corrosion and improve solar cells’ effectiveness [44]. The recent research focuses on developing new nanostructure architectures, maximizing the photoconversion efficiency by molecular design, and establishing the fundamental processes of assembling light harvesting. To develop the solid-state DSSC, the role of ionic liquids as a substitute for conventional solvents has given tremendous results [40]. If this research continues, we can hope that many exciting inventions will create and help aid in the conversion and capture of energy efficiently and economically. The future of NT in solar cells is bright. Here are some

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examples of the potentiality of bionanomaterials in solar cells: (a) poly power, (b) response to climate crisis, and (c) biopolymers, and NT for decentralizing energy supply [10]. Bionanotechnology will give high energy conversion, minimal use of polluting, low costs, and rare resources. Solar energy releases dangerous carbon into the atmosphere, but biopolymer and bionanotechnology will decrease economic and environmental energy costs and separate technological networks that need electricity to operate. Researchers are working hard to make this solar cell give long-term stability. According to the number of dimensions, there are three kinds of periodic structures: Bragg stacks, photonic crystals, and gratings. The plasmonic system is a new promising invention in this sector. Manufacturing cost is high for large-area substrate, so researchers are working on it to reduce its cost. Along with the positive impacts of bionanomaterial in energy conversion, adverse effects such as variable quality control, variation of properties with feedstock, the high production cost for scale-up, low yields for high surface area materials also need to be taken into consideration in working these materials [33]. 1.6  ROLE OF BIO-NANOMATERIALS IN THE PRODUCTION OF SOLAR ENERGY 1.6.1 PHOTOVOLTAICS Sunlight consists of small energy particles called photons. PVs can be reflected, adsorbed, or go right. Among all of them, only absorbed photons can produce electricity. The flow of free electrons is the reason for electricity. Doping is the conventional method of getting “n” and “p” type semiconductors that represent ‘positive’ and ‘negative’ [28]. “N”-type silicon contains surfeit electrons, and “p”-type silicon contains surplus holes-the PV consists of three-generation technology. It has a prohibitive production cost beginning with the first type, but the material used to construct was highly efficient silicon with a single crystal resulting apex of efficiency. The second generation has lower energy, but it reduces the production costs. And the third generation increases the secondgeneration efficiencies by maintaining low prices. Present generation solar cells possess high energetic photons, which is even higher than the semiconductor bandgap. These photons are responsible for the creation of free carriers. Nanostructure semiconducting materials aim to achieve high efficiency at a low cost. Chloroplasts create the production of metabolic

Usage of Bionanomaterials in Production of Solar Energy 13

energy like mitochondria. Sunlight is captured by chlorophyll to form usable energy, ATP, and NADPH. NMs like carbon, Au, and platinum are favored because they are highly biocompatible and have excellent electron transport properties. And because of having superior light transmittance and less internal resistance ITO, PET is mainly used. Nanoscale compositions have the feature of interacting closely with the extracellular membrane of algae as they come closer. The fuel cell design and the electrode are other vital parameters for increasing the density of PV devices [42]. 1.6.2  LIGHT ENERGY TO FUEL The solar panels use PV effects from light energy from the sun to convert light directly and produce electricity. The efficiency of electricity production can reduce due to high temperatures. Solar cells will absorb both light and heat. A PV cell is typically known as a solar cell. Light energy is converted into fuel by using this technology. The sun is a clean energy source, and it can provide a sustainable output to meet future energy needs. But unfortunately, this extracted energy is hard to store. There is one major problem, and it is hard to keep. Scientists have discovered a chemical process capable of making high-energy fuels directly from carbon dioxide and water by utilizing thermal energy coming from the sun. Thus, a new system is developed. The idea is to produce solar fuel hydrogen by special solar cells known as photoelectrochemical (PEC) cells and PV electrolysis reactors. This technology reserves energy through chemical bonds and later converts it into electrical energy by fuel cells. Platinum and iridium elements are sometimes used in PEC reactors, which are expensive and rare [16]. 1.6.3 BIOCATALYSIS It is the use of living systems or their parts to increase or speed up chemical reactions. Biocatalysis and solar energy conversion focus on the application of NT instability, high efficiency, and safety. Nanocatalysts are mainly used for improving the effectiveness of solar cells. The biggest problem for photocatalysts is the accumulation of small wavelengths of sunlight [21]. Catalyst helps raise the absorption spectrum, guide visible light, increase the cell performance, and increase electrons’ transition to the electrode. The recombination of the electrons with cavities will decrease, energy will rise, and energy transfer capability will increase [9].

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1.6.4  PHOTOCATALYTIC WATER SPLITTING Eco-friendly and energy issues are the most important things at this time. Photocatalytic water splitting is one of them. An artificial photosynthesis procedure minimizes global warming; photocatalytic water splitting is being considered to produce hydrogen. Water splitting grips unique potential since it uses water, a low-cost renewable resource. Photocatalytic water splitting has the ease of using a substance and daylight to To produce hydrogen from water. Hydrogen is one of the most plight sources of renewable energy as hydrogen has a high energy density. Hydrogen production using solar cells has been widely studied due to its environmentally friendly nature. Due to limited kinetic overpotential, water splitting through a single component conventional semiconductor is restricted. To solve this problem, there is a necessity for comprehensive photocatalysts with unique features like surface functionalization, nano-sized structure, decoration with co-catalyst, etc. NT in water splitting boosts the kinetics of a chemical reaction and delivers durability against electrochemical and photo-induced degradation. Sometimes precious metal like platinum is so much costly. It will be a significant barrier. NT in water-splitting solar cells gives long-lasting ability and helps to produce hydrogen most effectively and inexpensively. To increase durability, increase hydrogen production, and remove long-standing technical barriers, low-dimensional transitional metal dichalcogenide, earth-abundant NMs, and carbon-based platforms are mainly used [23]. 1.6.5  SOLAR THERMAL ENERGY PRODUCTION WITH THE HELP OF NANOTECHNOLOGY Nanotechnology mainly works on atomic, molecular, and supramolecular levels. It’s a length scale of 1–100 nm range. The main goal of NT is to create and use materials, systems, devices with new functions and properties of their small structures. NT plays a vital role in solar cells application. Nanostructures can produce higher efficiency solar cells using more ordinary cheaper materials such as titanium dioxide (TiO2) and silicon. NT will help to manufacture and design second-generation, thin-film PV cells [9]. About 10 to 30% of the available solar power can be converted into usable energy by the most efficient solar cells, which is relatively minor. If we use nanotech or nanocrystal, we can get greater efficiency. Using nanotech gives 6% more efficiency in plastic solar cells. It is more flexible, wrap-able, and home usable. These solar cells use in automobiles, roofing, soldiers, etc. NT’s

Usage of Bionanomaterials in Production of Solar Energy 15

mature form significantly impacts the industries for its long-lasting, safer, cleaner, and more innovative technology [4]. NMs are used in different ways to reduce energy consumption. Nanoparticle (NP) fuel additives are sometimes used to reduce carbon emissions and to increase the efficiency of combustion fuels. Solar energy is eco-friendly, pollution-free, and also free of GHGes. Solar energies are used in two different ways [21]. Sunlight is mainly used to produce direct energy. Solar thermal energy is mainly used to generate electricity at power plants at an excessive amount of temperature. Hot water and the ventilation of houses are used in low-temperature power plants to produce thermal energy. NT is so much helpful in this sector. Power generation and heat production are so much effective by using NT. A transparent solar cell is developed by using NT to produce thermal energy. Plastic or glass materials, a translucent substrate with nanolayers having optical thickness and properties, are used to make this type of solar cell [9]. 1.7  BIONANOMATERIAL-BASED SOLAR CELLS 1.7.1  DYE-SENSITIZED SOLAR CELL (DSSC) DSSC has a working mechanism slightly dissimilar to the traditional solar cells, yet it provides a 10% plus efficiency [26]. A DSSC is a technique that uses a semiconductor between an electrolyte, a photo-sensitized anode, and a PEC system (as shown in Figure 1.4). DSSC system has a glazed dye electrode of TiO2 containing nanopores. The electrode is moistened with iodide/triiodide, which is a redox electrolyte. In constructing this type of solar cell, selecting the suitable light-absorbing charge carrier dye for the system is essential. Sunlight penetrates through the transparent layer of the cell and strikes the coated dye of the TiO2 electrode [6]. To produce an unstable dye situation, electrons endeavor into the conduction band (CB) of TiO2. The journey of an electron to the anode by diffusion occurs because of the creation of a concentration band. If another electron is not given, then decomposition of the dye molecule will happen. As the dye strips one electron from the electrolyte, a quick oxidizing reaction happens to form triiodide. It comes from iodide in the electrolyte, which is situated below the TiO2. This oxidation reaction is very fast occurring compared to the recombination reaction. The recombination reaction can short-circuit the solar cell. To avoid this threatening situation, we must prevent this kind of reaction. The triiodide from the oxidizing response plays a vital role in

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using mechanical diffusion to recover the missing electron. The counter electrode re-introduces the electron directed by the external circuit because this diffusion occurs to the bottom of the cell. The thickness of DSSC in the nanostructure leads to a higher chance of absorbing a photon which means the dyes will be very effective in converting photons to electrons making DSSC more efficient. This type of solar cell has an efficiency greater than 10% and is much [3].

FIGURE 1.4  Schematic diagram of DSSC.

1.7.2  QUANTUM DOT-SENSITIZED SOLAR CELLS (QDSSC) The idea of QDSSC mainly came from the DSSCs. Because of the superior photoelectronic features of quantum dots (QDs), they are used to harvest light, unlike die sensitized solar cells where the organic die is used as light

Usage of Bionanomaterials in Production of Solar Energy 17

harvesters [30]. Many years of research on QDSSC have led to the successful increase of current generation efficiency of more than 12% from below 1% [37]. There are two semiconducting nanostructured materials according to the unity of nanometer-sized heterointerfaces. Among these, QDSSC is the one. CdSe, InP, PbS, and PbSe are short bandgap semiconductor QDs. These have tunable band edges and are utilized as light harvesters within the visible range. Becoming part of these cells, QDs are linked to broad bandgap material (such as TiO2 or ZnO) with the help of a linker. These are also linked with bifunctional molecules of the form X-R-Y (in which R is an alkyl group and X and Y represent functional groups). Occasionally, to the comprehensive bandgap material without a linker molecule, QDs are deliberately connected. A liquid electrolyte containing a thin layer and a hole conductor having a redox couple is sandwiched between this counter electrode and photoelectrode. Through the QDs, the incident photons are absorbed to create photoexcited electron-hole pairs. These photoexcited electron-hole pairs are restricted within the nanocrystal. To avoid recombination with the help of the device layout, the positive and negative photogenerated carriers were separated into different areas of the solar cell. In this arrangement, onto the surface of 10–30 nm, TiO2 particles QDs are chemisorbed. It sintered into a highly porous nanocrystalline 10–20 μm TiO2 film. Besides, a PV effect is generated through the movement of electrons from the excited state of QDs to the semiconductor’s CB. The redox electrolyte searches the holes (e.g., polysulfide/sulfide) and thus confirms regeneration of the CdSe [30]. 1.7.3  ORGANIC PHOTOVOLTAIC The technology through which sunlight is transformed into electricity by utilizing thin films of organic semiconductors is termed organic PV. This technology has the capability of giving rise to a new generation of costeffective, solar-powered products with thin and flexible form factors. In this PV cell, conductive organic polymers or organic molecules are used as absorber materials. Low-temperature processing is a great advantage of organic PV over inorganic counterparts. It is lightweight, highly applicable for flexible products, and low cost [20]. Materials for organic PV include carbon-based organic molecules or polymers having large conjugated systems. Common examples of such materials used in organic PVs are polythiophene derivatives poly(3-butyl thiophene) (P3BT), poly(arylene vinylene)s, (poly(3-alkyl thiophene)s (P3ATs), and

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poly(arylene ethynylene)s, perylene diimide (PDI), poly-(3-hexylthiophene) (P3HT)), cyano-substituted PPVs (CN-PPVs), phthalocyanine, and so on [47]. As all these materials are mostly maintained, massive linked systems. That’s why carbon atoms are covalently bonded with a turning single and double bond. Pz orbitals delocalize these hydrocarbons (HCs)’ electrons. It will form a delocalized bonding which is π* antibonding orbital and π orbital. The majority of the electrons are situated in the bonding state at room temperature. It is named the highest occupied molecular orbital (HOMO). The antibonding state can be regarded as the lowest unoccupied molecular orbital (LUMO). Between the LUMO and the HOMO energy levels, there is an energy dissociation gap. It is considered a bandgap of organic electronic materials. This range is 1–4 eV. For an exciton reaching the interface to dissociate, it is energetically advantageous. It will be leaving a positive polaron on the acceptor or a negative polaron on the donor. In the case of the ground state (HOMO) and the donor’s excited state (LUMO), material lies at energies sufficiently higher than the acceptor material. Charge separation (2) should compete successfully with the help of geminate recombination (4) to produce efficient photocurrent after a photon absorption event, and then transfer to contacts should be finished with interfacial recombination [20]. 1.8  INFLUENCE OF SILICON NANOPARTICLES Incorporating noble metal nanostructures is an efficient process of improving solar cell’s performance in many PV technologies [32]. These nanostructures increase light absorption and hence improve cell efficiency. Due to the effect of surface plasmons on the nanostructure, they enhance the absorbance of light in the broad spectral range of solar radiation. Zhang et al. [48] found a significant increase in perovskite-based solar cells by incorporating metal NPs. They exhibited photocurrent. They are embodying core-shell NPs accomplished by the efficiency of 11.4%. In this consequence, we also investigated the influence of silicon NPs. Silicon NP is a better alternative to metal NPs because of their thermal stability, chemical properties, availability, and low cost. Spherical Si NPs show electric and magnetic dipole resonances near-IR spectrum and visible region [22]. Because of the effect of resonant silicon NPs, Furasova et al. [8] carried out current research. In halide PSCs, it will improve light harvesting. By incorporating silicon NPs, they obtained a significant improvement in the execution of a lead halide PSC. The upgraded devices have exhibited high short-circuit current (up to JSC = 22.4 mA cm–2), efficiency (up to

Usage of Bionanomaterials in Production of Solar Energy 19

Eff = 18.8%), and FF (up to FF = 78.9%). The open-circuit voltage, light absorption around Si NPs, and the improved FF were developed to increase the crystallinity of the perovskite layer with the help of Si NPS. Thus the increase of JSC is originated. 1.9  PRESENT AND FUTURE PROSPECT 1.9.1  WORLDWIDE STANDING OF SOLAR ENERGY The sources of recycling energy available at a wide range are wind energy, solar energy, tidal wave energy, and hydro energy. They can change different parts of the world. Table 1.1 shows the comparability of the global power capacities among various kinds of renewable energy sectors [18]. TABLE 1.1  Comparative Study Based on Global Power Capacity Among Specific Renewable Energy Sectors Sequence

Power Capacity (Type)

1

Absolute recycling power

Year 2013

2015

2017

1,579

1,715

1,845

2

Hydropower energy

1,014

1,050

1,060

3

Bio-power energy

85

95

109

4

Geothermal energy

12.5

12.9

13.8

5

Solar PV energy

135

176

223

6

Concentrating solar thermal energy

3.3

4.1

4.4

7

Bio-gas energy

1,250

1,340

1,450

8

Wind power energy

315

374

430

Sustainable energy utilization has been followed competitively with a traditional energy source in different countries to make essential addition in national power generation. For instance, 8.9%, 8.6%, and 8.0% of total electricity requirements are met in Greece, Italy, and Germany, consequently by Solar PV. A remarkable increase in solar PV capacities has been observed, from 3.6 in 2004 to 225 GW by 2015 [18]. In 2015, a sum of $160 billion investment and an additional 60 GW (a 35% increment over 2014’s sum) in the field of solar energy led to augmenting installations of a total capacity of solar energy of 256 GW globally closing the year. However, Europe lies in the top position in the utilization of solar power with about 100 GW

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installed capacity. Germany remained the leading country among the solarized countries for many years, but China surpassed them in December 2015 with a solar power capacity of 43 GW. Besides, China plans to expand its overall total of solar power to 175 GW between 2020 and 2025. Following the Association of American Solar Energy Industries, the sum of the USA’s solar PV capacity has reached 45 GW by 2017 [18]. Meanwhile, in Australia, solar energy is now thought to be the leading energy source with their production of 913 MW, whereas 774 MW was extracted from wind energy. It is to be mentioned that in the same year, they withdrew 1,310 MW of coal power. Australia was highly praised worldwide for substituting traditional coal-based methods with eco-friendly renewable power generation methods [18]. India’s settled solar energy grid reached 3,743 MW in 2015, 6,762 MW in 2016, and 8,062 MW in July 2016. Following this progress, India is now aiming to extend their solar energy capacity to an astonishing 100,500 MW by 2023. Correspondingly, France intends to set up a 1,000-kilometer-long solar roadway on the European front, with each kilometer covering up to 5,000 homes [18]. Similarly, France intends to build a 1,000-kilometer-enlarge solar roadway on the European front, with each kilometer can provide sufficient clean energy to empower 6,000 homes [18]. The lists of world ranking and solar power generation capacities by 2019 are briefly showed in Table 1.2. TABLE 1.2  Recent Solar Power Generation Quantity and World Rankings After 2019 Order

Country

Capacity (GW)

1

China

205

2

USA

76

3

Japan

63.2

4

Germany

49.2

5

India

38

1.9.2  FUTURE PROSPECTS OF SOLAR ENERGY Considering key factors like accessibility, availability, capacity, cost-effectiveness, and efficiency in comparison to other sources of renewable energies, solar-based energy is undoubtedly among the best technologies to accommodate the impending challenges. Recently a group of researchers invented the magnitude of solar energy flow in various regions of photosynthetic organisms.

Usage of Bionanomaterials in Production of Solar Energy 21

The research may prove to be revolutionary in developing methodologies that utilize solar energy to attain greater efficiency. According to investigations related to the Graphene Flagship, PSCs’ life span could significantly enhance through the use of minor-layer MoS2 peels being an influential buffer interface band. By developing perovskite-silicon tandem, solar cell scholars in Hong Kong showed that they achieved a world record of power conversion with an impressive efficiency of 26.5%. When it was first invented back in 2009, traditional PSCs had an efficiency of approximately 3.8%. Therefore, highly efficient PSCs that are semi-transparent are created with the unique ability to reflect detectable light and impede infrared light, making them very suitable for the production of solar windows. Studies showed that polymer (3,4-ethylene dioxythiophene) might help produce highly efficient PSCs since the polymer is an excellent holes carrier. The result of the addition can also be very cost-effective [17]. At the Massachusetts Institute of Technology, USA, scientists successfully extracted extensive solar energy by developing a cell that unites two discrete layers of material to absorb sunlight. They used an insulating device made from tungsten and alumina layers and observed that the apparatus could produce electricity by absorbing broad-spectrum radiation from the sun [43]. Through DSSCs, researchers introduced a green polymer derived from biowaste. They developed phthaloyl chitosan electrolyte from chitosan extracted from the insects and crustaceans for the DSSCs to gain proficiency greater than 7%. In addition, Cu (In, Ga) Se and CdTe thin-film solar cells also proved their worth by attaining better efficiencies around 17.5% and 21%, correspondingly. Under ambient light conditions, they found that the cell can have high efficiency of power transformation. They achieved a greater magnitude open-circuit photovoltage of 1.1 V by their photosystem, which combined two suitably outlined sensitizers, redox shuttle (by, 4,4,’6,6’-tetramethyl-2,2’-bipyridine) with the copper complex Cu(II/I) (my), code D35 and XY1. The value of silicon solar cells can decrease soon, and today it is predicted that the decrease in cost will increase solar power production to 700% by 2050 in the USA [18]. In the meantime, researchers will continue to advance further to innovate more efficient solar cells. One day, the use of silicon on solar farms and rooftops will stop and be widely used as efficient bionanomaterial-based renewable energy alternatives. These innovations and improvements will be made possible with the exponential manufacture of solar energy sources shortly. The origins of solar energies will be cheaper and more efficient a few years later by bionanomaterials [18].

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1.10 SUMMARY The chapter elaborates on the influence of advanced bionanomaterial in the effective production of solar energy. The success of NT in the branches of modern technology is undoubtedly enormous. Today by nano-sized biomaterial, improving the performance of renewable energy devices is made possible, which was even theoretical some decades ago. The first part of this chapter describes precisely the term bionanotechnology. Then we explained why we should switch to solar energy and how solar energy can create usable electricity with conventional and recent advanced techniques. Bionanomaterial-based applications for converting renewable solar energies are explained in the middle part of the chapter. It was followed by the elaboration of potential bionanomaterial-based solar cells. The chapter was finalized with the illustration of present and future scenarios of this possible technology. We aim to provide the knowledge of this chapter to future researchers who will be contributing to the development of more renewable solar energy devices by dint of bionanomaterial. ACKNOWLEDGMENT I am declaring my utmost oblige to the persons related to this project for their immense support and love throughout our entire journey, especially during our hectic academic schedules. I cannot express enough gratitude to all the authors contributing to this work. Their dedication, optimism, and hard-working attitude made this project successful, just like it made my journey prestigious. KEYWORDS • • • • • •

building-integrated photovoltaics concentrating photovoltaic technology concentrating solar thermal power dye-sensitized solar cells photoelectrochemical photovoltaic

Usage of Bionanomaterials in Production of Solar Energy 23

REFERENCES 1. Abdin, Z., Alim, M. A., Saidur, R., Islam, M. R., Rashmi, W., Mekhilef, S., & Wadi, A., (2013). Solar energy harvesting with the application of nanotechnology. Renewable and Sustainable Energy Reviews, 26, 837–852. 2. Ameziane, M., (2017). Solar nanoantenna electromagnetic collectors for energy production. Environmental Science, 1, 1–52. 3. Chu, Y., & Meisen, P., (2011). Review and Comparison of Different Solar Energy Technologies (Vol. 1, pp. 1–56). Global Energy Network Institute. 4. Dowling, A., Clift, R., Grobert, N., Hutton, D., Oliver, R., & O’neill, O., (2020). Nanoscience and Nanotechnologies: Opportunities and Uncertainties (Vol. 46, p. 618). The Royal Academy of Engineering Report. 5. Fakruddin, M., Hossain, Z., & Afroz, H., (2012). Prospects and applications of nanobiotechnology: A medical perspective. Journal of Nanobiotechnology, 10, 1–8. 6. Ferber, J., Stangl, R., & Luther, J., (1998). An electrical model of the dye-sensitized solar cell. Solar Energy Materials and Solar Cells, 53, 29–54. 7. Fu, X., Xu, L., Li, J., Sun, X., & Peng, H., (2018). Flexible solar cells based on carbon nanomaterials. Carbon, 139, 1063–1073. 8. Furasova, A., Calabró, E., Lamanna, E., Tiguntseva, E., Ushakova, E., Ubyivovk, E., & Carlo, A., (2018). Resonant silicon nanoparticles for enhanced light harvesting in halide perovskite solar cells. Advanced Optical Materials, 6(21), 1–7. 9. Ghasemzadeh, F., & Esmaeili, S. M., (2020). Nanotechnology in the service of solar energy systems. Nanotechnology and the Environment, 1, 1–15. 10. Gjessing, J., Marstein, E. S., & Sudbø, A., (2010). 2D back-side diffraction grating for improved light trapping in thin silicon solar cells. Optics Express, 18(6), 5481–5495. 11. Green, M. A., (2002). Photovoltaic principles. Physica E: Low-Dimensional Systems and Nanostructures, 14(1, 2), 11–17. 12. Honek, J. F., (2013). Bionanotechnology and bionanomaterials: John Honek explains the good things that can come in very small packages. BMC Biochemistry, 14(1), 1, 2. 13. Hsu, J. W. P., & Lloyd, M. T., (2010). Organic/Inorganic hybrids for solar energy generation. MRS Bulletin, 35(6), 422–428. 14. Ismail, M., Prasad, R., Ibrahim, A. I. M., & Ahmed, A. I. S., (2017). Modern prospects of nanotechnology in plant pathology; Chapter 15. In: Prashad, R., Kumar, M., & Kumar, V., (eds.), Nanotechnology: An Agricultural Paradigm (pp. 305–317). Singapore-GE: Springer Nature Singapore Pvt Ltd. 15. Jacobson, M. Z., (2009). Review of solutions to global warming, air pollution, and energy security. Energy and Environmental Science, 2(2), 148–173. 16. Jacobsson, T. J., Fjällström, V., Edoff, M., & Edvinsson, T., (2014). Sustainable solar hydrogen production: From photoelectrochemical cells to pv-electrolyzers and back again. Energy and Environmental Science, 7(7), 2056–2070. 17. Jiang, X., Yu, Z., Zhang, Y., Lai, J., Li, J., Gurzadyan, G. G., & Sun, L., (2007). High-performance regular perovskite solar cells employing low-cost poly(ethylenedioxythiophene) as a hole-transporting material. Scientific Reports, 7, 1–9. 18. Kabir, E., Kumar, P., Kumar, S., Adelodun, A. A., & Kim, K. H., (2018). Solar energy: Potential and future prospects. Renewable and Sustainable Energy Reviews, 82, 894–900. 19. Kannan, N., & Vakeesan, D., (2016). Solar energy for future world: A review. Renewable and Sustainable Energy Reviews, 62, 1092–1105.

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20. Kippelen, B., & Brédas, J. L., (2009). Organic photovoltaics. Energy and Environmental Science, 2(3), 251–261. 21. Kuang, A., Zhou, T., Wang, G., Li, Y., Wu, G., Yuan, H., & Yang, X., (2016). Dehydrogenation of ammonia borane catalyzed by pristine and defective h-bn sheets. Applied Surface Science, 362, 562–571. 22. Kuznetsov, A. I., Miroshnichenko, A. E., Brongersma, M. L., Kivshar, Y. S., & Luk’yanchuk, B., (2016). Optically resonant dielectric nanostructures. Science, 354, 846–854. 23. Lin, H. Y., & Cian, L. T., (2018). Microwave-assisted hydrothermal synthesis of SrTiO3: Rh for photocatalytic Z-scheme overall water splitting. Applied Sciences (Switzerland), 9(1), 1–12. 24. Liu, C. J., Burghaus, U., Besenbacher, F., & Wang, Z. L., (2010). Preparation and characterization of nanomaterials for sustainable energy production. ACS Nano, 4(10), 5517–5526. 25. Luthra, S. K., Kaledhonkar, M. J., Singh, O. P., & Tyagi, N. K., (1997). Design and development of an auto irrigation system. Agricultural Water Management, 33, 169–181. 26. McConnell, R. D., (2002). Assessment of the dye-sensitized solar cell. Renewable and Sustainable Energy Reviews, 6(3), 271–293. 27. Mishra, R. K., Ha, S. K., Verma, K., & Tiwari, S. K., (2018). Recent progress in selected bio-nanomaterials and their engineering applications: An overview. Journal of Science: Advanced Materials and Devices, 3(3), 263–288. 28. Mosiori, C. O., (2011). The Solar Cell: Solar Cell Technology (p. 271). PhD Thesis; Rift Valley Institute of Science and Technology, Nakuru, Kenya. 29. Nuraje, N., Dang, X., Qi, J., Allen, M. A., Lei, Y., & Belcher, A. M., (2012). Biotemplated synthesis of perovskite nanomaterials for solar energy conversion. Advanced Materials, 24(21), 2885–2889. 30. Pan, Z., Rao, H., Mora-Seró, I., Bisquert, J., & Zhong, X., (2018). Quantum dot-sensitized solar cells. Chemical Society Reviews, 47(20), 7659–7702. 31. Papazoglou, E. S., & Parthasarathy, A., (2007). Bionanotechnology. Synthesis Lectures on Biomedical Engineering, 7(1), 1–139. 32. Pillai, S., Catchpole, K. R., Trupke, T., & Green, M. A., (2007). Surface plasmon enhanced silicon solar cells. Journal of Applied Physics, 101(9), 1–8. 33. Powell, M. D., LaCoste, J. D., Fetrow, C. J., Fei, L., & Wei, S., (2021). Bio-derived nanomaterials for energy storage and conversion. Nano-Select, 2(9), 1–25. 34. Qiao, Y., Li, S., Liu, W., Ran, M., Lu, H., & Yang, Y., (2018). Recent advances of rareearth ion doped luminescent nanomaterials in perovskite solar cells. Nanomaterials, 8(1), 1–11. 35. Reisner, D. E., Brauer, S., Zheng, W., Vulpe, C., Bawa, R., Alvelo, J., & Gericke, M., (2014). Bionanotechnology; Chapter 10. In: Abu-Faraj, Z. O., (eds.), Handbook of Research on Biomedical Engineering Education and Advanced Bioengineering Learning: Interdisciplinary Concepts (pp. 436–489). Hershey – PA: Medical Information Science Reference. 36. Rüther, R., Knob, P. J., Da Silva, J. C., & Rebechi, S. H., (2008). Potential of building integrated photovoltaic solar energy generators in assisting daytime peaking feeders in urban areas in Brazil. Energy Conversion and Management, 49(5), 1074–1079. 37. Sahu, A., Garg, A., & Dixit, A., (2010). A review on quantum dot sensitized solar cells: Past, present, and future towards carrier multiplication with a possibility for higher efficiency. Solar Energy, 203, 210–239.

Usage of Bionanomaterials in Production of Solar Energy 25 38. Sampaio, P. G. V., & González, M. O. A., (2017). Photovoltaic solar energy: Conceptual framework. Renewable and Sustainable Energy Reviews, 74, 590–601. 39. Serrano, E., Rus, G., & García-Martínez, J., (2009). Nanotechnology for sustainable energy. Renewable and Sustainable Energy Reviews, 13(9), 2373–2384. 40. Shi, D., Cao, Y., Pootrakulchote, N., Yi, Z., Xu, M., Zakeeruddin, S. M., & Wang, P., (2008). New organic sensitizer for stable dye-sensitized solar cells with solvent-free ionic liquid electrolytes. Journal of Physical Chemistry C, 112(44), 17478–17485. 41. Singh, K. R., Nayak, V., & Singh, R. P., (2021). Introduction to bionanomaterials: An overview; chapter 1. In: Singh, R. P., & Singh, K. R., (eds.), Bionanomaterials: Fundamentals and Biomedical Applications (pp. 1–21). IOP Publishing Ltd. 42. Sivakumar, P., Ilango, K., Praveena, N., Sircar, A., Balasubramanian, R., Sakthisaravanan, A., & Kannan, R., (2018). Algal fuel cell; chapter 5. In: Jacop-Lopes, E., (ed.), Microalgal Biotechnology (pp. 91–103). IntechOpen. 43. Solomon, E., (2016). New solar cell is more efficient, costs less than its counterparts. MIT News Office, 1, 1–4. 44. Tvrdy, K., & Kamat, P. V., (2009). Substrate driven photochemistry of CdSe quantum dot films: Charge injection and irreversible transformations on oxide surfaces. Journal of Physical Chemistry A, 113(16), 3765–3772. 45. Yu, S., Jeong, S. G., Chung, O., & Kim, S., (2013). Bio-based PCM/Carbon nanomaterials composites with enhanced thermal conductivity. Solar Energy Materials and Solar Cells, 120, 549–554. 46. Zarzycki, A., (2014). At source of nanotechnology. TecnoLógicas, 17(32), 9, 10. 47. Zhan, X., & Zhu, D., (2010). Conjugated polymers for high-efficiency organic photovoltaics. Polymer Chemistry, 1(4), 409–419. 48. Zhang, W., Saliba, M., Stranks, S. D., Sun, Y., Shi, X., Wiesner, U., & Snaith, H. J., (2013). Enhancement of perovskite-based solar cells employing core-shell metal nanoparticles. Nano-Letters, 13(9), 4505–4510.

CHAPTER 2

SCOPE OF BIONANOMATERIALS IN GENERATION OF SOLAR ENERGY AMBREEN ASHAR, MUHAMMAD ZESHAN, MUHAMMAD MOHSIN, NOSHIN AFSHAN, ZEESHAN AHMAD BHUTTA, and ALINA BARI

ABSTRACT Due to the ever-increasing demand for energy, the energy supply rate is going to be dropped in the near future. As the reserves of fossil fuels are declining speedily, solar energy is considered the non-exhausting renewable energy resource. The complicated fabrication technologies and high cost of solar cells have become the bottleneck of their application in every field to construct solar cells. The conversion efficiency of solar power by solar cells is the most limiting parameter. The efficient fabrication technologies and flexible structures of solar devices should be under significant consideration. The cost-effective and eco-friendly natural materials have replaced many chemicals used in solar cells as efficient solar light harvesters. Moreover, the biological materials hybridized into semiconductor solar cells are capable of providing high efficiency. Various bionanomaterials such as nanocellulose, bacterio-rhodopsin (BR) proteins, and Organic piezoelectric and triboelectric biomaterials are being investigated as next-generation solar cell materials. Biomolecule-sensitized solar cells (BSSCs) have also become popular as cost-effective photovoltaic (PV) power generators. In this chapter, it has been explained that how biological–synthetic interfacing techniques can be facilitated by the synergy of two components.

Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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2.1 INTRODUCTION Environmental difficulties have become a severe threat to our globe in recent years, including pollution, climate change, and infectious illnesses. Unplanned resource exploitation and the industrial revolution have resulted in the depletion of nonrenewable energy sources and an environmental disaster [8]. These global issues have gotten worse in underdeveloped countries due to the industrial revolution and insufficient monitoring and management. Resource management and cost-effective pollution mitigation technologies are promising solutions for many environmental challenges and disinfection [30]. Furthermore, the scarcity of fossil fuels and nonrenewable energy sources has raised scientific concern about bionanomaterials and sustainable strategies for reducing pollution and renewable power generation [14]. From energy packets (photons), different lengths of the light continuum (ultraviolet, red, and yellow) comprise sunlight. Energy is vital for human progress, and it is also a necessary component in our daily lives. The need for power enhanced significantly as human progress increased in population, industrialization, and urbanization. The critical worldwide energy sources consist of conventional fossil fuels, renewable energy, and nuclear power, from the fossil fuels still covering the bulk of world energy demand even now [36]. However, as fossil fuel supplies deplete, current energy sources are shifting their focus to other sources of energy. Regardless of the finite fossil fuel sources, the tremendous effects of fossil fuels on the ecosystem and climate are another concern. Several approaches have been developed to address the problems of renewable energy production. The most common techniques are sunlight capturing and conversion to power or fuels, particularly fuels which could be stored and transferred. However, the performance of existing renewable energy technology is insufficient to compete with conventional fossil energy sources [44]. Semiconductors, as materials that can capture sunlight and create electron (e–) and hole (h+) pairs, could convert solar power to electrical power and fuels. The e–/h+ generated by solar irradiation will be isolated on the surface of a semiconductor and travel on the material’s surface to either enter in an external circuit of PVs devices or initiate an oxidation/reduction reaction mechanism on the surface of semiconductors to yield sustainable fuels. With the increasing interest in nanomaterials (NMs), the production of NMs has recently opened a new avenue to the growth of renewable energy technologies [12]. The term “NM” refers to material that has at least one dimension less than 100 nm. It might take many forms, such as nanoparticles (NPs),

Scope of Bionanomaterials in Generation of Solar Energy 29

nanowires, and nanorods. The surface-area-to-volume ratio (SA:V) of the bionanomaterial increase as the size of the material decreases, resulting in specific unique characteristics of the bionanomaterials [41]. In this chapter, the efficient fabrication technologies for novel bionanomaterials to be used as non-exhausting renewable energy resources and flexible structures of the bionanomaterials based solar devices such as BSSCs have been highlighted in detail. 2.1.1  RENEWABLE ENERGY RESOURCES The atoms or electrons on the interface are often highly active and can form bonds with neighboring atoms or electrons, lowering the system’s total energy. This feature can enhance the chemical activity, and so initiate a catalytic process. This characteristic of NMs allows for the use of tiny amounts of materials to produce high reaction activity, which is very desirable for economic and environmental considerations. Another benefit of NMs is that their size influences their intrinsic characteristics. In semiconductor NMs, this indicates that the electronic bandgap will be increased as the size decreases. Because the electron transfer between both the valence band (VB) and the CB is the backbone of a semiconductor’s photonic absorption or emission, it can control the photocatalytic efficiency of the semiconductors by modifying the size of the NPs [48]. Furthermore, because the diffusion length of NMs is lower than that of bulk materials, the transfer of e-—h+ pair to the semiconductor surface for charge isolation and the reaction that occurs on the surface of NMs will be faster [23]. Because of the numerous characteristics of semiconductor NMs described above, numerous researches on photocatalytic activity (PCA) of semiconductor NM for renewable energy production have been conducted. TiO2 NPs are the most widely utilized materials in photocatalysts application; even with all of the research on TiO2 NM, its overall performance in renewable energy production still has a long way to go. A fantastic new NP has been designed to boost PCA significantly. In terms of solar energy usage, the bandgap of the novel photocatalysts must absorb primarily visible light. Initially, a few metal oxides (MO) and chalcogenides, such as WO3 and CdS, were generated [50]. The utilization of biomaterial, particularly enzyme, is the final point to highlight in the renewable energy generation using NM. The benefit of employing enzymes rather than photocatalysts is that enzymes may be selected based on the reaction. Being a complex of biomaterial, the enzyme can only catalyze specific responses that efficiently suppress powerful competing

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reactions in photocatalysis reactions. For example, in CO2 reduction, H2 production is a powerful competitive reaction due to their comparable redox potential, whereas most photocatalysts have output selection difficulties. However, enzymes can help with this issue. Using the fascinating topic of CO2 reduction as an example, detailed research work has been conducted using enzymes. Scientists are attempting to build more effective ways with the enzyme to decrease CO2, including combining enzymes with photocatalysts [26]. However, the performance of enzymes in the most desirable processes in renewable energy generation has a long way to go. 2.1.2  ROLE OF BIONANOTECHNOLOGY IN SOLAR ENERGY PRODUCTION 2.1.2.1  SELF-ASSEMBLY OF BIONANOMATERIALS Bionanoparticle (BNP) assembly is a critical field of nanoscience study. It is due to two primary reasons: firstly, the application efficiency of BNPs has always been dependent on collective instead of individual BNP efficiency, which necessitates a thorough investigation of structure-property interparticle interactions and correlations. Secondly, the BNPs have very high surface energy, which offers an enormous pushing force for lowering the Gibbs free energy [75]. BNPs must ultimately form an extensive and stable assembly as a result of their energy-driven spontaneous organization. By adjusting changing assembly methods and inter-particle interactions, it was possible to achieve accurate and controlled production of BNP ensembles. The characteristics of NP ensembles are distinct from those of individual and bulk BNPs. BNP assemblies exhibit new electrical, optical, magnetic, mechanical, and Opto-thermal attributes due to the collaboration and connection of individual BNPs. BNP assemblies show great promise in a variety of practical applications, including energy storage [65], biodegradable plastics, ultra-strong materials [60], photocatalysis, therapies [25], and adsorption [24]. DNA may be used to build one-dimensional, two-dimensional, or even three-dimensional structures. The most straightforward kind of DNA assembly consists of just two nanostructures. The single helical strand DNA has been used to link two Au-silver core-shell NPs to create a switchable dumbbell-shaped nanostructure. In the absence of plasmid Sequence, the single-strand DNA forms hairpins, reducing the distance of two NPs. In the presence of the plasmid Sequence, the single-strand DNA hybridizes with it to create linear DNA, increasing the interlayer distance. The variation in

Scope of Bionanomaterials in Generation of Solar Energy 31

inter-particle space alters the surface-enhanced Raman signal, which may be utilized as a biosensor [16]. Other biomolecules, in addition to DNA, may be utilized in the nanoassembly process. For example, the commonly used biotin-streptavidin pairs may link Au-NRs side-to-side owing to the absence of a ligand on the head of Au-NRs, which enables the biotin alteration to occur solely on the end of Au-NRs (as opposed to the middle of Au-NRs). In addition, the detection of toxic using side-by-side or end-to-end Au-NR assembly may be accomplished using comparable antibodies and antigens, as shown below [66]. Even though all other biomolecules can serve as templates for nanoself-assembly, DNA retains its own set of unique characteristics. One of the unique characteristics is the ability to conduct electricity. Double strand DNA is produced by stacking base pairs in a p-shaped pattern, and p-stacked materials often exhibit conductive properties, which opens the door to the potential that DNA will also have conductive properties [66]. 2.1.2.2  CHEMICAL METHODS FOR THE SYNTHESIS OF BIONANOMATERIALS The various methods for the synthesis of bionanomaterials have been given in subsections. 2.1.2.2.1  Sol-Gel Method Hydrolysis is controlled by the condensation of precursors (Alkoxides, metal chlorides, and nitrates). For the construction of MO, biopolymers serve as noble templates, i.e., chitosan, cellulose, and pectin, as they have amino and hydroxyl groups. The salts of metals are mixed into the polymer, which is then hydrolyzed. Composition and shape can be controlled and synthesized at lower temperatures, specific particle size, and surface area. In polymer matrix, NPs properties are maintained, e.g., Chitosan/TiO2 and chitosan/ polyethylene glycol (PEG)-Calcium silicate [79]. 2.1.2.2.2  Solvothermal/Hydrothermal Method This process requires formulation in an autoclave which is made up of steel. NMs agglomeration occurs when vapor pressure (VP) gets saturated and

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could eliminate this aggregation by utilizing various stabilizing agents. The main advantage of this method is that the manufacturing of nano- and microMO and other different metal compounds is possible. Utilizing reagents such as ammonium fluorides (NH4F), the shape control of a high degree can also be accomplished, e.g., Iron oxide (Fe2O3) coated hydrocalumite-chitosan composites [53], TiO2-cellulose [40], Methylpyrazolone (C4H6N2) functionalized TiO2-Fe3O4-chitosan [1]. 2.1.2.2.3  In-Situ Precipitation/Co-Precipitation Method In the existence of biopolymer through the catalyst precipitation from precursors, metallic NP is manufactured that is attained by heat treatment and refluxing. Occasionally grafting of bio NPs or in-situ precipitation of synthetic bio NPs is also done, and in this way, ultrasonic and microwave treatment are also helpful. It’s a simple method that works for most bio NPs and metal-based NPs composites. Onto the polymer, this ensures the binding of NPs, e.g., Fe3O4-cyclodextrin [31], and Chitosan-ZnO [83]. 2.1.2.2.4  Atomic Layer Deposition (ALD) The benefits of the chemical vapor deposition (CVD) and sol-gel method are combined in the ALD approach. The precursors are held in a vapor/gaseous condition before being injected into the reactor, where they are saturated with monolayers. The thickness of the films produced can be adjusted and modified, e.g., TiO2-cellulose [33]. 2.1.2.2.5  Electrospinning This method is exquisite and is utilized to manufacture 1 D NPs from different precursors, especially polymer and fibers (micro and nanometers range). The high voltage uses to create an electric field, and this electric field charges the polymer interface and influences the liquid injection from the spinneret. However, it should avoid different characteristics such as conductivity, viscosity, polymer weight, surface tension, etc. The shape, porosity, thickness, and SA:V of electrospun nanofibers can all be adjusted, e.g., chitosanpolyvinyl alcohol-zeolite, and CdS-Cotton cellulose nanofibers [39].

Scope of Bionanomaterials in Generation of Solar Energy 33

2.1.2.2.6 Immobilization Immobilizing NPs on the polymer matrix combines several methods, including encapsulation, covalent bonds, entrapment, and cross-linking as photocatalyst materials support starch, chitosan, and cellulose carboxymethyl cellulose (CMC), cellulose acetate, pectin, dextran, gums, gelatin, dextrins, and other biopolymers. The immobilized photocatalyst shows higher stability, higher surface area, and better dispersion. They also let charge carriers travel around more easily and decrease recombination. Furthermore, the catalysts can be employed in both fixed bed and suspended catalytic reactors, e.g., WS2-chitosan-polycaprolactone (PCL) [17], TiO2 immobilized cellulose matrix, and PDMS-SiO2-chitosan@TiO2 [57]. 2.1.2.3  MECHANICAL METHODS FOR THE SYNTHESIS OF BIONANOMATERIALS 2.1.2.3.1  Biological Synthetic Interfacing Techniques Introducing highly effective photo-absorbing synthesized NMs within biological systems might supplement some inadequate metabolic routes as well as natural photosynthetic processes’ poor photo absorptivity [59]. Semiartificial photosynthesis methods can use nature’s sophisticated catalytic mechanism to generate chemical energies whose processes are too complicated for completely synthetic photosynthetic processes to carry out. In this part, we will look at how inorganic NMs may be integrated into biological processes in various methods, including freely floating in the same fluid, binding to the microbial membranes, and internalization inside the microbe. Initially, research concentrated on free electrons processes like proton reduction to generate hydrogen utilizing synthetic photosynthetic techniques. Dukovic, King, and colleagues [6, 74] reported photocatalytic hydrogen generation by integrating hydrogenase isolated from C. acetobutylicum into sunlight-absorbing NPs. The speeds were restricted through the photoluminescence quantum yield of CdS nanorods or CdTe nanocrystals [74]. Furthermore, more kinetically complicated processes, like N2 reduction to NH3, were achieved by employing CdS nanocrystals as photosensitizers interfaced with a nitrogenase molybdenum iron protein [7]. The hydrolysis of adenosine triphosphate (ATP) provides chemical energy in natural systems. Photo-generated electrons from semiconductor nanocrystals may supply the

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power usually provided by ATP in biochemical hybrid systems. The transfer of electrons from inorganic light absorbers to active enzymatic sites restricted the energy conversion efficiency in these biomimetic methods. This highlights the necessity of establishing solid electrical coupling at the nano-biointerface and having tailored kinetics to prolong energy levels. Incorporating an inorganic substance into an entire biological system is another approach to create a bio-inorganic interface. The inorganic constituent may be utilized in the same way that modified nucleic acids and proteins are used in conventional synthetic biology [74]. Nocera and colleagues accelerated CO2 fixation by combining a bacterium (Ralstonia eutropha) with a water-splitting CoP alloy [37]. These bacteria generated biofuels by consuming the H2 provided by the inorganic catalyst. Whenever the bioinorganic hybrid system was combined with a solar system, CO2 reduction was accomplished with an absolute scale more efficiently than the photosynthesis process. Similarly, the Nocera group achieved NH3 production from N2 and water by merely changing the kind of bacteria. The merits and demerits of utilizing the isolated enzymes, namely oxidoreductases and whole live electroactive bacteria, have been examined [38]. Tight bio-inorganic interfaces may be created by using some bacteria’s unique capacity to mineralize metal ions to minimize heavy metal pollution in their habitat. Yang and colleagues produced the precipitation of CdS NPs on CO2-reducing bacteria by providing chemical precursors for Cd, and S. Acetic acid production was photosensitized by membrane-bounded CdS NPs. By combining inorganic compounds, this non-photosynthetic bacterium could carry out a photosynthetic CO2 absorption process that took use of both the high light absorptivity of the CdS NP and the bacteria’s speedy biosynthetic pathway [38]. To enhance the transfer of electron process even further, the investigators ingested photosensitizers, Au nanocrystals, in the same bacteria to avoid the sluggish mass transit of electrons across cell surfaces [84]. They used ligands to design the Au nanocrystal structure to extend the lifespan of photo-generated electrons. They can also move to the electron transfer network inside the cytoplasm. Future investigation may benefit from improved methods for characterizing NMs. Gratzel and colleagues [4], for example, discovered a kind of nanostructured materials with a photon-to-current conversion efficiency nearing the theoretical limit by examining the grain boundaries and high electric regions of NP aggregation. Sambur et al. [55] utilized a super-resolution scanning approach to determine the most effective method of modifying photoanodes with oxygen evolution catalysts, proposing an

Scope of Bionanomaterials in Generation of Solar Energy 35

action material engineering strategy for improved photo-electrochemical conversion. By utilizing advancements in the research of inorganic NMs (e.g., bandgap energy, carrier diffusion lengths, and band-edge locations relevant to required half-reactions) and synthetic biological linking methods, the genuine synergy of the four segments may be facilitated. These concepts have the potential to connect inorganic photo transducing nanostructures to more sophisticated biosystems, particularly eukaryotes, for the development of both basic biophysical research and possible therapeutic use [55]. 2.1.2.3.2  Biological Synthetic Interfacing of Voltaic Devices In microbial fuel cell research, photovoltaics (BPV) is a new direction, utilizing photosynthetic microorganisms transforming sunlight energy into electricity. Technology has attained enormous interest from the last three decades using the bacterial cell as a catalyst for producing electrical power, commonly microbial electrochemical technology. This is a facilitated face system called bioelectrochemical system (BES). The grouping of the system occurs based upon the energy resource and organism applied. BPV is the generation of electricity by partial or a complete phototropic microorganism by the sunlight illumination, having specific feature of producing direct energy by the utilization of natural photosynthesis: during the water splitting mechanism, incoming sunlight is used through oxygenic biomass, e.g., cyanobacteria, therefore, eliminated an anode and electricity capture electrons are generated, and the whole tool is defined recently, but it was studied the means of electron transformed a long time ago, and for a heterotrophic electron, the route of electron altered based hypothesis was presented [27]. Currently, sunlight to electricity performance is a limiting factor, and the BPV system seems to be primarily undefined. Lately, the theoretical possibility of genetically modifying cyanobacteria has enhanced photocurrent generation. The bio PV system through which the production of current with water and sunlight occurs is deliberated as a subdivision of photosynthetic microbial fuel cells [43]. Water is an original electron source. In most cases, there are two classes of electricity that can be recognized. Photosynthesis will be activated by the sunlight source and hence the photoelectron transport chain (PTEC) that is the foundation of all types of photoresponse and photocurrent. Eliminating the sunlight source will reduce the electricity flow, but only to the degree that it is still much higher than the abiotic baseline. These would be the

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dark currents (i.e., delayed photocurrent) caused by the decomposition of endogenously accumulated carbohydrates. However, the accrued carbohydrates were produced utilizing energy supplied and electrons through the photosynthetic materials [80]. Cyanobacterial species that have been tested till now in BPV include Synechococcus [56], Synechocystis sp. PCC 6803, Arthrospira platensis, Nostoc [73], Lyngbya, Oscillatoria limnetic, Anabaena variabilis M-2, and Leptolyngbia sp. [9]. So far, the maximum power density published was around 620 mW m–2 utilizing Synechococcus sp. BDU 130432 [28]. The electrogenic activity was compared between the various untamed cyanobacterial genera and unclassified phototropic consortium. The microbial consortium has the highest electrogenic production and only half of seven different pristine cultures media of cyanobacterial efficiency examined, but Synechocystis sp. PCC 6803 demonstrated a fourth of such ability and was thus just half as effective as the other seven cyanobacterial pure cultures examined. Synechocystis sp. PCC 6803 and WH 5701, respectively as well as two other algal species photo outputs also compared. On indium tin oxide coated polyethylene terephthalate film (ITOPET) anodes, Synechococcus had the best biofilm-forming characteristics and power density over two-fold of capacity greater than Synechocystis, which was just loosely connected to the electrodes and quickly washed away. Despite this, Synechocystis sp. PCC 6803 remains the most popular cyanobacterium for BPV research, possibly because Synechocystis is a reference organism in photosynthesis study, with a completely sequenced genome and a wealth of genetic modification tools [32]. 2.2  SOLAR ACTIVE BIONANOMATERIALS 2.2.1  BIONANOMATERIALS AS PHOTOCATALYSTS Multi-functional bio-beneficial materials play a critical role in cutting-edge technological advancements that promote positive, long-term progress in society. Nature’s complex and tiny materials have long astonished the scientific community. Nature is, in fact, a school for material design. There has been steady attention in improved attractive biomaterials to preserve humans and the environment using sustainable chemistry development concepts. Bio-inspired materials, based on biological materials concepts, have been a popular topic in recent years. Many scientists have concluded that natural hierarchical structures are considerably superior to laboratory-created materials and procedures [67].

Scope of Bionanomaterials in Generation of Solar Energy 37

2.2.2  BIONANOMATERIALS AS SOLAR POWER GENERATORS 2.2.2.1  SOLAR POWER GENERATION AND ITS MECHANISM From energy packets (photons), different lengths of the light continuum (ultraviolet, red, and yellow) comprise sunlight. These photons differ in their intensities depending upon their wavelength [21]. Solar cells collect the sunlight energy and convert it to electricity once exposed to the solar cell surface. Due to the photovoltaic effect of a solar cell that is a semiconductor electron, it can directly transform sunlight energy into electricity. If sunlight strikes the semiconductors, movement of an electron occurs to the semiconductor CB from the capacitance band, forming a pair of e––h+ that can participate in the semiconductors load transport cycles and generate potential fluctuations, allowing the load to be guided to the external circuit with the help of the user [42]. Detail of different type of bionanomaterials is given in Table 2.1. 2.2.2.2  Z-SCHEME SYSTEM OF SEMICONDUCTORS Despite all the development and modifications of semiconductor NMs, several fundamental properties remain an impediment to creating a photocatalyst powered by one-step photoexcitation. For a single component photocatalyst, it’s challenging to have a broader light absorption spectrum, maximizing the utilization of solar light, which necessitates a narrow bandgap while also having high redox ability and a wide bandgap. Nature has a lot to teach us, and it’s not just about remote systems like enzymes. Photosynthesis, also called Z-scheme photosynthesis, is a mechanism in which green plants utilize sunlight to transfer CO2 and H2O into carbohydrates and O2 for fuel. Two photoexcitation stages are involved in the photosynthesis Z-scheme. Sunlight is captured via photosystem I (PS I) and photosystem II (PS II), which stimulate electrons to the excited state. A chain of electron mediators connects the two photosystems. PS II is where water oxidation takes occurs. The excited electrons in PS II have flowed to the PS I ground state via electron mediators. PS I then pumps those electrons from the ground state to the excitation state, which has more incredible energy than that of the PS II excited state, and carries them via another set of electron mediators to decrease coenzyme NADP+ to the NADP, which is utilized in the dark reaction to convert CO2 into carbohydrate [34].

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TABLE 2.1  Types of Solar Active Bionanomaterials and Their Overview Entities Included

Methodologies

Characteristic

References

Biopolymers based bionanomaterials

Cellulose, Starch (C6H10O5)n, pectin (C6H10O7), chitosan (C6H11NO4) , gelatin (C102H151N31O39), acetate n (C2H3O2–), natural gums cellulose alginate, and inorganic materials are biopolymer-based nanoparticles

Atomic layer deposition, Sol-gel method, spin deposition, electrospinning, template-assisted synthesis, nanoencapsulation, and hot press method

Adsorption eliminations of heavy metals (i.e., Pd, Cd, Au, and Ag), the organic pollutants, and antimicrobial agents

[47, 61]

Biomimetic bionanomaterials

Natural oil, extract of plant, natural fibers extracts of seed, for templating, organic, and inorganic materials, and microbes

Reduction through greener process, sonication, co-utilizing, and microwave

Microbial fuel cells and photocatalytic applications

[58, 77]

Biochar based bionanomaterials

Thermal impregnation, Agriculture produces, bio-wastes, wood products, forest waste, organic thermal treatment, in-situ materials, and animal bones manufacturing in the presence of charcoal and in-situ loading

Plant growth, soil modifications, adsorbents, and the part of hybrid photocatalysts for managing waste

[35, 76]

Enzymes, proteins, and Enzymes, proteins, immobilized on peptides functionalized photocatalysts bionanomaterials Miscellaneous bionanomaterials

Functionalization, plasma, in-situ synthesis, coating, sonication, immobilization, and chemical route

Photocatalytic mineralization of [18, 64, 78] pollutants, biological applications, and biofuel cells

Photocatalytic treatment, coupling of Biological microbial photoca- Mineralization of organic microbial biological-adsorption talysis and oxidation pollutants by photocatalysis, and highly efficient fuel cell applications

[68, 82]

Sustainable Nanomaterials for Biosystems Engineering

Type of Bionanomaterials

Scope of Bionanomaterials in Generation of Solar Energy 39

In this system, the charge separation efficiency in PS I is nearly 100%, which is the main objective that researchers strive to achieve in photocatalysts. Researchers replaced the PS II and PS I in nature photosynthesis with two sorts of material structures that simultaneously generate exciting electrons to imitate the photosynthesis system in nature. The excitation site is generally a semiconductor or a dye molecule, with one acting as an electron donor and one as an electron acceptor. This method, like the natural photosynthesis system, improves charge separation efficiency while reducing the likelihood of reverse electron transfer and the recombination of electronhole. Furthermore, as the two gaps possess overlapping sections, the two materials can still have the gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) or have narrow bandgaps. The electron acceptor’s CB has enough energy to do the minimization work, while the electron donor’s VB is enough to process the oxidation reaction [81]. The co-existence of efficient light utilization and higher redox potential in one system is solved by the coordination of two semiconductors. Aside from the energy level, the artificial photosynthesis system’s stability is enhanced, and both photocatalysts may be more carefully selected to fall into oxidation and reduction reactions. The artificial photosynthetic process (Z-scheme) has been considered for generations, providing a lot of knowledge. With the advancement of technology in the field of NMs, we now have more opportunities to investigate the Z-scheme system and its influencing variables in greater depth [20]. 2.2.2.3  SELF-POWERED ELECTRONICS (SPE) AND BIONANOGENERATORS Wang [69] originally introduced SPE and systems in 2006 to address the electron power transfer issue. At the time, his group was developing very tiny energy harvesters capable of powering nanoscale electronics. The selfpowered nanosystem collects atmospheric energy to fuel itself, intending to function autonomously, sustainably, and wirelessly. The phrase “selfpowered sensor” has a dual interpretation. To start, it is a sensor that emits an electric signal automatically when mechanically activated without the need for an external power source [72]. As is well known, the majority of sensors utilized today are passive, meaning they cannot emit any signal in the absence of a power source. Second, the sensor’s operating power source is self-generated. This is achieved by taking into account a sensor’s active

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and sleeping modes. A self-powered sensor (Figure 2.1) is shown to be composed of components capable of communicating, detecting, reacting, and controlling. Apart from the processing components of data, transmitting, and sensing, the system’s energy harvesting, and storage activities are critical [71]. Solar, wind thermal, mechanical, biomass energy, and chemical sources are all possible. Solar cells have been utilized to collect solar energy in real-world applications; however, their high reliance on weather conditions significantly limits their viability as a power source for sensors [71].

FIGURE 2.1  The schematic representation of the unified self-powered mechanism.

Nanogenerators (NGS) are propelled by displacement current created via a fluctuation in the electric field over time, as well as by a term associated with the medium polarization. To generate power, the polarization should include a word supplied by the strain field, like the piezoelectric effect, electrification, and surface contact (e.g., triboelectric effect), unaffected by an electric field’s presence. Wang introduced an additional term Ps to the displacement vector D in 2017 to describe the contribution provided by CE-influence electrostatic charges in Maxwell’s equations [70]. NGS generates energy through a strain-induced piezoelectric (piezo potential) caused by ionic polarization inside the crystal. A piezoelectric nanogenerator (PENG) employing a single PZT nanowires array generates a current density of 4 A cm–2, a maximum output voltage of 0.7 V, and the standard power density 2.8 mW cm–3 [70]. A PV cell or photoelectric cell, or solar cell, is an electrical device consisting of a solid-state framework that captures the sunlight energy and converts it into electric power through PV, a chemical and physical phenomenon. In the case of bionanomaterials, a type of photoelectric cell is utilized

Scope of Bionanomaterials in Generation of Solar Energy 41

whose electrical properties, like resistance or voltage, the current varies when it is exposed to sunlight and generates electricity by capturing the photons of sunlight. The different types of solar cells are shown in Figure 2.2.

FIGURE 2.2  The categories of solar cells.

2.2.2.4  HYBRID SOLAR POWER GENERATORS PV alludes to the instantaneous transformation of light energy to electricity by a method of harnessing solar power. The PV phenomenon was initially reported in the mid-19th century in research utilizing an electrolytic cell by Alexandre Becquerel [54]. This cell comprised two platinum (Pt) electrodes submerged in an acid solution containing AgCl2, which created a photocurrent when illuminated with solar light. Revolutionary work in semiconductor principles and crystal formation occurred in the early 20th century [5]. Using these advancements, Bell laboratories constructed the first silicon (Si) based solar panel in 1946 and the first solar panel capable of producing sufficient electricity by 1954 [5]. Until recent times, Si-based solar panels dominated the PV industry. Maximum temperature and vacuum are required for the manufacturing of enhanced purity monocrystalline silicon, which increases both electricity input and expenditure [52].

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Over a decade, the enormous price of solar cells limited their use to the space sector. During the 1970s energy crisis, the necessity to reduce fossil fuels use drove researchers and innovators to build more cost-efficient solar panels [13]. This cost-cutting strategy has progressed with the introduction of new technology, manufacturing processes, and government funding, resulting in the widespread use of solid-state and Si-based solar panels. In the same way, that evolution has introduced robust light-capturing antennae designs to photosynthesis, the efficiency of low bandgap semiconductors can improve solar panels by adding a material with a broad absorption spectrum. The most spectacular achievements in the area of bio-based solar panels too far have been obtained utilizing titanium dioxide (TiO2) based bio-hybrid electrodes, such as those employed in the DSSCs [51]. 2.2.2.5  ADVANTAGES OF SOLAR POWER GENERATORS 2.2.2.5.1  Renewable Energy Source The essential feature of solar cells is that solar energy is a fully renewable energy resource. It could be utilized in any area of the world and therefore is accessible 24/7 hour. Solar energy, like certain alternative forms of energy, cannot be exhausted. Solar power will be obtainable for as long the sunlight exists; thus, it will be accessible to humanity for a minimum of 5.5 billion years [2]. 2.2.2.5.2  Lowers Electricity Bills The electricity costs will also be reduced even though you would fulfill several of the power generators’ electricity demands through the solar system. The money you can save on the bills is based on the capacity of the solar systems and the quantity of power or energy you consume. For example, if your firm employs commercial solar cells, this transition may be quite beneficial because the enormous generation capacity can offset a substantial portion of the energy expenses [29]. 2.2.2.5.3  Numerous Applications Solar power could be utilized for various types of applications. PVs can be used to generate heat or electricity. Solar power can be used to produce an

Scope of Bionanomaterials in Generation of Solar Energy 43

electric current in regions with no availability to the power resource, distilled water in areas with a scarcity of clean water, and power spacecraft in space. Solar power can also be utilized in construction materials [3]. 2.2.2.5.4  Low Maintenance Costs Solar power generators, overall, do not require a lot of maintenance. You only have to maintain them reasonably neat and clean, so having to clean them twice a year will be good. If you are in doubt, you always hire a specialized cleaner, which would cost you between £30 and £40 [3]. The majority of reliable solar cells companies provide warranties ranging from 25 to 30 years. There is also no wear and tear because there are no moving parts. The inverter is just the part that has to be replaced after 6–12 years due to its working capacity to transform sunlight radiation to proper heat and electricity. Aside from the inverters, must maintain the cables to guarantee that the solar energy system operates at peak efficiency. After paying for the original price of the solar system, you may anticipate investing relatively little on repairs and maintenance [3]. 2.2.2.5.5  Technological Advancement The technology in the solar power industry is constantly developing, and this development will continue for the foreseeable future. Advances in nanotechnology (NT) and quantum physics get the potential to enhance solar panel performance to double or triple the electrical output of solar power systems [3]. 2.2.3  BIOMOLECULE-SENSITIZED SOLAR CELLS (BSSCS) The BSSCs have been designed like a viable limited-cost PV power generating approach [49]. BSSCs work similarly to dye-sensitized solar cells (DSSCs). DSSCs are a novel type of solar device that has gotten a lot of interest as a potential replacement for existing PV devices. DSSCs have several benefits over silicon-based solar cells, including a simple manufacturing process, a wide range of material sources, relatively low price, and the ability to fabricate dynamic solar cells, even if their performance is still inferior to that of silicon-based solar panels [49].

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The photoanode in bR-based BSSCs is constructed of spongy-like semiconductors NPs (i.e., Zinc oxide (ZnO), titanium dioxide (TiO2)) that have been activated with bacteriorhodopsin proteins [62]. The bR collects solar light by moving up to the excited state and injecting photo-excited electrons into its semiconductor CB, which has an extensive absorption range in the visible area [46]. The CB of TiO2 is placed at a low energy state than LUMO of the bR compound; as a result, the infusion of photoelectrons from bR to TiO2 is energetically useful. Through all the external circuits, electrons move to the counter electrode. The bR has been employed as a sensitizer in BSSCs, in which bR was engaged in photo-induced charge carriers within the TiO2 semiconductors after immobilization. They found that a 3Glu mutant’s electrostatic potential map had a higher chance of binding effectively to TiO2, resulting in a more robust photoelectric response of the 3Glu mutant bR biosolar cell than the wild type bR bio-solar cell. Three negative charges Glu residues (E9, E204, and E194) have been changed to Gln (at the EC site of bR) in a 3Glu mutant, resulting in a significant shift in the surface potential map of bR. These modifications in a possible bR are most like maps [46]. Molaeirad et al. [49] have shown that co-sensitization of bacterioruberin and bR, which are comparable in their spectrum properties, can improve the PCA of BSSCs. They have recently enhanced the performance of bio-solar cells by immobilizing a Langmuir–Blodgett (LB) layer of bacteriorhodopsin on ZnO nonporous material. ZnO nanoparticles with a high equivalence point of around 9.5 are a suitable substrate for electrostatic attraction with excellent binding stability to bind bR, a low isoelectric point (IEP) protein [62]. The charge throughput at the TiO2/bR junction can be considerably reduced if the nanosized photoelectrode is loaded with more than just a coating of bR [46]. As a result, the stabilization of the LB layer of bacteriorhodopsin on the ZnO nanosized film, and the intrinsic properties of ZnO film, can be attributed to increased solar cell efficiency [46]. Mohammad Pour and Janfaza [46] devised a highly effective bR-based BSSC in 2015, which included material optimization at the nano-bio interface and morphological design. They demonstrated that applying TiCl4 to the surface of TiO2 NPs and adjusting the BR loading period can improve the charge transfer rate in a TiO2/bR interface. The power transform performance of 0.35%, open-circuit voltage (Voc) of 535 mV, and short-circuit current (Jsc) of 1 mA cm2 were attained using these two methodologies and coating a layer of light-scattering paste comprised of TiO2 nanofibers. However, when compared to DSSCs, the efficiency of bR-based BSSCs is insufficient. Unlike traditional DSSCs that utilize costly and hazardous ruthenium (Ru)

Scope of Bionanomaterials in Generation of Solar Energy 45

compounds, bR-based BSSCs use a cheap, reusable, environmentally safe, and anti-carcinogenic light collector with no disposal issues. It is hoped that innovative bio-sensitizers, such as wild-type BR and its mutations, would provide a viable alternative to traditional dyes [46]. 2.2.3.1  FACTORS AFFECTING THE EFFICIENCY OF BSSCS 2.2.3.1.1  Cell Temperature Following the p-n junction voltage temperature dependence observed in the diode factor q/kT, when the temperature goes up, the energy gap of the intrinsic semiconductor shrinks, and the open-circuit voltage (VOC) drops. As a result, the temperature coefficient of volatile organic compound (β) for solar cells is negative. Furthermore, the charge carriers at a relatively lower potential are released, resulting in lower power output for the same photocurrent. Under the same short-circuit current SCI, a decrease in Volatile Organic Compound leads to a lower theoretical maximum output Pmax = SCI’ VOC by utilizing the convention presented and calculating Fill Factor. The intrinsic semiconductor’s bandgap narrows as the temperature rises, absorbing more incident light because it has a more significant portion of adequate energy to elevate charge carriers from the VB to the CB. As a result of the increased photocurrent, Isc rises for given solar radiation, and the temperature coefficient of solar cells increases [19]. 2.2.3.1.2  Efficiency of Energy Conversion When a solar cell is linked to an electronic network, its efficacy of converting energy (η) is the percent of converting energy from captured light to electricity and accumulated. Under normal test circumstances, this factor is determined by dividing the highest PowerPoint (Pm) by the input solar energy (E, in W/ m2) and the solar cell’s surface area (Ac in m2) [45].

η=

Pm (1) ExAc

Energy conversion effectiveness is currently poor, necessitating vast areas for adequate insulation and generates concerns about adverse energy requirements for cell generation vs. energy collection. Two approaches are frequently utilized to improve the efficacy of energy conversion of the solar

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system by decreasing incident light reflection. The first is using an antireflection coating to reduce incident light reflection, and the second is the use of textured surfaces to restrict incident light optically. They demonstrated that altering the wavelength of sunlight may significantly enhance the spectral tolerance of a silicon photodiode substantially from the extreme ultraviolet to the visible range. The spectral range of the solar panel varies based on the type of module. As a result, changes in spectral irradiance affect solar energy generation. The spectral output of the solar panel varies based on the type of module. As a result, variations in light intensity have an impact on the production of solar energy. A black body of 5,900 K may simulate the solar spectrum, which yields an extensive range extending from ultraviolet to near-infrared. On the other hand, a semiconductor can only quickly transform charged particles with the energy of the bandgap. Absorption of lower energy photons are not will, whereas higher-energy photons by thermalization of photoinduced charge carriers are attenuated to gap energy [19]. 2.2.3.1.3  Maximum Tracking of Power Points (MTPP) Currently, the effectiveness of solar panels in converting power to electricity is relatively poor, usually around 14%. Various approaches should be utilized to increase the efficiency of solar panels. The MTPP uses a DC to DC highperformance transformer to provide the best and most appropriate output power. The photogenerated voltage LI is the same as the current generated by the cell when short-circuited (V = 0). When I = 0, the open-circuit voltage VOC may be calculated as described earlier [63]. In a short or open circuit, no energy is produced. At a certain point on the characteristic, the maximum power P generated by the transformation unit is attained. The fill-factor ff is commonly defined as:

= ff

Pmax Vm I m = (2) VOC VOC I I

where; Vm is the voltage; and Im is the current at the highest point of power. When the power output of the solar cells array is minimal, as the change in voltage occurs, output current varies little, making the PV cell cluster alike to a constant current source; when the voltage exceeds a critical value and continues to rise, the recent drops dramatically, making the PV cell array comparable to a constant voltage source. The output power reaches a maximum power point as the output voltage increases. The ultimate power tracker’s role is to modify the operating end of the PV cell array and change the equivalent load taken by

Scope of Bionanomaterials in Generation of Solar Energy 47

the PV cell matrix so that the PV cell array can work at the max output when the strength of light and temperature both vary [19]. 2.2.3.1.4  Series and Shunt Resistance Internal resistances induced parasitic effects in solar cells, resulting in power loss. A series resistance (RS) and a shunt resistance (SR) can be used to represent these resistances (RSH). The series resistance should ideally be zero. Metal contact or bulk substrate resistances, on the other hand, cause an extra power loss within the cell. So as the distance from EOC increases, the slope of the curve near EOC decreases. As a result, both the maximum voltage and area under the curve drop. This resistance is enormous in the ideal situation; therefore, there is no extra current route. The slope of the IV curve near the short circuit recent increases as RSH decreases. As a result, the open circuit potential EOC is reduced. A parallel resistor can be used to mimic the SR RSH. It is mainly caused via the cell by power dissipation, which is triggered by contaminants or manufacturing flaws [15]. 2.2.3.1.5  Flexibility and Life of BSSCs Bio-sensitized solar cells (BSSCs) have proved to be a significant potential candidate for the upcoming generation of solar cells. Owing to their advantages of being cost-effective, highly efficient, environment-friendly, and low angle dependency on incident light, they have grasped great recognition from the academy and industry. Many types of BSSCs have been evolved till now [11]. One of them is flexible BSSC. It is a novel area of research that is continuously changing and shows potential advantages and applications in electronic products, the building industry, and many others. They are easy to transport from one place to another and are pretty valuable for complex environments. The basic theme of flexible BSSCs is that they must fabricate a flexible working electrode, provided that the substrate is highly conductive, transparent, and able to bear high-temperature calcination as well as flexibility. Sensitization in BSSCs is attained by using light-sensitive biomolecules like proteins and chlorophylls. While choosing the sensitizer for applying solar cells, the ruling concern is the presence of thermal robustness in it. Also, it should have durable, functional activity for a persistent period during the efficient absorption of solar radiations to make photo-induced charge generation [22].

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2.2.3.2  COMPARISON OF DSSCS AND BSSCS For DSSCs, biomaterials have several benefits over-commercialized metalsynthetic dyes. Natural bio-based sources are a potential option for utilization in DSSCs that can be easily placed as rolls in various everyday things, including handbags and garments, and windows, walls of buildings, and incorporated bio-photovoltaics. Benefits of utilizing natural pigments from bio-molecular source materials include: (1) Bacteria, associated carotenoids, and protein complexes are low cost; (2) Bio-dye extraction is uncomplicated, practicable, and could be utilized in high levels; (3) Biological pigments are long-lasting, biodegradable, and renewable making them extremely practical; (4) Bacterial pigments are typically noncarcinogenic and cause minimal risks to live organisms, making them eco-friendly options; (5) Because of their broad absorption spectra, bio-sensitizers can absorb the majority of light energy [49]. 2.3  FUTURE PROSPECTS The popularity of bionanotechnology has been increasing day by day. There is a possibility that the future of bionanotechnology is very bright. There are many expectations regarding future applications of bionanotechnology. Bionanomaterials have been excellently biocompatible, offering various applications including environmental safety, solar energy production, renewable power generation, water treatment, packaging, electronics, construction, coatings, cosmetics, medicine, agriculture, and textiles. The research endeavors in solar energy-producing bionanomaterials have also expanded to serve humanity, including restoring mechanical damage and clean environmental remediation. The future applications of bionanotechnology depend drastically on the use of biological materials with conjugations of nanomaterials. Biological systems may be used for the improvement of bionanotechnology in a variety of ways. Currently, bionanotechnology has been applied in various fields such as medicine, electronics, biomaterials, and energy production. Along with the emerging technologies and tools of bionanotechnology, this field is benefiting [10]. 2.4 SUMMARY Bio-Nanotechnology is really a breakthrough discipline that is only getting started, with the direction in the near future would be its combination with

Scope of Bionanomaterials in Generation of Solar Energy 49

green chemistry. To conclude, we show how biomolecules may be used to assemble and nanocrystals to promote Z-schemes for PCA. The benefits of organic semiconductors and bio-nanoparticles will be combined with the characteristics of inorganic semiconductors in bio-hybrid solar cell development. When compared to ordinary inorganic semiconductors solar cells, their energy generation efficiency remains poor. For various kinds of Bio-hybrid solar cell technologies, more study and improvement for optimization is necessary. This chapter also discusses the factors that influence solar cell efficiency. An intrinsic property of solar cells causes temperature influences. They create more voltage when the temperature decreases and, inversely, lose voltage when the temperature rises. By adjusting these factors is essential for power conversion efficiency (PCE). The optimal parameters allow for the tremendous benefits of solar power to be obtained at a considerably reduced cost. The parameter field is vast, and only a subset of the potential possibilities has been implemented. Even these little attempts have garnered interest due to their easy tunability and inexpensive processing costs. These future researches are expected to offer new pathways in bio-nanoelectronics to biohybrid materials for power collecting and sustainable energy. KEYWORDS • • • • • • •

bacterio-rhodopsin biomolecule-sensitized solar cells chemical vapor deposition conduction band metal oxides photocatalytic activity valence band

REFERENCES 1. Abdelwahab, N., & Morsy, E., (2018). Synthesis and characterization of methyl pyrazolone functionalized magnetic chitosan composite for visible light photocatalytic degradation of methylene blue. International Journal of Biological Macromolecules, 108, 1035–1044.

50

Sustainable Nanomaterials for Biosystems Engineering

2. Arthur, R., Baidoo, M. F., & Antwi, E., (2011). Biogas is a potential renewable energy source: A Ghanaian case study. Renewable Energy, 36(5), 1510–1516. 3. Barlev, D., Vidu, R., & Stroeve, P., (2011). Innovation in concentrated solar power. Solar Energy Materials and Solar Cells, 95(10), 2703–2725. 4. Bisquert, J., (2013). The swift surge of perovskite photovoltaics. The Journal of Physical Chemistry Letters, 4(15), 2597, 2598. 5. Brinkman, W. F., Haggan, D. E., & Troutman, W. W., (1997). A history of the invention of the transistor and where it will lead us. IEEE Journal of Solid-State Circuits, 32(12), 1858–1865. 6. Brown, K. A., Dayal, S., Ai, X., Rumbles, G., & King, P. W., (2010). Controlled assembly of hydrogenase-CdTe nanocrystal hybrids for solar hydrogen production. Journal of the American Chemical Society, 132(28), 9672–9680. 7. Brown, K. A., Harris, D. F., Wilker, M. B., Rasmussen, A., Khadka, N., Hamby, H., Keable, S., et al., (2016). Light-driven dinitrogen reduction catalyzed by a CdS: Nitrogenase MoFe protein biohybrid. Science, 352(6284), 448–450. 8. Cai, T., Liu, Y., Wang, L., Dong, W., & Zeng, G., (2019). Recent advances in round-theclock photocatalytic system: Mechanisms, characterization techniques and applications. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 39, 58–75. 9. Çevik, E., Titiz, M., & Şenel, M., (2018). Light-dependent photocurrent generation: Novel electrochemical communication between biofilm and electrode by ferrocene cored poly (amidoamine) dendrimers. Electrochimica Acta, 291, 41–48. 10. Chang, J., Zhang, L., & Wang, P., (2018). Intelligent environmental nanomaterials. Environmental Science: Nano, 5(4), 811–836. 11. Chellamuthu, J., Nagaraj, P., Chidambaram, S. G., Sambandam, A., & Muthupandian, A., (2016). Enhanced photocurrent generation in bacteriorhodopsin based bio-sensitized solar cells using gel electrolyte. Journal of Photochemistry and Photobiology B: Biology, 162, 208–212. 12. Chen, X., Li, C., Grätzel, M., Kostecki, R., & Mao, S. S., (2012). Nanomaterials for renewable energy production and storage. Chemical Society Reviews, 41(23), 7909–7937. 13. Claassens, N. J., Sousa, D. Z., Dos, S. V. A. M., De Vos, W. M., & Van, D. O. J., (2016). Harnessing the power of microbial autotrophy. Nature Reviews Microbiology, 14(11), 692–706. 14. Corsi, I., Winther-Nielsen, M., Sethi, R., Punta, C., Della, T. C., Libralato, G., Lofrano, G., et al., (2018). Ecofriendly nanotechnologies and nanomaterials for environmental applications: Key issue and consensus recommendations for sustainable and ecosafe nanoremediation. Ecotoxicology and Environmental Safety, 154, 237–244. 15. Djurišić, A. B., Liu, X., & Leung, Y. H., (2014). Zinc oxide films and nanomaterials for photovoltaic applications. Physica Status Solidi (RRL)–Rapid Research Letters, 8(2), 123–132. 16. Duan, J., Yang, M., Lai, Y., Yuan, J., & Zhan, J., (2012). A colorimetric and surfaceenhanced Raman scattering dual-signal sensor for Hg2+ based on bismuthiol II-capped gold nanoparticles. Analytica Chimica Acta, 723, 88–93. 17. Fakhri, A., Gupta, V. K., Rabizadeh, H., Agarwal, S., Sadeghi, N., & Tahami, S., (2018). Preparation and characterization of WS2 decorated and immobilized on chitosan and polycaprolactone as biodegradable polymers nanofibers: Photocatalysis study and antibiotic-conjugated for antibacterial evaluation. International Journal of Biological Macromolecules, 120, 1789–1793.

Scope of Bionanomaterials in Generation of Solar Energy 51 18. Fathi, N., Almasi, H., & Pirouzifard, M. K., (2019). Sesame protein isolate based bionanocomposite films incorporated with TiO2 nanoparticles: Study on morphological, physical, and photocatalytic properties. Polymer Testing, 77, 1–9. 19. Furkan, D., & Mehmet, E. M., (2010). Critical factors that affecting the efficiency of solar cells. Smart Grid and Renewable Energy, 2(3), 47–50. 20. Zhou, P., Yu, J., & Jaroniec, M., (2014). All-solid-state Z-scheme photocatalytic systems. Advanced Materials, 26(29), 4920–4935. 21. Ghasemzadeh, F., Esmaeilzadeh, M., & Shayan, M. E., (2020). Photovoltaic temperature challenges and bismuthene monolayer properties. International Journal of Smart Grid, 4(4), 190–195. 22. Griep, M. H., Walczak, K. A., Winder, E. M., Lueking, D. R., & Friedrich, C. R., (2010). Quantum dot enhancement of bacteriorhodopsin-based electrodes. Biosensors and Bioelectronics, 25(6), 1493–1497. 23. Habisreutinger, S. N., Schmidt, M. L., & Stolarczyk, J. K., (2013). Photocatalytic reduction of CO2 on TiO2 and other semiconductors. Angewandte Chemie International Edition, 52(29), 7372–7408. 24. Huang, C., Qiao, X., Sun, W., Chen, H., Chen, X., Zhang, L., & Wang, T., (2019). Effective extraction of domoic acid from seafood based on post-synthetic-modified magnetic zeolite imidazolate framework-8 particles. Analytical Chemistry, 91(3), 2418–2424. 25. Huang, P., Lin, J., Li, W., Rong, P., Wang, Z., Wang, S., Wang, X., et al., (2013). Biodegradable gold nanovesicles with an ultrastrong plasmonic coupling effect for photoacoustic imaging and photothermal therapy. Angewandte Chemie, 125(52), 14208–14214. 26. Ji, X., Su, Z., Wang, P., Ma, G., & Zhang, S., (2015). Tethering of nicotinamide adenine dinucleotide inside hollow nanofibers for high-yield synthesis of methanol from carbon dioxide catalyzed by coencapsulated multienzymes. ACS Nano, 9(4), 4600–4610. 27. Kaushik, S., Sarma, M. K., & Goswami, P., (2017). FRET-guided surging of cyanobacterial photosystems improves and stabilizes current in photosynthetic microbial fuel cell. Journal of Materials Chemistry A, 5(17), 7885–7895. 28. Kaushik, S., Sarma, M. K., Thungon, P. D., Santhosh, M., & Goswami, P., (2016). Thin films of silk fibroin and its blend with chitosan strongly promote biofilm growth of Synechococcus sp. BDU 140432. Journal of Colloid and Interface Science, 479, 251–259. 29. Khan, I., Mahmood, A., Javaid, N., Razzaq, S., Khan, R., & Ilahi, M., (2013). Home energy management systems in future smart grids. Journal of Basic and Applied Scientific Research, 3(3), 1224–1231. 30. Kumar, A., Sharma, G., Naushad, M., Ahamad, T., Veses, R. C., & Stadler, F. J., (2019). Highly visible active Ag2CrO4/Ag/BiFeO3@RGO nano-junction for photoreduction of CO2 and photocatalytic removal of ciprofloxacin and bromate ions: The triggering effect of Ag and RGO. Chemical Engineering Journal, 370, 148–165. 31. Kumar, A., Sharma, G., Naushad, M., & Thakur, S., (2015). SPION/β-cyclodextrin core-shell nanostructures for oil spill remediation and organic pollutant removal from wastewater. Chemical Engineering Journal, 280, 175–187. 32. Lai, B., Schneider, H., Tschörtner, J., Schmid, A., & Krömer, J. O., (2021). Technicalscale biophotovoltaics for long-term photo-current generation from Synechocystis sp. PCC6803. Biotechnology and Bioengineering, 118(7), 2637–2648. 33. Leskelä, M., & Ritala, M., (2002). Atomic layer deposition (ALD): From precursors to thin film structures. Thin Solid Films, 409(1), 138–146.

52

Sustainable Nanomaterials for Biosystems Engineering

34. Li, H., Tu, W., Zhou, Y., & Zou, Z., (2016). Z-Scheme photocatalytic systems for promoting photocatalytic performance: Recent progress and future challenges. Advanced Science, 3(11), 1–12. 35. Li, X., Qian, X., An, X., & Huang, J., (2019). Preparation of a novel composite comprising biochar skeleton and “chrysanthemum” g-C3N4 for enhanced visible light photocatalytic degradation of formaldehyde. Applied Surface Science, 487, 1262–1270. 36. Lior, N., (2008). Energy resources and use: The present situation and possible paths to the future. Energy, 33(6), 842–857. 37. Liu, C., Colón, B. C., Ziesack, M., Silver, P. A., & Nocera, D. G., (2016). Water splitting– biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis. Science, 352(6290), 1210–1213. 38. Liu, C., Sakimoto, K. K., Colón, B. C., Silver, P. A., & Nocera, D. G., (2017). Ambient nitrogen reduction cycle using a hybrid inorganic–biological system. Proceedings of the National Academy of Sciences, 114(25), 6450–6455. 39. Lu, X., Wang, C., & Wei, Y., (2009). One-dimensional composite nanomaterials: Synthesis by electrospinning and their applications. Small, 5(21), 2349–2370. 40. Luo, Y., Xu, J., & Huang, J., (2014). Hierarchical nanofibrous anatase–titania–cellulose composite and its photocatalytic property. CrystEngComm, 16(3), 464–471. 41. Maduraiveeran, G., (2020). Bionanomaterial-based electrochemical biosensing platforms for biomedical applications. Analytical Methods, 12(13), 1688–1701. 42. Mahmoudi, T., Wang, Y., & Hahn, Y. B., (2018). Graphene and its derivatives for solar cells application. Nanoenergy, 47, 51–65. 43. McCormick, A. J., Bombelli, P., Bradley, R. W., Thorne, R., Wenzel, T., & Howe, C. J., (2015). Biophotovoltaics: Oxygenic photosynthetic organisms in the world of bioelectrochemical systems. Energy & Environmental Science, 8(4), 1092–1109. 44. Menanteau, P., Finon, D., & Lamy, M. L., (2003). Prices versus quantities: Choosing policies for promoting the development of renewable energy. Energy Policy, 31(8), 799–812. 45. Meral, M. E., & Dincer, F., (2011). A review of the factors affecting operation and efficiency of photovoltaic based electricity generation systems. Renewable and Sustainable Energy Reviews, 15(5), 2176–2184. 46. Mohammadpour, R., & Janfaza, S., (2015). Efficient nanostructured biophotovoltaic cell based on bacteriorhodopsin as biophotosensitizer. ACS Sustainable Chemistry & Engineering, 3(5), 809–813. 47. Mohandas, A., Deepthi, S., Biswas, R., & Jayakumar, R., (2018). Chitosan based metallic nanocomposite scaffolds as antimicrobial wound dressings. Bioactive Materials, 3(3), 267–277. 48. Mohsin, M., Bhatti, I. A., Ashar, A., Khan, M. W., Farooq, M. U., Khan, H., Hussain, M. T., et al., (2021). Iron-doped zinc oxide for photocatalyzed degradation of humic acid from municipal wastewater. Applied Materials Today, 23, 101047. doi: 10.1016/j. apmt.2021.101047. 49. Molaeirad, A., Janfaza, S., Karimi, F. A., & Mahyad, B., (2015). Photocurrent generation by adsorption of two main pigments of Halobacterium salinarum on TiO2 nanostructured electrode. Biotechnology and Applied Biochemistry, 62(1), 121–125. 50. Murillo-Sierra, J. C., Hernández-Ramírez, A., Hinojosa-Reyes, L., & Guzmán-Mar, J. L., (2021). A review on the development of visible light-responsive WO3-based photocatalysts for environmental applications. Chemical Engineering Journal Advances, 5, 1–19.

Scope of Bionanomaterials in Generation of Solar Energy 53 51. Musazade, E., Voloshin, R., Brady, N., Mondal, J., Atashova, S., Zharmukhamedov, S. K., Huseynova, I., et al., (2018). Biohybrid solar cells: Fundamentals, progress, and challenges. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 35, 134–156. 52. Nybo, S. E., Khan, N. E., Woolston, B. M., & Curtis, W. R., (2015). Metabolic engineering in chemolithoautotrophic hosts for the production of fuels and chemicals. Metabolic Engineering, 30, 105–120. 53. Pandi, K., Viswanathan, N., & Meenakshi, S., (2019). Hydrothermal synthesis of magnetic iron oxide encrusted hydrocalumite-chitosan composite for defluoridation studies. International Journal of Biological Macromolecules, 132, 600–605. 54. Razeghifard, R., (2013). Natural and Artificial Photosynthesis: Solar Power as an Energy Source (p. 488). John Wiley & Sons. 55. Sambur, J. B., Chen, T. Y., Choudhary, E., Chen, G., Nissen, E. J., Thomas, E. M., Zou, N., & Chen, P., (2016). Sub-particle reaction and photocurrent mapping to optimize catalyst-modified photoanodes. Nature, 530(7588), 77–80. 56. Sarma, M. K., Quadir, M. G. A., Bhaduri, R., Kaushik, S., & Goswami, P., (2018). Composite polymer-coated magnetic nanoparticles based anode enhances dye degradation and power production in microbial fuel cells. Biosensors and Bioelectronics, 119, 94–102. 57. Shao, L., Liu, H., Zeng, W., Zhou, C., Li, D., Wang, L., Lan, Y., Xu, F., & Liu, G., (2019). Immobilized and photocatalytic performances of PDMS-SiO2-chitosan@ TiO2 composites on pumice under simulated sunlight irradiation. Applied Surface Science, 478, 1017–1026. 58. Singh, J., Kumar, V., Kim, K. H., & Rawat, M., (2019). Biogenic synthesis of copper oxide nanoparticles using plant extract and its prodigious potential for photocatalytic degradation of dyes. Environmental Research, 177, 1–12. 59. Sokol, K. P., Robinson, W. E., Warnan, J., Kornienko, N., Nowaczyk, M. M., Ruff, A., Zhang, J. Z., & Reisner, E., (2018). Bias-free photoelectrochemical water splitting with photosystem II on a dye-sensitized photoanode wired to hydrogenase. Nature Energy, 3(11), 944–951. 60. Stankovich, S., Dikin, D. A., Compton, O. C., Dommett, G. H., Ruoff, R. S., & Nguyen, S. T., (2010). Systematic post-assembly modification of graphene oxide paper with primary alkylamines. Chemistry of Materials, 22(14), 4153–4157. 61. Thakur, M., Sharma, G., Ahamad, T., Ghfar, A. A., Pathania, D., & Naushad, M., (2017). Efficient photocatalytic degradation of toxic dyes from aqueous environment using gelatin-Zr (IV) phosphate nanocomposite and its antimicrobial activity. Colloids and Surfaces B: Biointerfaces, 157, 456–463. 62. Villarreal, C. C., Pham, T., Ramnani, P., & Mulchandani, A., (2018). Carbon allotropes as sensors for environmental monitoring. Current Opinion in Electrochemistry, 3(1), 106–113. 63. Vollbrecht, J., & Brus, V. V., (2021). Effects of recombination order on open-circuit voltage decay measurements of organic and perovskite solar cells. Energies, 14(16), 4800. 64. Wang, C., Zhang, L., Yang, J., Wang, D., Sun, Y., & Wang, J., (2018). Cuprous oxide nanostructures tuned by histidine-containing peptides and their photocatalytic activities. Applied Surface Science, 453, 173–181. 65. Wang, D., Kou, R., Choi, D., Yang, Z., Nie, Z., Li, J., Saraf, L. V., et al., (2010). Ternary self-assembly of ordered metal oxide–graphene nanocomposites for electrochemical energy storage. ACS Nano, 4(3), 1587–1595.

54

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66. Wang, L., Zhu, Y., Xu, L., Chen, W., Kuang, H., Liu, L., Agarwal, A., et al., (2010). Side by side and end to end gold nanorod assemblies for environmental toxin sensing. Angewandte Chemie, 122(32), 5604–5607. 67. Wang, S., Liu, K., Yao, X., & Jiang, L., (2015). Bioinspired surfaces with super wettability: New insight on theory, design, and applications. Chemical Reviews, 115(16), 8230–8293. 68. Wang, X., Hu, J., Chen, Q., Zhang, P., Wu, L., Li, J., Liu, B., et al., (2019). Synergic degradation of 2,4,6-trichlorophenol in microbial fuel cells with intimately coupled photocatalytic-electrogenic anode. Water Research, 156, 125–135. 69. Wang, Z. L., (2008). Towards self-powered nanosystems: From nanogenerators to nanopiezotronics, Advanced Functional Materials, 18(22), 3553–3567. 70. Wang, Z. L., (2017). On maxwell’s displacement current for energy and sensors: The origin of nanogenerators. Materials Today, 20(2), 74–82. 71. Wang, Z. L., (2012). Self-powered nanosensors and nanosystems. Advanced Materials, 24(2), 279–279. 72. Wang, Z. L., & Song, J., (2006). Piezoelectric nanogenerators based on zinc oxide nanowire arrays. Science, 312(5771), 242–246. 73. Wenzel, T., Härtter, D., Bombelli, P., Howe, C. J., & Steiner, U., (2018). Porous translucent electrodes enhance current generation from photosynthetic biofilms. Nature Communications, 9(1), 1–9. 74. Wilker, M. B., Shinopoulos, K. E., Brown, K. A., Mulder, D. W., King, P. W., & Dukovic, G., (2014). Electron transfer kinetics in CdS nanorod–[FeFe]-hydrogenase complexes and implications for photochemical H2 generation. Journal of the American Chemical Society, 136(11), 4316–4324. 75. Xue, Z., Yan, C., & Wang, T., (2019). From atoms to lives: The evolution of nanoparticle assemblies. Advanced Functional Materials, 29(12), 1–33. 76. Yang, X., Zhang, X., Wang, Z., Li, S., Zhao, J., Liang, G., & Xie, X., (2019). Mechanistic insights into removal of norfloxacin from water using different natural iron ore-biochar composites: More rich free radicals derived from natural pyrite-biochar composites than hematite-biochar composites. Applied Catalysis B: Environmental, 255, 1–13. 77. Yaragalla, S., Rajendran, R., AlMaadeed, M. A., Kalarikkal, N., & Thomas, S., (2019). Chemical modification of graphene with grape seed extract: Its structural, optical, and antimicrobial properties. Materials Science and Engineering: C, 102, 305–314. 78. Yi, H., Yan, M., Huang, D., Zeng, G., Lai, C., Li, M., Huo, X., Qin, L., Liu, S., & Liu, X., (2019). Synergistic effect of artificial enzyme and 2D nano-structured Bi2WO6 for eco-friendly and efficient biomimetic photocatalysis. Applied Catalysis B: Environmental, 250, 52–62. 79. Youssef, A. M., El-Nahrawy, A. M., & Abou, H. A. B., (2017). Sol-gel synthesis and characterizations of hybrid chitosan-PEG/calcium silicate nanocomposite modified with ZnO-NPs and (E102) for optical and antibacterial applications. International Journal of Biological Macromolecules, 97, 561–567. 80. Yu, G., Zhang, X., Sang, Y., Wang, Z., Hu, X., Xu, X., Li, L., et al., (2019). Synthesis and characterization of a coaxial carbon-TiO2 nanotube arrays film with spectral response from UV to NIR and its application in solar energy conversion. Electrochimica Acta, 301, 325–331. 81. Yu, J., Wang, S., Low, J., & Xiao, W., (2013). Enhanced photocatalytic performance of direct Z-scheme gC3N4–TiO2 photocatalysts for the decomposition of formaldehyde in air. Physical Chemistry Chemical Physics, 15(39), 16883–16890.

Scope of Bionanomaterials in Generation of Solar Energy 55 82. Yusoff, N., Ong, S. A., Ho, L. N., Rashid, N. A., Wong, Y. S., Saad, F. N. M., Khalik, W., & Lee, S. L., (2018). Development of simultaneous photo-biodegradation in the photocatalytic hybrid sequencing batch reactor (PHSBR) for mineralization of phenol. Biochemical Engineering Journal, 138, 131–140. 83. Zabihi, E., Babaei, A., Shahrampour, D., Arab-Bafrani, Z., Mirshahidi, K. S., & Majidi, H. J., (2019). Facile and rapid in-situ synthesis of chitosan-ZnO nano-hybrids applicable in medical purposes; a novel combination of biomineralization, ultrasound, and bio-safe morphology-conducting agent. International Journal of Biological Macromolecules, 131, 107–116. 84. Zhang, H., Liu, H., Tian, Z., Lu, D., Yu, Y., Cestellos-Blanco, S., Sakimoto, K. K., & Yang, P., (2018). Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production. Nature Nanotechnology, 13(10), 900–905.

CHAPTER 3

ADVANCED ELECTROCHEMICAL BIONANOMATERIALS FOR ENERGY CONVERSION AND STORAGE SUMAN GANDI, SARAN SRIHARI SRIPADA PANDA, SAIDI REDDY PARNE, NAGARAJU POTHUKANURI, and GANGARAJU GEDDA

ABSTRACT Within the last few years, the interaction between electrochemical bionanomaterials and renewable energy resources has created many opportunities to develop novel sustainable alternative emerging technologies such as batteries, fuel cells, and supercapacitors. Humans have used bionanomaterials since the beginning of time, though they were not aware of it. The progress of green technologies, which increasingly rely on biocompatible nanomaterials (NMs) with characteristics equivalent to traditional materials, is critical to meeting the urgent demand for sustainable energy development. These technologies represent the pathway to a more sustainable future. Electrochemical bionanomaterials with properties comparable to those of existing materials are becoming increasingly important. The present contribution aims to provide an overview of the progress of advanced electrochemical bionanomaterials, mainly linked to energy storage and conversion for a broad range of applications. 3.1 INTRODUCTION Recent advances in nanoscience and technology have made significant contributions to the development of functional materials, particularly Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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bionanomaterials, which have a wide variety of applications extending from electrochemical energy storage (EES) and conversion to biomedical applications, bioengineering, biotechnology, and so on [6, 18, 70, 100, 138]. Though traditional engineering NMs are intended to execute relatively basic and fixed jobs, they cannot adapt. In some cases, they may even lose their original functions and properties as environmental circumstances change [15, 28, 98]. Designing smart environmentally-friendly bionanomaterials allows them to have proactive characteristics that allow them to self-adjust their properties to improve performance even when exposed to changing environmental circumstances [78]. We all know that the synthesis and design of bionanomaterials may result in the development of certain disruptive technologies with improved performance to reform and move ahead with environmental engineering research and development (R&D) [99]. Furthermore, scientists have recently developed it as a significant branch of innovative biomaterials intended to recover primarily mechanical damage or surface functionalities under ambient settings without external provocations, and therefore without the need for energy input [68, 72, 99]. It has also been claimed that many bionanomaterials, including: biopolymer-based nanocomposites (NCs), biomass, biowaste, cellulose nanofibrils, carbon nanotubes, and polylactide, may be used in the production of NCs, which can be used in a variety of applications, including electrical energy storage systems (EESS), air pollution treatment, emerging sensors, aeronautics, automobiles, electrical devices, and underwater equipment, etc. [36, 78, 105, 111, 114]. Rapid advancements in consumer electronics, electric vehicles (EVs), and grid-scale stationary storage have increased the call for clean and alternative innovative energy storage technologies [5, 79, 80]. It is a cost-effective and self-contained method of generating electricity in off-grid systems using alternative renewable energy sources such as solar or wind, which opens up a wide range of opportunities and interest in a new emerging economy based on long-term, low-cost, high-performance energy systems [52, 118]. Though these energy sources are dependent on weather, they are subject to change. Due to their modularity and versatility, EES systems are ideal for ensuring reliable energy supply and limiting their intermittency [4]. In this view, considerable efforts have been made to advance renewable energy storage technologies, particularly rechargeable batteries, fuel cells, flow batteries, and supercapacitors [2]. Additionally, these devices are manufactured by using a variety of conventional toxic raw materials, including metals and non-metals, as well as flammable electrolytes, posing environmental concerns and limiting the

Advanced Electrochemical Bionanomaterials 59

use of compounds [55]. However, the transition from conventional toxic raw materials to low-carbon emitting technologies would increase demand for clean, sustainable energy storage and its basic materials. As a result, finding alternatives to some of these present materials in devices must focus on the following years. In this view, electrochemical bionanomaterials are an excellent choice for developing sustainable EES systems, owing to their ability to combine the desired characteristics of their constituents into an intelligent hierarchical design that the overall efficiency and energy optimization of their pieces exceeds in most circumstances [14, 22, 99, 124]. Additionally, it may readily change the structural characteristics of bionanomaterials (e.g., thermal, mechanical, and electrochemical capabilities) by altering the synergistic impact of their interfacial contacts with other materials. However, electrochemical storage device performance depends on the contributions made by multiple electrode and electrolyte components. The engineering of each component is critical to the successful development of sophisticated electrochemical storage devices with high energy storage capacities. Moreover, bionanomaterials possess the intrinsic diversity and complexity of their unique structural/compositional makeup due to their multiple functional groups, different structures, and a multitude of physicochemical properties [22, 97, 148]. Bionanomaterials are endowed with multifunctionality, alteration properties, and compatibility with present traditional materials due to these inheriting and favorable characteristics, which have a significant positive impact on the progress of a clean and viable energy economy. In reality, electrochemical bionanomaterials have been widely studied in a wide range of energy storage systems (ESS) (Figure 3.1), including alkali-ion batteries (e.g., Li/Na/K-ion batteries), flow batteries, supercapacitors, and other types of fuel cells [11, 23, 43, 56, 60, 74, 81, 85, 95, 120, 128, 130, 132, 152]. The present book chapter discusses recent advances in electrochemical bionanomaterials and research strategies used to develop EES devices. 3.2  ELECTROCHEMICAL BIONANOMATERIALS The rise of renewable energy, including solar and wind power, and the increased use of EVs and grid storage require enhanced and low-cost EES systems. To satisfy the future requirements for ESS, unique material systems with extraordinary energy densities, widely available raw materials, and safety are essential in an economical and low-carbon emission manufacturing

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environment [21, 37]. Many researchers are trying to develop suitable EES systems for e-mobility and stationary storage and set an objective of lifetime and cost. Recently, the use of organic, bio-nano, electrochemical bionanomaterials, and biopolymer electroactive materials that are generated and extracted from renewable sources is a promising approach for developing improved electrode/electrolyte materials and binders for batteries and other storage devices (Figure 3.2) [3, 55, 66].

FIGURE 3.1  Energy conversion and storage using advanced electrochemical bionanomaterials.

The majority of them do not include any expensive or environmentally harmful metals, and they may be found in abundance all over the world. When considering the scalability and widespread adoption of these materials worldwide, these characteristics become even more critical, especially in light of the projected growth in battery manufacturing over the next few years. Using these new and more efficient electrochemical bio-nano/bioinspired electrode/electrolyte materials (Figure 3.2) will limit the production of GHGes such as CO2, HCs, and N2O and an enormous amount of their byproducts, resulting in a significant positive impact on the environment. Using a combination of renewable energy generation technologies and

Advanced Electrochemical Bionanomaterials 61

environmentally-friendly electrochemical bionanomaterials will be a promising approach to deliver clean electricity directly to people’s homes, even in rural areas where there is no access to the power grid. Battery technologies such as Li-ion batteries (LIBs), lead-acid batteries (LABs), and vanadium flow batteries (VFBs), as previously mentioned, show potential and appropriate characteristics for grid-scale storage. However, they are still far from the grid’s storage requirements, including low cost, extended cycle life, safety, and high energy density. Na-ion, proton, and organic-based RFBs are presently the most promising low-cost and environmentally friendly battery technologies used in both grid and off-grid systems. The following sections will discuss the use of abundant and renewable bionanomaterials as electrodes and electrolytes in the production of ecologically safe batteries. The energy densities of the battery have been used to compare different battery chemistries up to this point, which is explained in greater detail later in this introduction.

FIGURE 3.2  Schematic illustration of sustainable electrochemical bionanomaterials: Electrodes, electrolytes, and binders.

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3.2.1  LITHIUM-ION BATTERIES (LIBS) In the race to produce an energy storage system capable of powering electronic devices, LIBs remain the most likely candidates. However, the primary difficulty is making them safe, cost-effective, and environmentally friendly. Additionally, electrode materials experiencing low EC, volume deformation, and cessation of electrodes in organic/ionic liquid electrolytes, all of which impede the flow of electrons, combine to create the net effect of slow conduction and pulverization of electrodes during the cycle process [110]. In this sense, bio-nanomaterials are a good alternative for improving the electrode performance of LIBs because they reduce the ion diffusion distance, improve the specific surface area available for electron conduction, and most essentially reduce the strain induced by volume changes during the cycling process. One viable method for creating bionanomaterials for LIBs is to replace harmful electrode materials with renewable biomass-produced cellulose derivatives, bio waste, and lignin-based compounds. In addition to sustainability, using these bionanomaterials also provides enhanced safety and disposal logistics for LIBs. In this section, we summarize recent breakthroughs in electrodes and binders and LIB materials technology based on bionanomaterials. 3.2.1.1  ADVANCED BIONANO-ANODE MATERIALS FOR LIBS Carbon is one of the most favorable potential anode materials for LIBs. However, the production of conventional carbon compounds from coal and petrochemical products is often energy demanding and involves harsh manufacturing conditions. Additionally, it is highly desired to develop a practical strategy for producing carbon compounds from renewable resources that are both high performing and have a minimal environmental impact is a top priority for researchers. Recent research has shown that bionanomaterials have an essential possibility for energy storage and conversion due to their ability to easily tweak electron-conduction pathways in terms of surface chemistry and porosity. In this sense, bionanomaterials with rich surface functional groups and easily adjustable porosity created from lignin, biomass, and biowaste may be a good contender for use as a sustainable carbon material [84]. Lignin is one of the essential structural components of a tree. It serves as the glue that holds the tree together and includes a significant quantity of elemental carbon, particularly aromatic carbons, which are required to

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produce high-grade carbon products [87]. Carbonizing biomass involves numerous heat and mechanical procedures that turn lignin into a technological carbon substance. In a straightforward procedure, Zhang et al. [146] successfully synthesized lignin-derived hierarchical porous carbon. It used a three-dimensional macroporous system with mesopores and micropores embellished on carbon walls to construct it. It demonstrated a high steady capacity of 470 mAh g–1 after 400 cycles at a current density of 200 mA g–1. Recently, an ideal biomass-derived nitrogen-doped fused carbon fiber mat was created by lignin–polyethylene oxide (90:10) composite through electrospinning and carbonization. The research highlights the significant promise of lignin-derived nanocarbon anode material shows the capacity of 445 mAh g–1 at a current density of 30 mAg–1 for LIBs [127]. Furthermore, anode materials made from biomass-based pomelo peel, banana peel, coconut oil, coffee oil, sugar, pistachio shell, peanut shell, and cotton fiber have recently demonstrated outstanding electrochemical stability for LiBs, and they have the potential to be cost-effective alternatives to graphite-based carbonaceous anode materials [142]. Following carbon, Silicon has been identified as the most favorable highcapacity anode material due to its extraordinarily high theoretical capacity of 4,200 mAh g–1, non-toxicity, and inexpensive cost [29]. Besides, throughout the charge/discharge procedure with Si, there is a volume change, electrode pulverization, an unstable solid electrolyte interphase (SEI), and the cessation of electron-conduction pathways, limiting the commercialization [29]. Although creating a conductive carbon shell on the Si surface can capably minimize the volume changes, stabilize SEI (passivation layer), and offer uninterrupted and steady electron-conduction [48]. Many C/Si composites have been described in the literature by employing carbon sources such as starch, glucose, cellulose, rice husk, and other biomasses [45, 131]. For example, under the influence of enzymes, a C/silicon composite was created by coating and carbonizing starch slurry [131]. Upon reaching 30% silicon content, the discharge capacity of the composite is 1,490 mAh g–1 when operating with a charge density of 0.2 Ag–1. Recently Jia and Huang [45] revealed that a Si/C composite composed of natural cellulose and a full silicon coating on carbon nanofibers (CNF) had a discharge capacity of 750.6 mAh g–1 after 150 cycles with a current density of 100 mA g–1. Furthermore, the presence of a binder is crucial in the preservation of electrode integrity when Si experiences significant volume changes throughout the charge/discharge processes, the design of an oxidized starch cross-linked sodium CMC water-soluble binder results in the creation of a 3D structure

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that demonstrates a reversible capacity of 1.92 Ah g–1 even after 100 cycles with a current density of 0.4 A g–1 [143]. In addition, metal oxides (MO) based tin, iron, antimony, manganese, vanadium, and cobalt anode materials have emerged as viable options, which offer a greater capacity than the graphite anode of the present day [16]. However, metal oxide anodes have poor EC and experience significant volume changes during the electrochemical charge/discharge process, severely limiting their application possibilities in LIBs. Through the use of bionanomaterials, hetero-atom (e.g., N, O, P, S, and Cl, etc.), doping contributes to improving the electrochemical reaction of metal oxide anodes. It has been demonstrated that MnO/N-C prepared by MnO coated on N-doped carbon framework is designed using the naturally abundant and renewable Metaplexis japonica fibers (MJFs) as the bio-template and heteroatom sources and that it has exceptionally high rate capacities of 951 mAh g–1 at the rate of 0.5 A g–1, along with admirable stability over more than 1,000 cycles [77]. Xiang et al. [136] stated that a C-coated Fe2O3 nanotube is produced by a bio-inspired coating process in which tannic acid is used as the coating agent. At 0.2 C-rate, the initial discharge capacity of the C/Fe2O3 is 1452.9 mAh g–1, which is significantly greater than the first discharge capacity of pristine Fe2O3 at the same temperature. The creation of pores in the C-layer throughout the carbonization route could account for the modest increase in the specific surface area observed in Fe2O3, which improves the performance of the anode. Various bionanomaterials based on anode materials for use in the LIBs studied in this section are given in Table 3.1. 3.2.1.2  ADVANCED BIONANO-CATHODE MATERIALS FOR LIBS It studied various cathode materials for LIBs, including layered MO, spinel oxides, olivine phosphates, NASICON, and other similar compounds [58, 137]. Even though these materials have been utilized in commercial LIBs, their poisonous nature, high cost, and safety issues have prompted the development of alternative cathode materials [109, 137]. In this section aimed at tackling the critical challenges associated with various cathodes, it has been determined that the suitable design of porous materials for sustaining cathode materials is the most crucial method to be employing LIBS [106]. The loading capacity for cathodes and the highly porous carbon’s ion-conduction kinetics are improved by using porous carbon. Many biomaterials, including as biomass-sources consist of kapok fiber [75], bamboo [39], catkin [147], seaweed [107], agaric [17], lignin [38], and reed flowers [149], banana peel [24], bio-char [101],

Anode Material

Biomaterial Used

Structure

Capacity (mAh g–1)

Current Rate References

C

Coir pith

Porous

837

100 mA g–1

[83]

N/C

Human hair

Porous

3,800

100 mA g

[108]

–1

C

Lignin

Nanofibers

611 (after 700 cycles)

0.5 C

C

Prawn shells

Porous

740

100 mA g–1

[19] [94]

C

Portobello mushroom

Nanoribbons

260 (after 700 cycles)

100 mA g

[9]

C

Sweet potato

Porous

965

100 mA g–1

[150] [67]

–1

Si/C

Okra gum

Porous

1,434

0.1 C

Si/C

Starch

Porous

1,490

200 mA g–1

[131]

Si/C

Cellulose

Nanofiber

750 (after 150 cycle)

100 mA g

–1

[45]

Fe3O4–TiO2–carbon composite Cellulose

Nanofiber

1,340

100 mA g

–1

[63]

NiO/C

Glucose

Hollow microspheres

602

100 mA g–1

[122]

MnO/C

Kapok fibers

Porous

1,454

200 mA g

[121]

MnO/N-C

Metaplexis japonica fiber

Nanotube

951

500 mA g–1

[77]

1452.9

0.2

[136]

–1

Fe2O3/C

Polyphenol

Nanotube

SnS/C

Cellulose

Nanofibrous (3D porous) 1,396

100 mA g–1

Sb2S3/C

Coir pith

Porous

1,100

100 mA g

SnO2/C

Cellulose

Porous

623 (after 120 cycle)

0.2 C

[125]

TiO2/C

Bengal gram beans

Porous structured nanoparticles

164 (after 100 cycle)

33 mA g–1

[49]

–1

[61] [82]

Advanced Electrochemical Bionanomaterials 65

TABLE 3.1  Bionanoanode Materials for Advanced LIBs

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proteins, and so on [57], have been used in the fabrication of cathode materials for LIBs via various forms of porous carbon or heteroatom-doped porous carbon by researchers. These investigations mostly used a carbonization method in conjunction with chemical activation (e.g., using KOH) or etching (e.g., using HF) to form porous carbonaceous materials that can achieve the following desirable objectives: i) to get maximum structural strength and reliability of the electrodes modify the composition of the electrolyte to ensure superior electron-conduction ii) liquid electrolytes increase the dispersion eminence of cathodes and the high surface contact area of internal cathodes iii) enhance the weight ratio of cathodes guaranteed by using a binder-free design. Because most electrode frameworks are electrically conductive to facilitate electron transfer, bionanomaterials have a great deal of potential to be used as electrode frameworks after carbonization. Apart from that, because some bionanomaterials can self-assemble into novel configurations such as 1D-nanofibers, 2D-nanosheets, 3D continuous networks, and foams, they are excellent electrode framework options for LIBs. Ultrathin electrodes have the potential to increase the specific energy of LIBs without affecting the material’s chemistry. Using a sol-gel technique, Lu et al. [71] discovered the ultralong Li-ion transport pathway in the woodinspired LiCoO2 (LCO) cathode. It can be effectively replicated microstructures of wood into ultrathick bulk LCO cathode to achieve high area capacity and rate capability yield a high areal capacity of 22.7 mAh cm2 during the dynamic discharge test, which is considerably more significant than the areal loading capacity of the commercial LCO cathode used in the test. The study shows natural hierarchical structure will be possible for LIBs according to the purported wood-inspired architectural design. In a recent study, Fan et al. [26] developed a method for synthesizing LiFePO4/C matrixes using pollen (a fine yellowish powder substance consisting of pollen grains) as both the bio-template and carbon supply, with the carbonized pollen templates being introduced into porous carbon structures. The developed LiFePO4/C matrixes have an outstanding electrochemical high reversible capacity as 165 mAh g–1 (0.1 C) and rate capability without conductive agents. These can be due to the well crystalline nano-LiFePO4 and the carbonized bio-templates providing a good electronic connection. Xia et al. [135] created Layered@Spinel@Carbon heterostructure, which utilizes a bio-inspired coating approach to provide an integrated natural carbonization-reduction process in addition to the previously mentioned benefits. The findings reveal that this structure contains a core of Li-rich layered oxide, an interlayer of spinel phase oxide, and a carbon nanocoating, all of which creates a novel structure and exhibits extraordinarily

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high reversible capacity (334.5 mAh g–1) with a maximum charge/discharge rate. These results can be due to the electrostatic interaction between a high capacity Li-rich layered structure, spinel structure with three-dimensional fast Li+ diffusion pathways, and the high conductivity of the carbon coating. As a result of this technology, new insights into designing and manufacturing a wide range of cathode electrode materials for high-performance LIBs have been discovered. Ma et al. [76] reported using scavenging free radicals and lignin binder prevents electrolyte oxidation/solubilization of manganese ions. These resulted in solution polymerization, and the cathode/electrolyte interphase (CEI) development by capturing radicals can effectively reduce the production of unstable CEI and electrolyte usage. The researchers developed a mechanism for lignin and polyvinylidene fluoride (PVDF) caliber to capture radicals. Due to its abundance of phenol structural groups, lignin scavenged radicals better than PVDF. Using lignin as a binder produced a thin and compact CEI layer on LiNi0.5Mn1.5O4; however, PVDF produced a compressed and uneven CEI layer. It can be proved that lignin helped establish a stable CEI layer that preserved the electrolyte from oxidation. Therefore, the lignin-based electrode had a capacity of 110.8 mAh g–1 and a coulombic efficiency (CE) of 100% even after 1,000 cycles, compared to 100 mAh g–1 for the PVDF electrode. In summary, bionanomaterial’s diversity in structure and composition led to wealthy functional groups (polar and non-polar groups). Biomaterials with complex intra/intermolecular connections had good mechanical characteristics. Thus, bio-based binders have many advantages: (i) trapping electrochemical intermediates, (ii) maintaining electrode/electrolyte interphase, and (iii) “green” processes in aqueous solvents. These bio-based binder’s properties improved electrode microstructures (comprehensiveness, homogeneity, ease of use, etc.), and hence structural stability. More importantly, bio-based binders have proven unique contributions to sulfur and high-voltage cathodes (3.5>) by reducing the damage of active materials or minimizing side reactions to electrolytes. 3.2.2  SODIUM-ION BATTERIES (SIBS) The research on SIBs is progressing quickly toward reducing the price of batteries, allowing them to be used for storing vast amounts of renewable energy in the future [115]. Because of their long life and low cost, SIBs are “without a doubt the most enticing option LIBs technology from a

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sustainability standpoint” [27, 40]. Because of the following factors, there is a great deal of interest: (i) Sodium’s abundance and global distribution; (ii) sodium’s same energy density to lithium’s; (iii) The replacement of copper current collectors with lightweight aluminum reduces the gravimetric energy density; and (iv) increased long-term demand is expected to raise lithium prices [140]. Many inorganic compounds, primarily oxides, phosphates, and sodium alloys with elements from the fourth and fifth groups of the periodic table, have been investigated as electrodes for the NIBs. However, some difficulties associated with kinetic constraints during the sodium-ion charge/ discharge process, stability, and structural changes remain unresolved in the R&D process [116]. Organic electrode materials (ideally produced from reclaimed biomass) have recently witnessed a resurgence in popularity, and they have been thoroughly investigated. In the following sections, we will discuss various “sustainable” chemistries used in NIBs [141]. 3.2.2.1  ELECTRODE MATERIALS Several different materials have been proposed for use as an electrode (both cathode and anodes) in NIBs, including graphite, layered MO, metal alloys, polyanions, etc. [32–35, 50, 53, 86, 104, 119, 140]. Nonetheless, in most cases, these electrode materials that do not contain Na ions work via anion insertion rather than cation extraction when exposed to extremely high voltages. Instead of serving as cathodes for NIBs, use them in more appropriately referred to as dual-ion batteries. Due to their potential high voltages, dual ion batteries are being explored extensively; nevertheless, various difficulties associated with electrolytes prevent their commercialization, and there are currently no commercial prototypes available [20]. Recently, scientists have focused a great deal of interest on utilizing bio-systems and bionanomaterials such as biomass, bio-derived polymers, lignin, DNA, polypeptides, bacteria, and viruses to the synthesis of regulated and specified micro/nanostructures of functional materials, which are inspired by the intricate structures that exist in the natural world. The hierarchical self-assembly structure of bionanomaterials provides elegant and powerful bottom-up methodologies for the fabrication of complex materials. Using recombinant engineering, it is now feasible for these bionanomaterials to incorporate with specific precursors under accommodating conditions and form inorganic nanostructures in which the composition, phase, shape, and size of the nanostructures can all be precisely controlled. In summary, we show in this section that bio-inspired

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Micro/nanostructured functional materials are indeed a promising strategy for NIBs. 3.2.2.1.1  Cathode Materials Typically, cathode materials are operative in the voltage range of 2–4.3 V; however, when the voltage is raised above 4 V vs. Na+/Na, the electrolytic salt decomposes, resulting in the formation of Na+/Na layer. Jo et al. [47] recently published a paper on a bioinspired surface layer for a high-end NIBs cathode. Observations have been made to develop a bioinspired β-NaCaPO4 nanolayer on a P2-type layered structured Na2/3[Ni1/3Mn2/3]O2 cathode material. Using a Na2/3[Ni1/3Mn2/3]O2-coated β-NaCaPO4 electrode, which has excellent capacity retention due to the coating layer’s ability to effectively capture hydrogen fluoride (HF) and water (H2O), excellent capacity retention can be achieved. It is believed that the generation of HF is the leading cause of long-term cycling failure because it continuously attacks the active materials, causing severe disintegration. Aside from the electrochemical performance, the coating layers also suppressed oxygen evolution from the crystal structure when the electrodes were highly charged. In addition to P2-type layer materials, these synergetic effects of bioinspired surface coating technologies are believed to be possible for all cathode materials used in rechargeable NIBS. Furthermore, a bio-inspired NIB cathode based on P2-Na0.57CoO2 nanoparticles (NPs) was developed and tested in aqueous NIBs [90]. The NPs were derived from an aqueous extract of the dry silk of the Zea mays lea plant. The charge/discharge capacities of the positive and negative electrodes, which were Na0.57CoO2 and activated carbon, were about 68 and 57 mAh g–1 (0.7 C). When cycled at 7°C for 1,000 cycles, the cell maintained 79% of its inceptive capacity and 98% CE from the 200th to the 1000th cycle, indicating that it was still in good condition. As a result, bio-synthesized Na0.57CoO2 NPs can serve as a positive electrode material for SIBs. Nwanya et al. [89] investigated Na0.8Ni0.33Co0.33Mn0.33O2 NPs made from a water-based extract of dried maize (Zea mays lea) silk. The positive electrode of an aqueous NIB was made of Na0.8Ni0.33Co0.33Mn0.33O2 produced a rechargeable discharge capacity of approximately 86 mAh g–1 with a current density of 10 mA g–1. However, an entire cell using P25 Degussa TiO2 as the negative electrode and biosynthesized Na0.8Ni0.33Co0.33Mn0.33O2 as the positive electrode had a capacity retained by 49 mAh g–1 with a current density of 5 mA g–1.

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In addition, hollow porous microspheres directed by biochemistry were investigated as bottom-up/self-assembled polyanion-based cathodes Na3V2(PO4)3 and Na3.12Fe2.44(P2O7)2 for NIBs [65]. The microalgae cell (unicellular photosynthetic microorganisms) forms a sphere-shaped bioprecursor. Its tiny core is destroyed, and its hard shell carbonizes in the healing process, resulting in the top product is “hollow porous microspheres.” The hollow microsphere’s highly conductive framework enwraps the nanoscale polyanion crystals, resulting in a hierarchical nano-microstructure. The entire construction process is described as “bottom-up.” The biochemistryderived self-assembly process is also confirmed to be important in the final architecture. Polyanion materials benefit from the well-defined hollowmicrosphere structural design, rich internal voids, and highly conductive networks. Both materials can cycle at high rates. Each material retains 96.2 and 93.1% of its first to 500 cycles at 20°C and 10°C, respectively. As a result, the biochemistry-derived method provides a cheaper, highly efficient, and broadly valid approach for producing high-capacity polyanion-based cathodes for NIBs. A high-performance pyrophosphate cathode material for SIBs made of Na2FePO4F/biocarbon NC hollow microspheres derived from a biological cell template method has been developed [59]. The cathode was developed by using FeIII precursor in a yeast cell biotemplate and sol-gel technique. A mesoporous carbon coating on the NPs surface promotes electron diffusion into Na2FePO4F crystal particles. The superior electrochemical stability and rate performance of Na2FePO4F/biocarbon NCs over Na2FePO4F/C NCs are ascribed to the higher electrode and electrolyte contact area and more Na+ active sites on the surface of hollow microspheres. The Na2FePO4F/ biocarbon NC has a higher initial discharge capacity (114.3 mAh g–1) and rate capability (70.2 mAh g–1) than the Na2FePO4F/C. This novel structure (hollow microsphere) can be used to improve other cathode materials used in high-power NIBs. In addition, controllable synthesis of biochemistry-enabled 2D hierarchical nanosheets composite Na7V3(P2O7)4/C for high potential cathode for NIBs was also reported [51]. Changes in material structure allow for the development of new functional properties. The yielding design of controlled electrode materials is a necessary procedure in developing a bio nano-directed strategy for developing high-performance NIBs. The natural structure of fern (i.e., Cibotium) spores appreciates creating a 3D hexahedral bio-precursor to a 2D hierarchical nanosheet due to its core or shell destruction. This study uses sodium vanadium pyrophosphate as an electrochemically active material.

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Controllable damage is discussed in the preparation of diverse mechanisms for NIBs. The connection between external mechanisms, internal microstructures, and the Nacharge capacity of bio-composites is also clarified. The two-dimensional nanosheet with hierarchical structures has the smallest NPs size and the highest surface area for fast sodium intercalation. As a result, it can cycle at high rates for long periods, achieving 93% efficiency even after 500 cycles at 20°C rate. However, a three-dimensional hollow hexahedron’s heavy shell and poor surface properties limit Na transport kinetics and performance. 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) is a poor organic cathode material for SIBs due to its poor conductivity, low kinetic responses, poor cycle performance, and short cycle life. These characteristics make it an inadequate organic cathode material for NIBs. Recently, Zhou et al. [151] reported nanofibrous organic cathode consists of PTCDA/ nitrogen-doped carbon/carbon nanotubes (PTCDA/NC/CNT) for SIBs, motivated by the most potent capillarity of wood’s associated hierarchical microchannels toward ions and water throughout metabolism. The PTCDA/ NC/CNT cathode shows excellent ionic and electronic transport properties and high kinetic reactions due to the synergistic properties of the interconnected conductive networks. Furthermore, the PTCDA/NC/CNT has a highly reversible capacity of 135.6 mAh g–1, outstanding rate capabilities, and ultra-long cyclic stability with over 95% capacity retention after 500 cycles at 1,000 mA g–1. Interestingly, an all-organic sodium-ion battery with PTCDA/NC/CNT cathode and conjugated sodium carboxylate/CNT anode exhibits 85 Wh kg–1 energy and 665 W kg–1 power, which incorporating bioinspired design principles into next-generation NIBs. Microorganisms (e.g., bacteria, fungi, and viruses) have contributed to the development of high-performance electrodes, owing to their exceptional capacity in rapid reproduction, biomineralization, gene alteration, and selfassembly, among other things. Recently, it has been discovered that large numbers of bacteria and fungi can be used as biofactories and templates to biomineralize metal ions into carbon-based composites [113]. Aside from that, viruses with functional groups are directly used as bio templates for self-assembling active materials. Recently, nanostructured Bio-FePO4-CNT for NIBs by using a virus-inspired nanostructured composite by employing an energy-efficient bio template route [91]. To improve the active material’s electronic conductivity, self-assembled M13 viruses and Single-walled carbon nanotubes were used as templates to grow amorphous FePO4 NPs at room temperature. Preliminary tests exhibited an initial capacity of 166 mAh

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g–1 at a 0.1°C rate for Na0.9FePO4. The present amorphous FePO4 cathode has the maximum rate capability and performance than reported amorphous FePO4 electrodes. 3.2.2.1.2  Anode Materials Hard carbons and graphite are the most commercialized anodes for LIBS [62]. However, these anodes are not suitable for NIBs because the size of Na is heavier than that of Li. The layer structure faces volume changes and mechanical strain in the host structure during the cycling processes, which reduces the battery’s capacity [40]. Moreover, these materials’ production relies heavily on high-temperature annealing under inert gas, which is energy-intensive and environmentally damaging. To address these issues, sustainable bionanomaterials produced from natural abundant and low-cost raw materials such as biochars, biomass, pitch, lignin, organic conducting polymers, and carboxylates are an excellent choice for NIBs due to (i) lowcost and natural abundant; (ii) high porosity; (iii) minimum or no volume changes in host structure; (iv) high electronic conductivity; and (v) depolymerization during battery charge to achieve the low voltage. Furthermore, these materials contain aromatic rings, which contribute to forming a favorable host structure for the recovery of energy during the battery discharge procedure. Recently, research has focused on ionic liquid-encouraged low-temperature graphitization of cellulose-derived biochar for high-performance NIBs [144]. Rich graphitic carbon is produced by high-temperature carbonization (2,273 K>) or metal-based catalysis by using biomass. Yet, no report has been published on the graphitization of biochar at low temperatures using imidazolium-based ionic liquids. In this regard, Yu et al. [144] discovered the carbonization of microcrystalline cellulose and 1-butyl-3-methylimidazolium acetate (BMIM-OAc) at temperatures ranging from 1,023 K to 1,623 K resulted in increased high-quality biochar graphitization. The interaction of imidazolium rings in the carbon network was more important in the growth of graphite with a high nitrogen concentration. At 1,273 K, the ionic liquidinduced cellulose carbon (ICC) with 5.67% nitrogen-doped anode showed a stable discharge capacity of 0.39 Ah g–1 at 0.001 A g–1 for the first 100 cycles and 136 mAh g–1 at 0.5 A g–1 for 1,000 cycles, which shows outstanding performance for NIBs due to interconnected graphitic nanosheets with 4.88 Å interlayer spacing and a high density of micro and macropores on the surface, and rich mesopores/macropores surface. Kinetic analysis of Na+ ion

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storage demonstrated that the ICC showed better electrochemical characteristics and improved electric conductivity. For the first time, inexpensive amorphous carbon (AC) as anode material made from the pitch is reported by Li et al. [64] for NIBs. The use of the emulsification (a system comprising of two immiscible liquids) interaction between pitch and lignin to inhibit the graphitization of pitch during the carbonization resulted in an extraordinary high carbon rate of return of 57%. With the help of optimization of experimental conditions like the effects of heat-treatment temperature and mass ratios of pitch/lignin on the morphology, microstructure, and electrochemical performance of AC have been studied in detail. When cycling this device, it exhibits promising characteristics such as a high discharge capacity of 254 mAh g–1, remarkable cycle stability with repeated cycling, and an extremely high initial CE of 82%. Electroactive polymeric Schiff bases are the best choices for usage as anode materials for SIBs because of their high electroactivity [13]. In polymers and salts hybridized with carboxylate end groups, it has been demonstrated that the oxidation-reduction reaction is composed of two Schiff base groups connected to a phenyl ring (–N=CH–Ar–HC–N–) is active for NIBs (Ar=aromatic group) as well. Terephthalaldehyde units can be formed by a strengthening mechanism between non-conjugated aliphatic or conjugated aromatic diamine blocks, resulting in the formation of these chemical compounds [93, 139]. At the low potentials required for anodes in NIBs (between 0 V and 1.5 V vs. Na+/Na), crystalline polymeric Schiff bases can electrochemically store more than one sodium atom/azomethine group [102]. The redox potential can be adjusted by conjugating the polymeric chain and injecting electrons into the aromatic rings through donor substituents in the aromatic rings, respectively. Moreover, the carbon mixture is improved with carbon additions, reversible capacities of up to 350 mAh g–1 can be attained, which is significant for NIBs. It is noteworthy that the “reverse” structure (–CH=N–Ar–N=HC–) is not electrochemically active, even though it is isoelectric [13]. Nevertheless, disconnected molecules are formed, and an easy process is not obtained in hybrid carboxylate/Schiff base units because of the intermediate voltages of reaction between the two end groups. Jeffrey® (–NH2–PEO–NH2–) is a polymer backbone modification that introduces ethylene oxide groups into the polymer backbone, allowing for the manufacture of self-binding polymeric electrodes that may be cast onto Cu and Al current collectors [30]. Jeffamine® concentrations can be controlled to ensure that the charge/ discharge performance of the parent polymeric electrodes is maintained. This procedure involved the addition of Jeffamines to anodes to convey the

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solubility or adhesion used in a variety of applications, including polymeric cathodes and electrolytes [1]. Instead of imine groups, azo groups were somewhat lower and more favorable for Na insertion [73]. It compared to their Schiff base equivalents’ voltages. Two-dimensional-covalent organic frameworks (COFs) have exhibited better electrochemical performance at low voltages, making them the proper choice for use as an anode in NIBs [96]. The high CE and gravimetric capacities of nanospheres and nanosphere-like structures may be due to their spherical shape (nanospheres) and enormous internal surface area (nanospheres). The reaction mechanism is unknown, and however, given the voltage, it is likely that the electrochemical activity is due to Schiff base functionality rather than triazine units in the reaction mixture. Many metalorganic frameworks (MOFs) have been demonstrated as electrodes in NIBs, which is a framework material development (and even more in LIBs) [96]. In fact, due to their ease of preparation techniques (at ambient temperature in water), several MOFs may be suitable for future NIBs. While iron and manganese are the least expensive, most common, and most minor toxic metals, the observed performance in Iron-MOFs is not very spectacular, except for exceptionally stable cyanide-based ligand Prussian Blue cathode materials [31, 117, 134]. 3.2.3  K AND MG-ION BATTERIES (KIBS AND MIBS) Due to the increase in the energy demand, there are many scopes to develop alternative suitable battery chemistries, such as K, MIBs [41, 46, 133]. After LIBs and NIBs, KIBS, and MIBs are an excellent choice to develop green, economical batteries. Their more abundant can become the primary grid storage applications, substituting toxic LABs, low energy density NIBs, and expensive LIBs [112, 129]. A few advantages of KIBS and MIBs over NIBs/ LIBs: Despite being widely distributed in the earth’s crust, the low voltage of K/Mg (similar to Li) may allow for KIBS/ MIBs with higher volumetric energy density than NIBs [12]. Al current collectors can also be used on the anode by replacing Cu collectors because they don’t alloy at low voltage (650 mAh g–1) and stability (>500 cycles) by simply tuning the electrolyte compositions, without the need for nanostructural control and carbon modification [8, 126, 128, 145]. For example, a novel Fex–1Sex is prepared on a fungus-derived carbon matrix encapsulated by 2D Ti3C2TxMXene highly conductive layers, which exhibits high specific Na and K storage capacities 610.9 and 449.3 mAh g–1 at a current density of 0.1 A g–1 [10]. In addition, bio-derived hierarchically porous heteroatoms doped carbon anode materials also exhibit excellent performance for KIBs. 3.2.4  PROTON-BASED BATTERIES (PBBS) Since 2014, the proton flow battery concept has gained popularity by combining facts of hydrogen fuel-cell systems with battery technology [91]. For example, H-ion systems operating at a 1.0–1.5 V voltage can compete with LIBs if they are constructed using electrode resources with high gravimetric/volumetric capacities. In this regard, emerging PBBs using bioinspired/bio-delivered hybrid electrode materials with organic molecules and polymers are enticing and challenging. For example, Emanuelsson et al. [25] recently developed a proton battery by using all-organic electrode materials, by using with conducting poly(3,4-ethylene dioxythiophene)

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(PEDOT), demonstrated with anthraquinone (PEDOT-AQ) or benzoquinone (PEDOT-BQ) pendant groups as both anode and cathode electrode materials, which delivers a high specific capacity of 103 and 120 mAh g–1. These results demonstrate the feasibility of assembling all-organic PBBs that do not require the use of conductive additives and identify the “challenges and opportunities” associated with the development of plastic batteries. 3.2.5  REDOX FLOW BATTERIES (RFBS) Redox flow batteries (RFBs) are made up of two half cells, one positive and one negative, separated by a membrane. The use of liquid tanks to store the two different electrolytes is a unique feature of this battery type. These are connected to the galvanic cell, where the electron transfer takes place through tubing and pumps. RFBs are among the best possibilities for storing clean electricity generated by intermittent renewable energy sources. However, the development of high-energy-density RFBs with long lifetimes, which results in new chemistries based on less expensive and environmentally friendly earth-abundant elements, is a priority. Additionally, should be carried out redox chemistry in aqueous solutions to minimize the flammability of organic solvents and associated environmental problems. Accordingly, the following section will cover the latest developments in active organic species in aqueous electrolytes and novel fabrication techniques that do not use Nafion membranes. Sustainable electrode materials and manufacturing methods with zero CO2 emissions will be critical. Organic redox-active substances are an alternative to vanadium as a vanadium substitute. Anthraquinones, anthocyanins, and flavonoids are the compounds that have piqued our interest in this instance [42, 44, 88]. In nature, these substances can be found in abundance, and they can be produced from renewable resources. Anthraquinones are found in plants such as rhubarb and senna. As an anolyte for RFB, it has a redox potential of approximately 0.02 V compared to Reversible Hydrogen Electrode (RHE) and is well suited for this application. Grapes, apples, cherries, and other fruits and vegetables contain anthocyanins and flavonoids. Anthocyanins and flavonoids have a redox potential of approximately 0.9 V vs. RHE and can be used as a catholyte because of this. Those electrolytes have the potential to replace the toxic and highly corrosive vanadium electrolytes. With this combination of catholyte and anolyte, it is possible to construct a redox-flow battery entirely composed of biological materials. Liu et al. [69] describe a total organic aqueous RFB

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that utilizes cheaper and long-lasting methyl viologen (MV, anolyte) and 4-hydroxy-2,2,6,6-tetramethyl piperidine-1-oxyl (4-HO-TEMPO, catholyte) as well as a non-toxic NaCl supporting electrolyte for operation. With the help of cyclic voltammetry (CV) and rotating disc electrode voltammetry, the electrochemical performance of the organic redox-active materials has been investigated. Compared to other organic RFBs, the MV/4-HO-TEMPO has a remarkably cell voltage of 1.25 V. Prototypes of the organic RFBs can operate at high current densities extending from 20 to 100 mA cm2 and exhibits ultra-stable performance for 100 cycles while achieving nearly 100% CE. The MV/4-HO-TEMPORFBs demonstrate impressive practical advantages and, as a result, represent a significant advancement in RFBs. 3.2.6 SUPERCAPACITORS The development of bionanomaterial-based supercapacitors necessitates the advancement of the field of EES. Supercapacitors made of graphene are an excellent example of this. Using an alternative material with a hybrid composition, it is possible to obtain a comparable outcome. The progress of cheaper, ecologically friendly, and energy-efficient materials following these specifications represents a promising new path for expanding ESS. According to research, biopolymer materials that do not include any chemicals are safe for both customers and the environment. From both a scientific and practical standpoint, tremendous progress has been achieved in the preparation, characterization, and application of polysaccharides over the previous decade. According to previous studies, specific capacitance values have grown in the sequence of starch, cellulose, chitosan, and lignin, making them suitable for use in supercapacitor applications. However, much more work needs to be done to produce biopolymer products with various architectures, compositions, and qualities in a wide range of diverse and exciting applications. Numerous electrode modification approaches have been developed to obtain functionalities suited for supercapacitor applications during the last several decades. Additionally, the academic community has developed a slew of innovative concepts for supercapacitors of all shapes, including nanowires, hybrids, flexible materials, and self-contained systems. These concepts have the potential to improve specific capacitor performance while simultaneously reducing environmental impact and manufacturing costs. However, efforts to put these novel ideas into practice for biopolymers are still in their starting stages of evolvement. Improvements in performance

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and functionality are critical for the future research and applications of supercapacitors. Still, sustainability, energy consumption, and environmental pollution should also be considered when designing next-generation supercapacitors. Over time, we expect that these hybrid materials will produce even more exciting outcomes and will help to encourage further the widespread use of supercapacitors on a big scale. In short, there are still numerous concerns and opportunities in academics and industry that have not been handled. 3.3 SUMMARY Since earth-abundant and renewable materials are used in energy storage, it is inspiring to think about how we may construct ecologically friendly, safe, and economical energy storage in the future. The development of offgrid, which will allow clean electricity to be delivered to rural villages and isolated places, will be made possible by using sustainable energy storage devices to store solar and wind energy at reasonable costs. Some of the energy storage technologies are capable of meeting the requirements for achieving these long-term goals. However, others are not. It can decide to compile the most recent findings on environment-friendly electrochemical bionanomaterials and bio-inspired materials (typically organic or polymeric materials fabricated from non-energy-consumption processes and green synthesis) for NIBs, PBBs, RFBs, fuel cells, and supercapacitors in this book chapter. These included future considerations as well as current bottlenecks in the development of sustainable materials. In addition, essential areas of battery sustainability, such as cycle stability and performance, are discussed in detail. The development of new materials, particularly electrochemical bionanomaterials, has entailed a great deal of effort, and the results have been impressive in terms of improving energy storage mechanisms that are of fundamental significance (such as voltage, energy density, capacity, rate performance, and stability), as has been discussed in this chapter. However, other aspects of EES R&D are often overlooked, such as ecological strategy, reuse, and recycling of future new materials and configurations, which require to be taken into consideration. This study has said that these issues are of essential importance since, without advancements in these sectors, the future need for energy storage devices would not be met, resulting in irreversible damage to the environment. The incorporation of these considerations into present investigations will lead to additional developments and novel

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technology, which will necessitate a firm commitment from researchers, manufacturers, lawmakers, and end-users to be successful. ACKNOWLEDGMENTS The authors would like to express their sincere gratitude to Prof. (Dr.) Gopal Mugeraya, Director, National Institute of Technology Goa, India, for his kind encouragement and motivation in all parts of this work. KEYWORDS • • • • • •

electric vehicles electrical energy storage systems electrochemical energy storage lead-acid batteries Li-ion batteries vanadium flow batteries

REFERENCES 1. Aldalur, I., Armand, M., & Zhang, H., (2020). Jeffamine-based polymers for rechargeable batteries. Batteries & Supercaps, 3(1), 30–46. 2. Amrouche, S. O., Rekioua, D., Rekioua, T., & Bacha, S., (2016). Overview of energy storage in renewable energy systems. International Journal of Hydrogen Energy, 41(45), 20914–20927. 3. Baldinelli, A., Dou, X., Buchholz, D., Marinaro, M., Passerini, S., & Barelli, L., (2018). Addressing the energy sustainability of biowaste-derived hard carbon materials for battery electrodes. Green Chemistry, 20(7), 1527–1537. 4. Barton, J. P., & Infield, D. G., (2004). Energy storage and its use with intermittent renewable energy. IEEE Transactions on Energy Conversion, 19(2), 441–448. 5. Bebelis, S., Bouzek, K., Cornell, A., Ferreira, M., Kelsall, G., Lapicque, F., De León, C. P., et al., (2013). Highlights during the development of electrochemical engineering. Chemical Engineering Research and Design, 91(10), 1998–2020. 6. Bjornmalm, M., Faria, M., & Caruso, F., (2016). Increasing the impact of materials in and beyond bio-nanoscience. Journal of the American Chemical Society, 138(41), 13449–13456.

80

Sustainable Nanomaterials for Biosystems Engineering

7. Bucur, C. B., (2017). Challenges of a Rechargeable Magnesium Battery: A Guide to the Viability of this Post Lithium-Ion Battery (p. 67). Springer. 8. Bucur, C. B., Gregory, T., Oliver, A. G., & Muldoon, J., (2015). Confession of a magnesium battery. The Journal of Physical Chemistry Letters, 6(18), 3578–3591. 9. Campbell, B., Ionescu, R., Favors, Z., Ozkan, C. S., & Ozkan, M., (2015). Bio-derived, binderless, hierarchically porous carbon anodes for Li-ion batteries. Scientific Reports, 5(1), 1–9. 10. Cao, J., Wang, L., Li, D., Yuan, Z., Xu, H., Li, J., Chen, R., Shulga, V., Shen, G., & Han, W., (2021). Ti3C2Tx MXene conductive layers supported bio-derived Fex-1Sex/MXene/ Carbonaceous nanoribbons for high-performance half/full sodium-ion and potassium-ion batteries. Advanced Materials, 33(34), 2101535. doi: 10.1002/adma.202101535. 11. Cao, W., Zhang, E., Wang, J., Liu, Z., Ge, J., Yu, X., Yang, H., & Lu, B., (2019). Potato derived biomass porous carbon as anode for potassium ion batteries. Electrochimica Acta, 293, 364–370. 12. Cao, W., Zhang, J., & Li, H., (2020). Batteries with high theoretical energy densities. Energy Storage Materials, 26, 46–55. 13. Castillo-Martínez, E., Carretero-González, J., & Armand, M., (2014). Polymeric Schiff bases as low-voltage redox centers for sodium-ion batteries. Angewandte Chemie International Edition, 53(21), 5341–5345. 14. Cernat, A., Tertiş, M., Săndulescu, R., Bedioui, F., Cristea, A., & Cristea, C., (2015). Electrochemical sensors based on carbon nanomaterials for acetaminophen detection: A review. Analytica Chimica Acta, 886, 16–28. 15. Chang, J., Zhang, L., & Wang, P., (2018). Intelligent environmental nanomaterials. Environmental Science: Nano, 5(4), 811–836. 16. Chen, Y., Chen, X., & Zhang, Y., (2021). A comprehensive review on metal-oxide nanocomposites for high-performance lithium-ion battery anodes. Energy & Fuels, 35(8), 6420–6442. 17. Cheng, Y., Feng, K., Wang, H., Zhang, H., Li, X., & Zhang, H., (2017). “Three-in-One:” a new 3D hybrid structure of Li3V2(PO4)3@ biomorphic carbon for high-rate and low-temperature lithium-ion batteries. Advanced Materials Interfaces, 4(22), 1700686. doi: 10.1002/admi.201700686. 18. Cui, D., & Gao, H., (2003). Advance and prospect of bionanomaterials. Biotechnology Progress, 19(3), 683–692. 19. Culebras, M., Geaney, H., Beaucamp, A., Upadhyaya, P., Dalton, E. D., Ryan, K. M., & Collins, M. N., (2019). Bio-derived carbon nanofibers from lignin as high performance Li-ion anode materials. ChemSusChem, 12(19), 4516–4521. 20. Delmas, C., (2018). Sodium and sodium-ion batteries: 50 years of research. Advanced Energy Materials, 8(17), 1703137. doi: 10.1002/aenm.201703137. 21. Dincer, I., (2000). Renewable energy and sustainable development: A crucial review. Renewable and Sustainable Energy Reviews, 4(2), 157–175. 22. Ding, M., Chen, G., Xu, W., Jia, C., & Luo, H., (2020). Bio-inspired synthesis of nanomaterials and smart structures for electrochemical energy storage and conversion. Nanomaterials Science, 2(3), 264–280. 23. Edberg, J., Brooke, R., Granberg, H., Engquist, I., & Berggren, M., (2019). Improving the performance of paper supercapacitors using redox molecules from plants. Advanced Sustainable Systems, 3(8), 1900050. doi: 10.1002/adsu.201900050.

Advanced Electrochemical Bionanomaterials 81 24. Ehsani, A., & Parsimehr, H., (2020). Electrochemical energy storage electrodes from fruit biochar. Advances in Colloid and Interface Science, 284, 102263. doi: 10.1016/j. cis.2020.102263. 25. Emanuelsson, R., Sterby, M., Strømme, M., & Sjödin, M., (2017). An all-organic proton battery. Journal of the American Chemical Society, 139(13), 4828–4834. 26. Fan, Q., Lei, L., Chen, Y., & Sun, Y., (2013). Bio template synthesis of LiFePO4/C matrixes for the conductive agent-free cathode of lithium-ion batteries. Journal of Power Sources, 244, 702–706. 27. Fang, Y., Xiao, L., Chen, Z., Ai, X., Cao, Y., & Yang, H., (2018). Recent advances in sodium-ion battery materials. Electrochemical Energy Reviews, 1(3), 294–323. 28. Farré, M., Sanchís, J., & Barceló, D., (2011). Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment. TrAC Trends in Analytical Chemistry, 30(3), 517–527. 29. Feng, K., Li, M., Zhang, Y., Liu, W., Kashkooli, A. G., Xiao, X., & Chen, Z., (2019). Micron-sized secondary Si/C composite with in situ crosslinked polymeric binder for high-energy-density lithium-ion battery anode. Electrochimica Acta, 309, 157–165. 30. Fernández, N., Sánchez-Fontecoba, P., Castillo-Martínez, E., Carretero-González, J., Rojo, T., & Armand, M., (2018). Polymeric redox-active electrodes for sodium-ion batteries. ChemSusChem, 11(1), 311–319. 31. Gallis, D. F. S., Pratt, III. H. D., Anderson, T. M., & Chapman, K. W., (2016). Electrochemical activity of Fe-MIL-100 as a positive electrode for Na-Ion batteries. Journal of Materials Chemistry A, 4(36), 13764–13770. 32. Gandi, S., Chinta, S. R., Katari, N. K., & Ravuri, B. R., (2018). Electrochemical performance of SnO–V2O5–SiO2 glass anode for Na-Ion batteries. Materials for Renewable and Sustainable Energy, 7(4), 1–4. 33. Gandi, S., Mekprasart, W., Pecharapa, W., Dutta, D. P., Jayasankar, C., & Ravuri, B. R., (2020). Na–Ge glass anode network mixed with bismuth oxide nanocrystallites: A high capacity anode material for use in advanced sodium-ion battery design. Materials Chemistry and Physics, 242, 122568. doi: 10.1016/j.matchemphys.2019.122568. 34. Gandi, S., Katta, V. K., Dutta, D. P., & Ravuri, B. R., (2020). A mixed polyanion NaFe1–x(VO)x PO4 glass-ceramic cathode system for safe and large-scale economic Na-ion battery applications. New Journal of Chemistry, 44(7), 2897–2906. 35. Gandi, S., Chinta, S. R., Ojha, P. K., & Ravuri, B. R., (2018). Electrical conductivity and charge/discharge profiles of mixed polyanion glass-ceramic cathodes for use in Na-ion batteries. Journal of Non-Crystalline Solids, 493, 41–47. 36. García-Mayagoitia, S., Pérez-Hernández, H., Medina-Pérez, G., Campos-Montiel, R. G., & Fernández-Luqueño, F., (2020). Bio-nanomaterials in the air pollution treatment; chapter 12. In: Amrane, A., Assadi, A. A., Nguyen-Tri, P., Nguyen, T. A., & Rtimi, S., (eds.), Nanomaterials for Air Remediation (pp. 227–248). Elsevier. 37. Gielen, D., Boshell, F., Saygin, D., Bazilian, M. D., Wagner, N., & Gorini, R., (2019). The role of renewable energy in the global energy transformation. Energy Strategy Reviews, 24, 38–50. 38. Gnedenkov, S. V., Opra, D. P., Zemnukhova, L. A., Sinebryukhov, S. L., Kedrinskii, I. A., Patrusheva, O. V., & Sergienko, V. I., (2015). Electrochemical performance of Klason lignin as a low-cost cathode-active material for primary lithium battery. Journal of Energy Chemistry, 24(3), 346–352.

82

Sustainable Nanomaterials for Biosystems Engineering

39. Gu, X., Wang, Y., Lai, C., Qiu, J., Li, S., Hou, Y., Martens, W., et al., (2015). Microporous bamboo biochar for lithium-sulfur batteries. Nano-Research, 8(1), 129–139. 40. Hirsh, H. S., Li, Y., Tan, D. H., Zhang, M., Zhao, E., & Meng, Y. S., (2020). Sodium-ion batteries paving the way for grid energy storage. Advanced Energy Materials, 10(32), 2001274. doi: 10.1002/aenm.202001274. 41. Hosaka, T., Kubota, K., Hameed, A. S., & Komaba, S., (2020). Research development on K-Ion batteries. Chemical Reviews, 120(14), 6358–6466. 42. Hu, B., DeBruler, C., Rhodes, Z., & Liu, T. L., (2017). Long-cycling aqueous organic redox flow battery (AORFB) toward sustainable and safe energy storage. Journal of the American Chemical Society, 139(3), 1207–1214. 43. Hu, P., Lan, H., Wang, X., Yang, Y., Liu, X., Wang, H., & Guo, L., (2019). Renewablelawsone-based sustainable and high-voltage aqueous flow battery. Energy Storage Materials, 19, 62–68. 44. Huskinson, B., Marshak, M. P., Suh, C., Er, S., Gerhardt, M. R., Galvin, C. J., Chen, X., et al., (2014). A metal-free organic-inorganic aqueous flow battery. Nature, 505(7482), 195–198. 45. Jia, D., & Huang, J., (2017). A bio-inspired nanofibrous silicon/carbon composite as an anode material for lithium-ion batteries. New Journal of Chemistry, 41(12), 4887–4900. 46. Jiang, L., Lu, Y., Zhao, C., Liu, L., Zhang, J., Zhang, Q., Shen, X., et al., (2019). Building aqueous K-Ion batteries for energy storage. Nature Energy, 4(6), 495–503. 47. Jo, C. H., Jo, J. H., Yashiro, H., Kim, S. J., Sun, Y. K., & Myung, S. T., (2018). Bioinspired surface layer for the cathode material of high-energy-density sodium-ion batteries. Advanced Energy Materials, 8(13), 1702942. doi: 10.1002/aenm.201702942. 48. Jung, Y. S., Lee, K. T., & Oh, S. M., (2007). Si-carbon core-shell composite anode in lithium secondary batteries. Electrochimica Acta, 52(24), 7061–7067. 49. Kashale, A. A., Gattu, K. P., Ghule, K., Ingole, V. H., Dhanayat, S., Sharma, R., Chang, J. Y., & Ghule, A. V., (2016). Biomediated green synthesis of TiO2 nanoparticles for lithium-ion battery application. Composites Part B: Engineering, 99, 297–304. 50. Katta, V. K., Gandi, S., Katari, N. K., Mekprasart, W., Pecharapa, W., Dutta, D. P., & Ravuri, B. R., (2021). Mixed polyanion Na-Mn-V-P glass–ceramic cathode network: Improved electrochemical performance and stability. Energy Technology, 9(2), 2000845. doi: 10.1002/ente.202000845. 51. Ke, L., Yu, T., Lin, B., Liu, B., Zhang, S., & Deng, C., (2016). From a 3D hollow hexahedron to 2D hierarchical nanosheets: Controllable synthesis of biochemistryenabled Na7V3(P2O7)4/C composites for high-potential and long-life sodium-ion batteries. Nanoscale, 8(45), 19120–19128. 52. Khare, V., Nema, S., & Baredar, P., (2016). Solar–wind hybrid renewable energy system: A review. Renewable and Sustainable Energy Reviews, 58, 23–33. 53. Kim, S. W., Seo, D. H., Ma, X., Ceder, G., & Kang, K., (2012). Electrode materials for rechargeable sodium-ion batteries: Potential alternatives to current lithium-ion batteries. Advanced Energy Materials, 2(7), 710–721. 54. Kubota, K., Dahbi, M., Hosaka, T., Kumakura, S., & Komaba, S., (2018). Towards K-ion and Na-ion batteries as “beyond Li-ion.” The Chemical Record, 18(4), 459–479. 55. Larcher, D., & Tarascon, J. M., (2015). Towards greener and more sustainable batteries for electrical energy storage. Nature Chemistry, 7(1), 19–29. 56. Lee, S. H., Lee, J. H., Nam, D. H., Cho, M., Kim, J., Chanthad, C., & Lee, Y., (2018). Epoxidized natural rubber/chitosan network binder for silicon anode in lithium-ion battery. ACS Applied Materials & Interfaces, 10(19), 16449–16457.

Advanced Electrochemical Bionanomaterials 83 57. Lee, Y. J., Yi, H., Kim, W. J., Kang, K., Yun, D. S., Strano, M. S., Ceder, G., & Belcher, A. M., (2009). Fabricating genetically engineered high-power lithium-ion batteries using multiple virus genes. Science, 324(5930), 1051–1055. 58. Li, C., Zhang, H., Fu, L., Liu, H., Wu, Y., Rahm, E., Holze, R., & Wu, H., (2006). Cathode materials modified by surface coating for lithium-ion batteries. Electrochimica Acta, 51(19), 3872–3883. 59. Li, H., Wang, T., Wang, X., Li, G., Shen, J., & Chai, J., (2021). Na2FePO4F/Biocarbon nanocomposite hollow microspheres derived from biological cell template as highperformance cathode material for sodium-ion batteries. Chemistry: A European Journal, 27(35), 9022–9030. 60. Li, H., Cheng, Z., Zhang, Q., Natan, A., Yang, Y., Cao, D., & Zhu, H., (2018). Bacterialderived, compressible, and hierarchical porous carbon for high-performance potassium-ion batteries. Nano-Letters, 18(11), 7407–7413. 61. Li, J., Wang, M., & Huang, J., (2021). Bio-inspired hierarchical nanofibrous SnS/C composite with enhanced anodic performances in lithium-ion batteries. Journal of Alloys and Compounds, 860, 157897. 62. Li, M., Lu, J., Chen, Z., & Amine, K., (2018). 30 years of lithium-ion batteries. Advanced Materials, 30(33), 1800561. 63. Li, S., Wang, M., Luo, Y., & Huang, J., (2016). Bio-inspired hierarchical nanofibrous Fe3O4–TiO2–Carbon composite as a high-performance anode material for lithium-ion batteries. ACS Applied Materials & Interfaces, 8(27), 17343–17351. 64. Li, Y., Hu, Y. S., Li, H., Chen, L., & Huang, X., (2016). A superior low-cost amorphous carbon anode made from pitch and lignin for sodium-ion batteries. Journal of Materials Chemistry A, 4(1), 96–104. 65. Lin, B., Li, Q., Liu, B., Zhang, S., & Deng, C., (2016). Biochemistry-directed hollow porous microspheres: Bottom-up self-assembled polyanion-based cathodes for sodium-ion batteries. Nanoscale, 8(15), 8178–8188. 66. Ling, H. Y., Chen, H., Wu, Z., Hencz, L., Qian, S., Liu, X., Liu, T., & Zhang, S., (2021). Sustainable bio-derived materials for addressing critical problems of nextgeneration high-capacity lithium-ion batteries. Materials Chemistry Frontiers, 5(16), 5932–5953. 67. Ling, H. Y., Hencz, L., Chen, H., Wu, Z., Su, Z., Chen, S., Yan, C., et al., (2021). Sustainable okra gum for silicon anode in lithium-ion batteries. Sustainable Materials and Technologies, 28, e00283. 68. Liu, K., Tian, Y., & Jiang, L., (2013). Bio-inspired superoleophobic and smart materials: Design, fabrication, and application. Progress in Materials Science, 58(4), 503–564. 69. Liu, T., Wei, X., Nie, Z., Sprenkle, V., & Wang, W., (2016). A total organic aqueous redox flow battery employing a low cost and sustainable methyl viologen anolyte and 4-Ho-tempo catholyte. Advanced Energy Materials, 6(3), 1501449. 70. Lloyd, J. R., Byrne, J. M., & Coker, V. S., (2011). Biotechnological synthesis of functional nanomaterials. Current Opinion in Biotechnology, 22(4), 509–515. 71. Lu, L. L., Lu, Y. Y., Xiao, Z. J., Zhang, T. W., Zhou, F., Ma, T., Ni, Y., et al., (2018). Wood-inspired high-performance ultrathick bulk battery electrodes. Advanced Materials, 30(20), 1706745. 72. Lucibello, S., & Rotondi, C., (2019). The biological encoding of design and the premises for a new generation of living products: The example of sinapsi. Temes de Disseny, 35, 116–139.

84

Sustainable Nanomaterials for Biosystems Engineering

73. Luo, C., Xu, G. L., Ji, X., Hou, S., Chen, L., Wang, F., Jiang, J., et al., (2018). Reversible redox chemistry of azo compounds for sodium-ion batteries. Angewandte Chemie International Edition, 57(11), 2879–2883. 74. Luo, H., Chen, M., Cao, J., Zhang, M., Tan, S., Wang, L., Zhong, J., et al., (2020). Cocoon silk-derived, hierarchically porous carbon as anode for highly robust potassium-ion hybrid capacitors. Nano-Micro Letters, 12, 1–13. 75. Ma, J., Xiu, Y. X., Zhang, H., Zhen, Q. M., & Kai, W. Z., (2020). A reinforced-concretelike ultrathick cathode supported by carbonization kapok fibers for high loading lithium-sulfur batteries. Materials Letters, 264, 127312. 76. Ma, Y., Chen, K., Ma, J., Xu, G., Dong, S., Chen, B., Li, J., et al., (2019). A biomass based free radical scavenger binder endowing a compatible cathode interface for 5 V lithium-ion batteries. Energy & Environmental Science, 12(1), 273–280. 77. Ming, J., Wang, L., Sun, Q., Zhou, L., Sun, L., Wang, C., Wu, Y., & Wang, X., (2018). Bio-inspired architectures and hetero-atom doping to construct metal oxide based anode for high performance lithium-ion batteries. Chemistry-A European Journal, 24(63), 16902–16909. 78. Mishra, R. K., Ha, S. K., Verma, K., & Tiwari, S. K., (2018). Recent progress in selected bio-nanomaterials and their engineering applications: An overview. Journal of Science: Advanced Materials and Devices, 3(3), 263–288. 79. Mishra, R. K., Sabu, A., & Tiwari, S. K., (2018). Materials chemistry and the futurist eco-friendly applications of nanocellulose: Status and prospect. Journal of Saudi Chemical Society, 22(8), 949–978. 80. Mongird, K., Viswanathan, V., Balducci, P., Alam, J., Fotedar, V., Koritarov, V., & Hadjerioua, B., (2020). An evaluation of energy storage cost and performance characteristics. Energies, 13(13), 3307. 81. Mukhopadhyay, A., Hamel, J., Katahira, R., & Zhu, H., (2018). Metal-free aqueous flow battery with novel ultrafiltered lignin as electrolyte. ACS Sustainable Chemistry & Engineering, 6(4), 5394–5400. 82. Mullaivananathan, V., & Kalaiselvi, N., (2019). Sb2S3 added bio-carbon: Demonstration of potential anode in lithium and sodium-ion batteries. Carbon, 144, 772–780. 83. Mullaivananathan, V., Sathish, R., & Kalaiselvi, N., (2017). Coir pith derived bio-carbon: Demonstration of potential anode behavior in lithium-ion batteries. Electrochimica Acta, 225, 143–150. 84. Myung, Y., Jung, S., Tung, T. T., Tripathi, K. M., & Kim, T., (2019). Graphene-based aerogels derived from biomass for energy storage and environmental remediation. ACS Sustainable Chemistry & Engineering, 7(4), 3772–3782. 85. Navalpotro, P., Castillo-Martínez, E., & Carretero-González, J., (2021). Sustainable materials for off-grid battery applications: Advances, challenges, and prospects. Sustainable Energy & Fuels, 5(2), 310–331. 86. Nayak, P. K., Yang, L., Brehm, W., & Adelhelm, P., (2018). From lithium-ion to sodium-ion batteries: Advantages, challenges, and surprises. Angewandte Chemie International Edition, 57(1), 102–120. 87. Nirmale, T. C., Kale, B. B., & Varma, A. J., (2017). A review on cellulose and lignin based binders and electrodes: Small steps towards a sustainable lithium-ion battery. International Journal of Biological Macromolecules, 103, 1032–1043. 88. Noack, J., Roznyatovskaya, N., Herr, T., & Fischer, P., (2015). The chemistry of redoxflow batteries. Angewandte Chemie International Edition, 54(34), 9776–9809.

Advanced Electrochemical Bionanomaterials 85 89. Nwanya, A. C., Ndipingwi, M. M., Anthony, O., Ezema, F. I., Maaza, M., & Iwuoha, E. I., (2021). Impedance studies of biosynthesized Na0.8Ni0.33Co0.33Mn0.33O2 applied in an aqueous sodium-ion battery. International Journal of Energy Research, 45(7), 11123–11134. 90. Nwanya, A. C., Ndipingwi, M. M., Ezema, F. I., Iwuoha, E. I., & Maaza, M., (2020). Bio-synthesized P2-Na0.57CoO2 nanoparticles as cathode for aqueous sodium-ion battery. Journal of Electroanalytical Chemistry, 878, 114600. 91. Oberoi, A. S., Nijhawan, P., & Singh, P., (2019). A novel electrochemical hydrogen storage-based proton battery for renewable energy storage. Energies, 12(1), 82. 92. Okoshi, M., Yamada, Y., Komaba, S., Yamada, A., & Nakai, H., (2016). Theoretical analysis of interactions between potassium ions and organic electrolyte solvents: A comparison with lithium, sodium, and magnesium ions. Journal of The Electrochemical Society, 164(2), A54–A60. 93. Oltean, V. A., Philippe, B., Renault, S., Félix, D. R., Rensmo, H., & Brandell, D., (2016). Investigating the interfacial chemistry of organic electrodes in Li-and Na-ion batteries. Chemistry of Materials, 28(23), 8742–8751. 94. Panda, M. R., Dutta, D. P., & Mitra, S., (2019). Bio-derived mesoporous disordered carbon: An excellent anode in sodium-ion battery and full-cell lab prototype. Carbon, 143, 402–412. 95. Patil, N., Jerome, C., & Detrembleur, C., (2018). Recent advances in the synthesis of catechol-derived (bio) polymers for applications in energy storage and environment. Progress in Polymer Science, 82, 34–91. 96. Patra, B. C., Das, S. K., Ghosh, A., Moitra, P., Addicoat, M., Mitra, S., Bhaumik, A., et al., (2018). Covalent organic framework based microspheres as an anode material for rechargeable sodium batteries. Journal of Materials Chemistry A, 6(34), 16655–16663. 97. Patwardhan, S. V., Manning, J. R., & Chiacchia, M., (2018). Bioinspired synthesis as a potential green method for the preparation of nanomaterials: Opportunities and challenges. Current Opinion in Green and Sustainable Chemistry, 12, 110–116. 98. Peijnenburg, W. J., Baalousha, M., Chen, J., Chaudry, Q., Von, D. K. F., Kuhlbusch, T. A., Lead, J., et al., (2015). A review of the properties and processes determining the fate of engineered nanomaterials in the aquatic environment. Critical Reviews in Environmental Science and Technology, 45(19), 2084–2134. 99. Peng, S., Jin, G., Li, L., Li, K., Srinivasan, M., Ramakrishna, S., & Chen, J., (2016). Multi-functional electrospun nanofibres for advances in tissue regeneration, energy conversion & storage, and water treatment. Chemical Society Reviews, 45(5), 1225–1241. 100. Pulido-Reyes, G., Leganes, F., Fernández-Piñas, F., & Rosal, R., (2017). Bio-nanointerface and environment: A critical review. Environmental Toxicology and Chemistry, 36(12), 3181–3193. 101. Rahman, M. Z., Edvinsson, T., & Kwong, P., (2020). Biochar for electrochemical applications. Current Opinion in Green and Sustainable Chemistry, 23, 25–30. 102. Rajagopalan, R., Tang, Y., Jia, C., Ji, X., & Wang, H., (2020). Understanding the sodium storage mechanisms of organic electrodes in sodium-ion batteries: Issues and solutions. Energy & Environmental Science, 13(6), 1568–1592. 103. Rasul, S., Suzuki, S., Yamaguchi, S., & Miyayama, M., (2012). High capacity positive electrodes for secondary Mg-ion batteries. Electrochimica Acta, 82, 243–249. 104. Ravuri, B. R., Gandi, S., & Chinta, S. R., (2018). Zn–Ge–Sb glass composite mixed with Ba2+ ions: A high capacity anode material for Na-Ion batteries. Applied Nanoscience, 8(6), 1569–1577.

86

Sustainable Nanomaterials for Biosystems Engineering

105. Ruiz-Hitzky, E., Darder, M., Aranda, P., & Ariga, K., (2010). Advances in biomimetic and nanostructured biohybrid materials. Advanced Materials, 22(3), 323–336. 106. Rybarczyk, M. K., Peng, H. J., Tang, C., Lieder, M., Zhang, Q., & Titirici, M. M., (2016). Porous carbon derived from rice husks as sustainable bioresources: Insights into the role of micro-/mesoporous hierarchy in hosting active species for lithium-sulfur batteries. Green Chemistry, 18(19), 5169–5179. 107. Ryou, M. H., Hong, S., Winter, M., Lee, H., & Choi, J. W., (2013). Improved cycle lives of LiMn2O4 cathodes in lithium-ion batteries by an alginate biopolymer from seaweed. Journal of Materials Chemistry A, 1(48), 15224–15229. 108. Saravanan, K., & Kalaiselvi, N., (2015). Nitrogen containing bio-carbon as a potential anode for lithium batteries. Carbon, 81, 43–53. 109. Schipper, F., & Aurbach, D., (2016). A brief review: Past, present, and future of lithium-ion batteries. Russian Journal of Electrochemistry, 52(12), 1095–1121. 110. Scrosati, B., Hassoun, J., & Sun, Y. K., (2011). Lithium-ion batteries. A look into the future. Energy & Environmental Science, 4(9), 3287–3295. 111. Sharma, D., Kanchi, S., & Bisetty, K., (2019). Biogenic synthesis of nanoparticles: A review. Arabian Journal of Chemistry, 12(8), 3576–3600. 112. Shea, J. J., & Luo, C., (2020). Organic electrode materials for metal ion batteries. ACS Applied Materials & Interfaces, 12(5), 5361–5380. 113. Shen, S., Zhou, R., Li, Y., Liu, B., Pan, G., Liu, Q., Xiong, Q., et al., (2019). Bacterium, fungus, and virus microorganisms for energy storage and conversion. Small Methods, 3(12), 1900596. 114. Shi, Y., Zhang, J., Pan, L., Shi, Y., & Yu, G., (2016). Energy gels: A bio-inspired material platform for advanced energy applications. Nano-Today, 11(6), 738–762. 115. Slater, M. D., Kim, D., Lee, E., & Johnson, C. S., (2013). Sodium-Ion batteries. Advanced Functional Materials, 23(8), 947–958. 116. Song, J., Xiao, B., Lin, Y., Xu, K., & Li, X., (2018). Interphases in sodium-ion batteries. Advanced Energy Materials, 8(17), 1703082. 117. Song, X., Song, S., Wang, D., & Zhang, H., (2021). Prussian blue analogs and their derived nanomaterials for electrochemical energy storage and electrocatalysis. Small Methods, 5(4), 2001000. 118. Stram, B. N., (2016). Key challenges to expanding renewable energy. Energy Policy, 96, 728–734. 119. Suman, G., Rao, C. S., Ojha, P. K., Babu, M. S., & Rao, R. B., (2017). Mixed polyanion NaCo1-x(VO)xPO4 glass–ceramic cathode: Role of ‘Co’on structural behavior and electrochemical performance. Journal of Materials Science, 52(9), 5038–5047. 120. Suzuki, S., Usuki, T., Sugawara, K., Ito, T., Kato, S., & Suganuma, H., (2018). Investigation of bio-degradable organic species for redox flow battery. Journal of Arid Land Studies, 28(S), 177–180. 121. Tao, X., Chai, W., Xu, F., Luo, J., Xiao, H., Liang, C., Gan, Yet al., (2015). Bio-templated fabrication of highly defective carbon anchored MnO anode materials with high reversible capacity. Electrochimica Acta, 169, 159–167. 122. Tian, J., Shao, Q., Dong, X., Zheng, J., Pan, D., Zhang, X., Cao, H., et al., (2018). Bio-template synthesized NiO/C hollow microspheres with enhanced Li-ion battery electrochemical performance. Electrochimica Acta, 261, 236–245. 123. Wang, F., Wu, X., Li, C., Zhu, Y., Fu, L., Wu, Y., & Liu, X., (2016). Nanostructured positive electrode materials for post-lithium ion batteries. Energy & Environmental Science, 9(12), 3570–3611.

Advanced Electrochemical Bionanomaterials 87 124. Wang, H., Yang, Y., & Guo, L., (2017). Nature-inspired electrochemical energy-storage materials and devices. Advanced Energy Materials, 7(5), 1601709. 125. Wang, M., Li, S., Zhang, Y., & Huang, J., (2015). Hierarchical SnO2/carbon nanofibrous composite derived from cellulose substance as anode material for lithium-ion batteries. Chemistry: A European Journal, 21(45), 16195–16202. 126. Wang, Q., Gao, C., Zhang, W., Luo, S., Zhou, M., Liu, Y., Liu, R., et al., (2019). Biomorphic carbon derived from corn husk as promising anode materials for potassium ion battery. Electrochimica Acta, 324, 134902. 127. Wang, S. X., Yang, L., Stubbs, L. P., Li, X., & He, C., (2013). Lignin-derived fused electrospun carbon fibrous mats as high performance anode materials for lithium-ion batteries. ACS Applied Materials & Interfaces, 5(23), 12275–12282. 128. Wang, X., Zhao, J., Yao, D., Xu, Y., Xu, P., Chen, Y., Chen, Y., et al., (2020). Bio-derived hierarchically porous heteroatoms doped‑carbon as anode for high performance potassium-ion batteries. Journal of Electroanalytical Chemistry, 871, 114272. 129. Wang, Y., Chen, R., Chen, T., Lv, H., Zhu, G., Ma, L., Wang, C., et al., (2019). Emerging non-lithium ion batteries. Energy Storage Materials, 4, 103–129. 130. Wang, Z., Yun, S., Wang, X., Wang, C., Si, Y., Zhang, Y., & Xu, H., (2019). Aloe peel-derived honeycomb-like bio-based carbon with controllable morphology and its superior electrochemical properties for new energy devices. Ceramics International, 45(4), 4208–4218. 131. Wei, R., Xu, R., Zhang, K., Liang, F., & Yao, Y., (2020). Biological enzyme treatment of starch-based lithium-ion battery silicon-carbon composite. Nanotechnology, 32(4), 45605. 132. Wu, L., Buchholz, D., Vaalma, C., Giffin, G. A., & Passerini, S., (2016). Apple-biowastederived hard carbon as a powerful anode material for Na-ion batteries. ChemElectroChem, 3(2), 292–298. 133. Wu, X., Leonard, D. P., & Ji, X., (2017). Emerging non-aqueous potassium-ion batteries: Challenges and opportunities. Chemistry of Materials, 29(12), 5031–5042. 134. Wu, Z., Xie, J., Xu, Z. J., Zhang, S., & Zhang, Q., (2019). Recent progress in metalorganic polymers as promising electrodes for lithium/sodium rechargeable batteries. Journal of Materials Chemistry A, 7(9), 4259–4290. 135. Xia, Q., Zhao, X., Xu, M., Ding, Z., Liu, J., Chen, L., Ivey, D. G., & Wei, W., (2015). A Li-rich layered@ spinel@ carbon heterostructured cathode material for high capacity and high rate lithium-ion batteries fabricated via an in situ synchronous carbonizationreduction method. Journal of Materials Chemistry A, 3(7), 3995–4003. 136. Xiang, Y., Zhu, W., Guo, W., Lou, F., Deng, B., Liu, D., Xie, Z., et al., (2017). Controlled carbon coating of Fe2O3 nanotube with tannic acid: A bio-inspired approach toward high performance lithium-ion battery anode. Journal of Alloys and Compounds, 719, 347–352. 137. Xu, J., Dou, S., Liu, H., & Dai, L., (2013). Cathode materials for next generation lithium-ion batteries. Nano-Energy, 2(4), 439–442. 138. Xu, Y., & Wang, E., (2012). Electrochemical biosensors based on magnetic micro/ nanoparticles. Electrochimica Acta, 84, 62–73. 139. Xu, Y., Zhou, M., & Lei, Y., (2018). Organic materials for rechargeable sodium-ion batteries. Materials Today, 21(1), 60–78. 140. Yabuuchi, N., Kubota, K., Dahbi, M., & Komaba, S., (2014). Research development on sodium-ion batteries. Chemical Reviews, 114(23), 11636–11682. 141. Yin, X., Sarkar, S., Shi, S., Huang, Q. A., Zhao, H., Yan, L., Zhao, Y., & Zhang, J., (2020). Recent progress in advanced organic electrode materials for sodium-ion batteries:

88

Sustainable Nanomaterials for Biosystems Engineering

Synthesis, mechanisms, challenges, and perspectives. Advanced Functional Materials, 30(11), 1908445. 142. Yokokura, T. J., Rodriguez, J. R., & Pol, V. G., (2020). Waste biomass-derived carbon anode for enhanced lithium storage. ACS Omega, 5(31), 19715–19720. 143. You, R., Han, X., Zhang, Z., Li, L., Li, C., Huang, W., Wang, J., et al., (2019). An environmental friendly cross-linked polysaccharide binder for silicon anode in lithium-ion batteries. Ionics, 25(9), 4109–4118. 144. Yu, Y., Ren, Z., Shang, Q., Han, J., Li, L., Chen, J., Fakudze, S., et al., (2021). Ionic liquid-induced low temperature graphitization of cellulose-derived biochar for high performance sodium storage. Surface and Coatings Technology, 412, 127034. 145. Zeng, L., Kang, B., Luo, F., Fang, Y., Zheng, C., Liu, J., Liu, R., et al., (2019). Facile synthesis of ultra-small few-layer nanostructured MoSe2 embedded on N, P Co-doped bio-carbon for high-performance half/full sodium-ion and potassium-ion batteries. Chemistry: A European Journal, 25(58), 13411–13421. 146. Zhang, W., Yin, J., Lin, Z., Lin, H., Lu, H., Wang, Y., & Huang, W., (2015). Facile preparation of 3D hierarchical porous carbon from lignin for the anode material in lithium-ion battery with high rate performance. Electrochimica Acta, 176, 1136–1142. 147. Zhang, Y., Zhao, Y., Konarov, A., Li, Z., & Chen, P., (2015). Effect of mesoporous carbon microtube prepared by carbonizing the poplar catkin on sulfur cathode performance in Li/S batteries. Journal of Alloys and Compounds, 619, 298–302. 148. Zhang, Y., Mei, J., Yan, C., Liao, T., Bell, J., & Sun, Z., (2020). Bioinspired 2D nanomaterials for sustainable applications. Advanced Materials, 2(18), 1902806. 149. Zhao, W., Wen, J., Zhao, Y., Wang, Z., Shi, Y., & Zhao, Y., (2020). Hierarchically porous carbon derived from biomass reed flowers as highly stable Li-ion battery anode. Nanomaterials, 10(2), 346. 150. Zheng, P., Liu, T., Zhang, J., Zhang, L., Liu, Y., Huang, J., & Guo, S., (2015). Sweet potato-derived carbon nanoparticles as anode for lithium-ion battery. RSC Advances, 5(51), 40737–40741. 151. Zhou, G., Mo, L., Zhou, C., Wu, Y., Lai, F., Lv, Y., Ma, J., et al., (2021). Ultra-strong capillarity of bioinspired micro/nanotunnels in organic cathodes enabled high-performance all-organic sodium-ion full batteries. Chemical Engineering Journal, 420, 127597. 152. Zhu, H., Jia, Z., Chen, Y., Weadock, N., Wan, J., Vaaland, O., Han, X., et al., (2013). Tin anode for sodium-ion batteries using natural wood fiber as a mechanical buffer and electrolyte reservoir. Nano-Letters, 13(7), 3093–3100.

PART II NANOMATERIALS FOR BIOSENSING APPLICATIONS

CHAPTER 4

CARBON NANOMATERIALS FOR OPTICAL AND ELECTRICAL BIOSENSORS HRIDOY JYOTI BORA, GAUTOMI GOGOI, SAMIRAN UPADHYAYA, KANGKAN JYOTI GOSWAMI, GEETI KABERI DUTTA, and ANAMIKA KALITA

ABSTRACT “Biosensor” signifies an analytical platform that has acquired paramount importance due to their inherent simplicity, cost-effectiveness, fast analysis, and miniaturization, which can detect the presence as well as the quantity of biological systems, especially biomolecules, and promote a major advancement in wider sectors like drug discovery, clinical diagnostics, and environmental monitoring. The main components of a biosensor include a sensing unit, signal transducer, and processing units. Generally, nanomaterials (NMs), at the nanoscale level, are currently experiencing rapid development and can act as a transducer material that are an important part of developing a biosensor structure. Such transducers interpret the interaction of analyte and the biomolecules of interest and convert it into electrical or optical signals. Among various NMs applied, dimensional carbon nanomaterials (CNMs) (i.e., carbon nanotubes, carbon quantum dots (QDs), carbon nanofibers (CNFs), graphene, etc.), are being intensively explored in the growth of advanced technology for sensing purposes. Therefore, this chapter mainly includes an overview on diverse aspects of CNMs together with their characteristic features, specially focusing on optical and electrical properties, towards detection of biological entities. Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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4.1 INTRODUCTION Optical biosensors are analytical devices that contain biorecognition sensing element joined with a transducer system (Figure 4.1). The aim of an optical biosensor is to build a signal which can relate to the concentration of the analyte. The main components of a biosensor include a sensing unit, signal transducer, and processing units. Optical biosensors acquire more attention for analytical applications as they have many advantageous factors compared to that of the conventional analytical techniques. This is mainly because of the simple working principle and hardware set-ups. They permit direct labelfree detection of many chemical and biological substances due to which they can be used in environment monitoring applications as well as in human health conditions also [1]. They are highly sensitive, have high specificity, cost-effective and is of very small size. The mechanism of sensing works by detecting the changing of light intensity, when it gets interacted with sensing receptors before and after the exposure of light to the analyte. The research related to the optical biosensors are directed mainly for the environmental applications, health care and for the biotechnology industry. The applications of biosensors in these fields, viz. environment, medicines, and biotechnology, are countless, but each field has its own requirements related to that of the concentration of analyte, time required, cleaning requirements, reusability of biosensors and various different factors [2]. With the advancement of efforts in the area of biosensors is to make the biosensors as small as possible, which will consume less power, offers greater sensitivity, selectivity, and can be utilized in harsh and sophisticated sensing situations. Nowadays, nanotechnology (NT) gains much importance in this growing world due to its high surface area to the volume ratio, small size and also for the other properties. Its development revolutionizes the design of biosensors in nanometer scale, which are also called nano-probes. Due to this, biosensors are becoming more powerful and much effective as it increases its possibility to enter in much smaller environs and to identify the health-related issues in molecular and biological levels. The main objective of using NMs in sensing is that the NMs should show some interactions with the interested biomolecules, when the surfaces are modified with organic species. The NMs must have some distinct properties in order to get suited for optical biosensors, i.e., their data should be recordable, such as optical signal, electronic signals, or surface plasmonic waves which will give some response upon interaction between the analyte of interest and the biomolecules. Those NMs which have some luminescence property are of popular choices as it can easily

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detect when the light detector is used. There is a definite connection present between the concentration of the analyte that is present in that particular microenvironment, like a particular cell, and the degree of intensification or degree of quenching of the luminescence [3].

FIGURE 4.1  Schematic representation of optical biosensor.

The accidental discovery of C-dots for biosensing applications as a side product while making single-walled carbon nanotubes (SWCNT), have picturized many characteristics which are required to make an optical nanoprobe [4]. The structure of carbon dots (C-dots) has some hybrid sp3 and sp3 carbon conjugated core, with structure varies from crystalline to amorphous [3] and have some oxygen content in the form of species which contains oxygen like hydroxyl, aldehyde, and carboxyl [5]. C-dots, which are also known as Carbon nanodots/carbon or graphene quantum dots (GQDs) are the nanoparticles (NPs) whose size ranges from 1 to 10 nm, having properties (chemical and physical) similar to that of the quantum dots (Q-dots) but C-dots are less toxic, due to the presence of only carbon

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blocks which are non-toxic, and therefore C-dots have better biocompatibility with living cells. Their sizes are also different from that of graphene oxide (GO). This is the major advantage of C-dots in comparison with the Q-dots that can be used in optical nanoprobes. This can remove the major issue of heavy metal leaching which are present in Q-dots. Due to its advantageous properties, C-dots are applied in many fields like catalysis, sensing, energy conversion, bioimaging, UV degradation, and so on. C-dots have biocompatibility, they are photostable and is capable of photoluminescent radiation which is mainly dependent on excitation wavelength (260–360 nm) and due to this, C-dots can be used in photolytic applications and with the view of increase photoluminescence and water solubility, small organic molecules, polymers, and some metals are incorporated on the C-dots surface [6]. Because of the above properties of C-dots, they can be employed in numerous biological applications viz. drug delivery [7], in-vivo, and in-vitro probes, PDT agents [8] and many more. C-dots can maintain their photoluminescence behavior after the loading of drug or gene and for this reason, they can be employed in drug delivery [9], delivering genetic material [10] and small interfering ribonucleic acid (siRNA) [11]. C-dots can be produced via many processes, including green approaches, and the advantage is that C-dots can be prepared using a vast choice of starting precursors ranging from pure to complex compounds. Figure 4.2 shows some of the important aspects in the development of C-dots, which can be used mainly in biological applications.

FIGURE 4.2  Important aspects for the development of C-dots as nanoprobes for biosensing applications.

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Application of C-dots in sensing instruments are of prime importance nowadays as they are very small in size, and they have fluorescence emitting property which can be used for sensing signals. There are various methods present till date for the preparation of C-dots, which is the main advantageous factor compared to that of synthesis of Q-dots. In fact, the first C-dots are prepared as a side-product while purifying SWCNTs [4], which gives an indication for a simple and easy synthesis procedure. From that time, a vast number of reports has been appeared in the literature which shows different procedures for the preparation of C-dots with similar properties. Some of the common examples include electrochemical oxidation, laser ablation, and carbonization. Many methods for the synthesis are unique as many of them are prepared by using waste, such as agriculture renewables [12] and waste foods [13], which also supports the sustainability concept and green chemistry principles. In spite of having various synthesis procedures and different starting precursors, synthesis of C-dots is divided in two different categories, they are bottom-up and top-down methods (Figure 4.3). C-dots are either prepared in bulk format by using the top-down, or in smaller format by using bottom-up methods. The instruments used in the top-down method are quite advanced and costly because their starting precursors are taken in bulk from carbon sources, for example, graphene, which can be crushed to form small nanoparticles via some complicated processes and harsh reaction conditions. Most of the carbon NPs which are prepared by some harsh process, needs to undergo some surface passivation techniques, viz. reflux in acid, so that the fluorescence property is introduced to the C-dots. Advantageous factor of C-dots is that their properties are consistent, such as their structure and chemical content, which is most important for utilizing C-dots in biosensing applications. Even the chemical properties of C-dots are homogenous in nature. Some of the preparation techniques of C-dots provides large scale production, which is very important to meet the commercial demands. Large scale production of C-dots also makes the whole process cost-effective. It is possible to make a 10 g solution of C-dots, which are used for ink in printing purpose [14], as C-dots are NMs, so producing C-dots in gram scale can be considered as large-scale production. Recently, C-dots from about 100 kg of waste food by using ultrasound irradiation at room temperature [13]. There is also concern regarding the assurance of forming the C-dots, as the reliability of the carbon nanoprobes depends on the quality of the C-dots formed. For this, one detailed investigation has been done using bee pollens as beginning material and studied the effect of differences for synthesis [15].

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FIGURE 4.3  Synthesis processes for nanoparticles.

C-dots have several advantages compared to that of other materials for the use of biosensor receptors. This consideration is made based on the overall process of development, which starts from the synthesis of raw C-dots to its utilization in different applications. Major aspects include for each process are sustainability, quality assurance, and suitability for real applications. In carbon nanoprobes, C-dots functions as a platform which will interact with the analyte, and it will show some fluorescence pattern which reflects the presence of some specific species of the corresponding analyte. It is very important to have some functional terminals to be present on the platform of C-dots for the interactions to occur. There are several methods for introducing the functional terminals on C-dots, some of them are discussed in the next section. For the introduction of functional terminals in the C-dots surface, surface passivation by acid oxidation is the earliest approach. The presence of various groups which have oxygen in them, such as –OH or the –COOH [12]. In fact, this process is not performed directly to introduce some functionality in the C-dots, but due to this, it increases the binding affinity towards other species, which is the main interest that should be monitored, and it shows that the

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surface passivated C-dots turned into a sensing application. The sensing of sensitive ions, like Sn (II), by using surface passivated C-dots, which shows quenching when the C-dots are added to the Sn (II) ions [16]. Other methods for introducing the functionalities in C-dots are the thermal and hydrothermal carbonization process. C-dots by thermal carbonization process of sago waste, which shows the presence of carbonyl functional group [17]. C-dots which are being prepared by using the hydrothermal carbonization method are effective in detecting many metal ions irrespective of changes or modifications required on the C-dots surface [18]. Fourier Transform Infrared Spectroscopy (FT-IR) is generally used to detect different types of functional groups which are present on the C-dots surface. C-dots from pork meat through hydrothermal carbonization process and found different groups, like –COOH, –NH2 and –OH, which are present in C-dots surface and found that they are under negative charge condition in an alkaline medium [19]. The prime effort is focused on grafting specific receptors on C-dots as they are the main components for nanoprobes which will be used in biosensing applications. Some distinct functionality of different sizes and shapes are attached on C-dots surface for better binding affinities. Decorated tyrosinase in the C-dots surface which is used as nanoprobe and is found effective and sensitive for detection of levodopa [20]. Boric acid functionalized C-dots, which shows greater sensitivity towards quenching mechanism in the presence of glucose [21]. As glucose-boronic acid moieties are formed, which will aggregate the C-dots and destroys the luminescence behavior of C-dots. Organ silanes (inert layers) on C-dots, which shows low toxicity and greater stability to the cell lines tested [21]. Nanoprobes are used to detect the cancer cells when they are tagged with AS1411, a nucleolin aptamer [23]. Those C-dots which are tagged with aptamer or the RNA/DNA oligonucleotides shows high specificity and greater binding affinity. The aptamers are generally released from the C-dots when they detect cancer cells and simultaneously increasing the fluorescence of the C-dots. Dopamine (DA) aptamer is tagged on C-dots surface and can be used for the detection of DA [24]. Antibodies can also be tagged on the C-dots surface for the detection of several biomolecules that are present in human bodies [25, 26]. For the nanoprobes, which are developed from C-dots and utilized mainly for biosensing applications, are found to have longer wavelengths of both excitation and emission spectra as Ultra-Violet (UV) excitation is very harmful for our biological systems. Several attempts are there to redshift the fluorescence. A most common method is to introduce some heteroatoms, viz. oxygen, nitrogen, sulfur, and phosphorus, to the C-dots. Among all

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these elements, nitrogen is the most famous element as it has five outermost electrons to bind with carbon atoms and the size is also similar. The shift of fluorescence peak to a longer wavelength when nitrogen content is increases in C-dots [27]. C-dots doped with nitrogen is shifting the fluorescence profile in longer wavelength, but also it increases the emission efficiency [28]. When C-dots are doped with sulfur atom, C-dots quantum yields are increased, which will help to enhance the sensitivity of the nanoprobes [29]. Another promising element which can be doped in C-dots to increase the fluorescence is oxygen atom. Oxygen can be present in C-dots in different forms such as hydroxyl, carboxyl, carbonyl, etc. The presence of oxygen rich content improves/promotes the aromatic character of starting materials which enhances the sp2 hybrid network, i.e., the fluorescence origin of C-dots. Requires less time to make oxygen doped C-dots and parallelly increases the quantum yield [30]. Phosphorus doped C-dots initially shows a red shift in emission profile only if, the carbonization of starting precursors is carried out by taking dissimilar acids, one having phosphorus content while the other does not. The increment in shift of emission profile of the C-dots only when sulfuric acid is replaced with phosphoric acid for the carbonization of sucrose [31]. The size of phosphorus is large compared to that of carbon, but it can still make defects in thin films of sp3 network of diamond [32]. The phosphorus doped C-dots have increased fluorescence [6]. This chapter describes the various aspects of carbon-based NMs together with their characteristic features, specially focusing on optical and electrical properties, towards detection of biological entities. 4.2  C-DOTS AS OPTICAL BIOSENSORS Nanoprobes of C-dots have been used as biosensing applications which includes the detection of different biomolecules. Due to its small size, C-dots can be introduced in the biological environment, even in a single cell, and can interact with the analyte. The instrumentation includes the presence of low power excitation light for the excitation of the C-dots and this will change the optical property of C-dots, light emitting diode (LED) is used in replacement of conventional light (UV light), a light detector which will detect, record, and analyze based on mathematical equations to generate the useful analytical information’s. The application of metal detection with the help of an interaction between metal ions and the functionalities that are present on the C-dots surface [17, 33]. In fact, some of the metals are important for our biological systems so if the monitoring or metal ions occur in molecular level, it will

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be a great advantage. Metal ions are very crucial for a biological system as some of the ions are essential, like metabolism, electrolytic role for transmitting signals, while some might damage the biological system or can say it is harmful for the system. So, monitoring of the same by using C-dots as nanoprobes is an additional benefit for biomedical diagnosis. C-dots as nanoprobes can detect the presence of metabolites such as cholesterol and xanthine in hydrogen peroxide (H2O2) as other than metal ions, different other metabolites that are produced in-situ by some biological processes are also important as they are used as biological markers for different diseases [34]. The detection of dipicolinic acid by using C-dots, which is a biological marker for anthrax that cause infection in biological systems [35]. C-dots-based nanoprobes are used for detection of cancerous cells and disease biomarkers [36]. In some biomedical fields, the detection is not fully dependent on analyte considering different conditions such as under contamination or under high pressure, but it is also dependent on some indirect measurements, such as proteins. Proteins are nothing but the biomolecules of a certain size and shape, which shows biological properties. Protein sensing by ethylenediamine, polyethylenimine (PEI) branched functionalized C-dots [37]. This report is successful in detecting eight different types of proteins in between 5 nM and 40 nM detection range. Detection of DNA which is affected by human immunodeficiency viruses (HIV) using C-dot nanoprobes [38]. To detect the different types of bacteria’s and viruses, DNA-based C-dots are also used. Florescence imaging technique is the main working principle for the detection of larger areas such as tumors or the tissues. The C-dots are reformed in such a way that they will be able to diffuse in layers of tissues such that upon the exposure to excitation wavelength, that particular zone will illuminate and shows margins for different functionalities. This unique technique has been used for the detection of tumors or the cancerous cells and the C-dots exhibit very good nucleus targeting and cancer cell cytoplasm in MCF-7 [39]. The uptake of cancerous cells when C-dots are coupled with folic acid, which in turn is very useful for the diagnostic purposes [40]. 4.3  C-DOTS AS ELECTRICAL BIOSENSORS Carbon nanotubes (CNT) can be divided into two groups based on their structural difference: one is SWCNT and the other is multi-walled carbon nanotube (MWCNT) shown in Figure 4.4. Carbon materials possess various types of microstructures, including nanotubes, graphite, carbon fiber, glassy carbon, diamond, and amorphous powders [41].

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FIGURE 4.4  (a) SWCNT; and (b) MWCNT.

Due to its outstanding properties, CNT’s paved the way to use it as a biosensor. Among the biosensing applications, both the optical and electrochemical nature turns out to be effective. CNT’s can be used as an electrode material as electron transfer reactions can be meditated by this [42]. In electrochemical biosensors, three or two electrodes (working, reference, and counter) convert a biological signal to electrochemical one. CNT-based electrochemical biosensors exhibit many advantageous applications of having low production cost, high sensitivity, faster response, promising portability and ease of operation. There are also enzyme specific electronically active CNMs present. The various electrodes for these electrochemical applications are: • CNT paste enzyme electrodes; • CNT forest electrodes immobilized enzymes; and • CNT-modified electrodes immobilized enzymes. First electrode based on carbon nanotube to oxidize dopamine (DA) [42]. This electrode was made by mixing CNT (10 mg) and bromoform (10 μl) followed by packing the obtained paste into a glass tube having a diameter of 1.5 mm and a length of 8 cm. A copper or platinum wire was passed into the glass tube through the unpacked end and this unpacked end was covered by a scotch tape (Figure 4.5). Carbon electrode was also used to oxidize methanol and electrocatalyze O2 reduction [43]. Carbon nanotube in membrane form was used here. This membrane of carbon nanotube was prepared by a templating method of CVD

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of carbon having the pores of alumina membranes. Single-walled carbon nanotube with a modification with glassy carbon electrode has been used to oxidize 3,4-dihydroxyphenylacetic acid (the metabolite of neurotransmitter DA) electrically [44]. Here, the Single-walled carbon nanotube (SWNT) film was prepared by dropping a supernatant of SWNT (15 mm3, 0.1 mg cm–3) on the GC electrode in DMF solvent followed by evaporating the solvent under an infrared lamp.

FIGURE 4.5  Schematic of a carbon nanotube electrode.

SWNT have very stable electrochemical behavior. Rather than DA, other biomolecules including ascorbic acid (AA) and epinephrine can also be measured using SWNT electrode [45]. CNM-based electrochemical biosensors have a wide range of applications: 1. In Stripping as well as Metal Deposition Process: CNFs with paraffin wax have been employed in stripping and metal deposition process [46]. CNF can be modified by including a dopant having significant catalytic activity towards O2 reduction [47]. 2. In Electrochemical Sensing: The first electrochemical biosensor was used to detect glucose [48]. Glucose to gluconic acid’s oxidation reaction was reported by them. The use of glassy carbon electrodes made of CNF in NADH detection [49]. This NADH detection can

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also be done without any mediator with the use of carbon fiber made by electrospinning process [50]. This electrochemical sensor showed low detection limits (nmol L–1-level), along with sufficient selectivity and a broad linear range for the detection of NADH. The flow injection of amphoteric detection of H2O2 on Metal NP loaded CNF shows high electrocatalytic activities towards the oxidation of NADH and the reduction of H2O2 having detection limit of 0.2 mM [51, 52]. 3. In Mediators in Amperometric Sensors and Transducers: CNM in its different forms: CNT, fullerenes, and CNFs tend to provide good candidature as mediators in amperometric sensors and transducers [53]. 4. As Biosensor: CNFs (CNF) have larger surface are for functionalization as compared to CNT. Therefore, the type and the number of groups can be well controlled on the outer surface of CNFs, allows for selective stabilization and immobilization of biomolecules such as DNA, proteins, and enzymes. It also exhibits a higher rate of conductivity [54]. It can be also used as acetylcholine esterase and tyrosinase biosensor [55], dehydrogenase biosensor [56], cell sensor and immunosensor [57]. In electrochemical biosensors, CNTs serves a dual purpose: electrical conductivity (EC) can be achieved for electrochemical transduction as well as they act as immobilization support for biomolecules [58]. A schematic of a biosensor employing CNMs is shown in Figure 4.6.

FIGURE 4.6  Schematic of a biosensor using carbon nanoparticles.

At present time, the worldwide threatening disease which shakes all of us and pause our life for more than one year that is novel SARS-CoV-2 coronavirus can be detected with electrodes modified with CNM. Fabiani et al. [38] have reported an electrochemical immunoassay procedure to detect this virus in saliva (Figure 4.7).

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FIGURE 4.7  SARS-CoV-2 detection by using carbon black NM electrode.

This sensor configuration having CNM provide their candidature to detect sulfur and nitrogen containing proteins in untreated saliva in which the detection limit found to be 19 ng/mL and 8 ng/mL respectively. CNM electrode can also be used for the application in energy storage of supercapacitor. CNM from biomass waste of leaves including pineapple leaves, acacia leaves, Pandanus tectorius leaves, and Terminalia catappa leaves [59, 60]. In the field of food safety, these NMs emerge as a potential tool to determine the safety level as well as quality control of the food products. A review on the food safety controlled by CNMs in detecting adulterants like food glucose, melamine, urea, etc.), and spoilage like toxins, pathogens, gases, pH changes, etc. [61]. Pongamia pinnata shell was also used for the synthesis of CNMs to be used for supercapacitor [62]. Heteroatom doped CNM is also found to be beneficial in this application. Synthesized nitrogen and phosphorus co-doped CNMs showing high specific capacitance of 367.5 F/g at 0.5 A/g with a ~ 95% capacity retention after 10,000 cycles at 10 A/g [63]. For the optoelectronic application, carbon QDs along with GQDs modified device shows open circuit voltage up to 1.136 V and efficiency up to 18.89% [64]. Carbon nanowalls is also used as photoanode and counter electrode in this regard having the potential to show photocurrent density up to 830 µA cm–2 with excellent power conversion efficiency (PCE) [65].

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4.4  GRAPHENE MATERIALS FOR OPTICAL BIOSENSORS Graphene is a 2D structure, with an arrangement of sp2 hybridized carbon atoms in a hexagonal fashion and a thickness of 0.345 nm with carbon-carbon bond length 1.42 Å, which exhibits unique morphological properties. The 2D graphene layers are held together by weak Van Der Waal forces, in three dimensional graphite that can easily be separated by using different approaches [66]. On oxidation, the graphite layered crystal is breakdown to single-atomic-layered structure decorated by oxygen containing functional group (–COOH, –OH, –O, etc.), called graphene oxide (GO). These hydrophilic group present in the surface, increases the interlayer distance between two GO layers considerably to make it easy to disperse. Most importantly, by removing these oxygenated functional group from GOS, we can regenerate its conjugated monolayer structure by using a cost-effective reduction process. These single layered sheets are now termed as reduced graphene oxide (rGO). GO can be further chemically functionalized using a variety of chemical group to endow it with high colloidal stability. There are two kinds of approaches for modification of GO. (i)Covalent functionalization, which include transformation of functional group through a covalent bond formation using electrophilic addition, condensation, or nucleophilic substitution reactions. (ii)Non covalent functionalization: consist of electrostatic, Van Der Waals hydrophobic, and p-p interactions [67, 68]. Further, functionalization of GO leads to fragmented graphene fragments, with high optical properties, termed as GQDs. A 3-dimensional representation of graphene, GO, rGO, and GQD is presented in Figure 4.8.

FIGURE 4.8  3D representation of graphene, graphene oxide, rGO, and graphene quantum dot, respectively.

Due to its zero optical band gap, graphene exhibits no fluorescence. Incorporation of functional groups to graphene leads to formation of

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graphene sheets with mixture of sp2 and sp3 C-atoms, which may open the optical bandgap, resulting in fluorescence [69]. The fluorescence properties of graphene-based materials are observed when the two-dimensional GOSs are converted into zero-dimensional GQDs. In simple terms, GQD can be defined as the graphene-based fragments, having a size range from 1 to 10 nm. GQDs are obtained via cutting of the GOSs to atomic layer of nano-dimension. GQDs are the materials with high importance because of their excellent optical properties, arising due to the edge effect and quantum confinement [70]. GQDs can be synthesized using two different methodologies, namely “top-down” and “bottom-up” methods. Usually, “top-down” methods are more easily compared to “bottom-up” method via different sub-routes, as depicted in Figure 4.9.

FIGURE 4.9  Different routes leading to the synthesis of GQD.

Apart from being optically active, GQDs are bio-compatible, watersoluble, low-cost, environment friendly and photo-stable. GQDs are known to possess excellent optical properties, which make them suitable for extensive use in wide fields, such as bio-imaging, medicines, environmental remediation, drug delivery, sensing, and electronics. Among all the known

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applications, fluorescent sensing using GQDs have been in demand in the recent years. The tunable 2D surface of GQDs further enhances its optical characteristic for applications in fluorescent sensing. Photoluminescence is the most fascinating property of GQD, which enable it to be used as a sensing probe. Based on the different preparation methods, GQDs can emit different colors, such as green, blue, red, orange, and yellow. Doping with other heteroatoms can further tune their fluorescent properties [71]. Graphene-based fluorescent sensors are also obtained via the tuning of the GO surface and via incorporation of certain photo-active moieties for applications in sensors in various fields. Figure 4.10 shows the wide range sensing applications of graphene-based fluorescent probes for the analysis of pollutants, along with different biologically and environmentally important molecules.

FIGURE 4.10  Applications of graphene-based fluorescent sensors in various fields.

In this section, the main focus lies on the optical properties of graphenederived materials due to their photoluminescence character arising from

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GQDs, and their role as bio-sensing materials. The active photoluminescence of GQD enables it to be used as an efficient material for optical sensing. The sensing applications are carried out via the quenching of fluorescent intensity of GQD, selectively in the presence of the analyte, via Forster Resonance energy transfer (FRET) or charge transfer mechanisms [72]. Metal ions and salts at optimum concentrations are an important part of the biological and the environmental system [73], and hence their detection is of utmost importance. The first work of the use of GQDs for detection of Fe3+ [74]. S-doped GQDs have also been reported for sensing of Fe3+ in human serum via the co-ordination interactions [75]. In addition, Guo, and co-workers reported the rhodamine-B functionalized GQD (RDB-GQD) was by for the detection of Fe3+ in cancerous stem cells via the change of fluorescence from yellow to orange-red, with detection limit of 20 nM [76]. Further modifications of GQD led to many other appreciable works on the detection of Fe3+ [77–83]. GQD-derived Hg2+ sensors are found in literature and the first work for the same [84]. Developed a GQD-based sensor for the detection of mercury (Hg2+) in Hela cells, with a detection limit of 0.25 nM [85]. With improvements in research, several other notable works of Hg2+ detection were developed [86–90]. GQD-based Hg2+ sensor with the lowest LOD of 0.00248 nM [91]. GQD for the detection of lead (Pb2+), where they used GQD for the detection of cerebral Pb [92]. Subsequently, a reduced-GQD-based sensor for Pb2+, with LOD of 0.6 nM [93]. More effective GQD-derived sensors for Pb2+ have been reported in literatures [94–96]. Depicting the use of GQD for Cu2+, with LOD of 6.9 nM [97]. Other important works on sensing Cu2+ using GQDs have been reported and many more are under progress [98, 99]. The earliest known report for Ag+ detection using GQD was reported with LOD of 3.5 nM [100]. Later, based on the common charge transfer mechanism, nitrogen doped GQDs (N-GQDs) were synthesized for the selective determination of Ag+ [101]. Other notable works have also been found in the literature for selective detection of Ag+ [102–104]. Apart from the most common metal ions mentioned above, GQD has been prominently used for the detection of other metal ions, such as Al3+ [105], Cd2+ [106], Co2+ [107] and Ni2+ ions [108]. Furthermore, effective strategies have also been reported via GQD functionalization for simultaneous detecting multiple metal ions [109, 110]. An interesting the use of GQDs to simultaneously sense Cu2+, Fe3+ and Ag+ ions [111]. Lots of works are available on GQD for detection of various metal ions shown in Table 4.1 [112–124].

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TABLE 4.1  A Few Notable Works of GQD-Based Fluorescence Sensor for Detection of Metal Ions SL. Sensing System No. 1. BMIM+-functionalized GQDs prepared by electrocuting 3-D graphene Fe3+ detection 2. N-GQD from MOF-derived carbon for Fe3+ detection, via photo-induced charge transfer 3. S-GQD formed via electrolysis of graphite for sensing of Fe3+ 4. Nitrogen and amino acids functionalized GQD (NA-GQD) for sensing of Fe3+ 5. GQD derived from pyrolysis of citric acid for selective detection of Hg2+ 6. Core-satellite hybrid GQDs-based spheres for Hg2+ detection 7. GQD coordinated thymine-appended zinc phthalocyanine for Hg2+ sensing 8. Glutathione-functionalized GQD for Pb2+ detection 9. Diethyl dithiocarbamate-doped GQDs for Pb2+ detection 10. GQD from carbon nano-onion precursor for Cu2+ detection 11. GQD-based nanosensor for Cu2+ detection 12. S-GQD synthesized via hydrothermal process for Ag+ detection 13. Greenish yellow luminescent GQD for Cd2+ sensing

LOD

References

7.2 µM

[112]

80 nM

[113]

4.2 nM [114] 100 nM [115] 0.44 nM [116] 3.3 nM [117] 0.05 nM [118] 2.2 nM 3.86 nM 20 nM 20 nM 30 nM

[119] [120] [121] [122] [123]

13 nM

[124]

Graphene derived fluorescent sensors for the sensing of various important biomolecules, biomarkers, and growth factors are also in literature [125]. GO-derived fluorescent materials, and GQD are considered remarkable for the fabrication of advanced probes for biosensing [126]. Notable works involving graphene-based sensors include intracellular detection of cytochrome C using GQD, MnO2 functionalized GQD for glutathione detection [127] to name a few. Specifically, GO has been known to be functionalized to obtain fluorescent graphene material to be used as fluorescent sensors [128]. GO-derived sensors have been reported to selectively detect DA [129], adenosine [130], vascular endothelial growth factor [131], ssDNA [132], adenosine triphosphate (ATP) [133] and glucose [134]. Further, a GO-based aptasensor for sensing miRNA in living tissue samples, along with telomerase [135], and a GO-based integrin αvβ3 sensor have also been reported [136]. A GO modified sodium dodecyl benzene sulfonate-based thrombin sensor was also reported [137]. For the first time, estriol was detected using GO-based fluorescent

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sensor [138]. Gonadotropin (hormone released by anterior pituitary) sensor based on GO-aptamer conjugate [139]. Many other applications graphenebased sensors for the detection of biomolecules [140]. Other graphene-based optical sensors have been designed by functionalization of the GO with certain biomolecules, like proteins and RNA and proteins. Because of the ability of GO to bind with DNA, DNA-functionalized graphene materials have been in focus since last two decades. The aptamers, which are the single-strands of DNA, can selectively bind to the target receptors, leading to the wide-range applications in sensing, specifically for metal ions detection. Wu and the group developed a DNA-GO-based fluorescent probe for detection of Hg2+ with LOD of 0.92 nM [141]. Similarly, DNA modified GO-based sensor for Cu2+ have also been reported [142]. Other DNA-GO-based sensors to selectively detect of other metal ions, bio-analytes, and other important analytes are also found in literature [143]. Apart from metal ions and biomolecules, graphene derived fluorescent sensors are also prominently used in the detection of environmental toxic chemicals and gasses with high efficiency [144–146]. Thus, graphene can be considered as an important C-based precursor to develop of fluorescent probes for the detection of various analytes. With advancement in research, efforts are under progress to develop more advanced graphene-based portable devices and prototypes for sensing of different analytes. 4.5  GRAPHENE MATERIALS FOR ELECTRICAL BIOSENSORS With the introduction of carbon-based NMs, 2D graphene nanosheets (GNSs) are mainly investigated for the construction of biosensors because of their excellent inherent properties like electrical, chemical, and thermal properties. Further, the properties like high surface area, high electron mobility due to the presence of conjugation, high charge carrier concentrations and biocompatibility makes graphene exceptional and are under active research [147]. Moreover, the possibility of functionalizing graphene in their edges and in the basal planes make graphene-based biosensors possess surfeit advantages like as the graphene itself has low production cost, good stability, high loading efficiency, biocompatibility, etc., (Figure 4.11) which makes them advantageous over other NM-based biosensors. Hence, functionalized derivatives of graphene should be exploited judiciously in accordance to targeted applications. Among different functionalized graphenes, GQDs, GO, rGO, and polycrystalline graphene are most commonly used and suitable NM

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for fabricating biosensors [148]. GO is a matrix which consist of sp2 hybridized carbon atoms forming 2D sheets with defects being incorporated by the presence of functional groups which have oxygen and thereby disrupting a few sp2 carbon atoms into sp3 carbon atoms. The oxygenated functional groups limit the application of GO in the electrical field, however, the presence of these groups make GO hydrophilic which adds to other potential different applications. Also, these groups influence the electrochemical performance significantly in terms of the rate of heterogeneous electron transfer which can be either beneficial or unfavorable for sensing applications [149–151]. However, rGO can be achieved either by thermal or chemical reduction. Though rGO is the reduced form expected to be free of defect and oxygen functionalities, however, their complete removal is not practically applicable. Also, rGO can be further functionalized with hydrophilic moieties in its edges and basal planes which can add hydrophilic character to the rGOSs. Thus, depending on the preponderance of the hydrophilic groups, water dispersibility properties can be introduced to GO and rGO which is often crucial for biosensing. Also, high electrical property and fine selectivity with specific binding affinity of rGO sheets make them efficient biosensors [147, 152]. Further, GQDs are the zero-dimensional graphene nanocrystals with diameter range less than 20 nm; possessing exclusive properties like photoluminescent properties with edge effects and quantum confinement for biosensing applications [153–155]. However, in this chapter, graphene-based electrical biosensors will be focused specifically to limit the scope of this chapter.

FIGURE 4.11  Inherent properties of graphene.

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While considering the electrical aspect of the sensors, the most outstanding feature is that with very less power consumption, it can sense multiple operations. The measurements by these sensors can be read out by using various techniques including voltammetric, impedimetric, and potentiometric techniques. Voltammetric technique is on the basis of measurement of the current which is required to initiate an electron-transfer reaction with controlled electrode potential [156]. In the impedimetric technique, the biosensors monitor changes in the interfacial properties including conductance and capacitance at the surface of the electrode surface when target selective of the binding occur [157]. Later, in potentiometric technique, electrical potential of an electrode is measured in the absence of any voltage. The electrical aspects of graphene and their derivatives are basically based on their conjugated structure. However, their semi metallic behavior allows charge carriers to be altered from electrons to holes which enables the Dirac point by using external electric fields [148]. Further, the presence of such functional groups which have oxygen in them, number of defects, thickness, edge architecture and the impurities which are present in the graphene sheets also affect the rate of transfer of electrons in the graphene derivatives. Thus, the effective transfer of electrons from the graphene’s surface and its derivatives determines their electrochemical behavior which shows graphene as a good electrode material and therefore can be used as high performing electrochemical sensors [158, 159]. Depending on the detection of the analyte, a graphene-based electrochemical biosensor can be mainly categorized as enzyme sensor, immunesensors, and DNA sensors. These biosensors are used to detect the change coming from a chemical reaction and measure it in voltage (potentiometry), current (amperometry or voltammetry), impedance or capacitance as shown in Figure 4.12 [160]. Numerous graphene-based electrical biosensors for bioanalysis and ecological analysis have been established, and in the following section, a few different commonly used graphene-based electrical biosensors will be discussed [161, 162]. Electrical biosensors have been widely used in areas such as health care, environmental monitoring, food safety, etc. One of the widely studied examples of electrochemical enzyme biosensor is glucose sensor which is important for diagnosis of diabetes as it determines the glucose level in the body. These sensors are prepared by placing glucose oxidase enzyme (GOx) on the surface of the electrode. However, the enzyme has a protein layer which surrounds the redox-active centers of the electrode and thereby making them unable for direct electron transfer to the its interface. As graphene possesses unique properties with effective electron transfer possibilities, it is used to

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coat the electrode enabling the electron transfer directly in between electrode and enzyme in addition to easy loading of biomolecules, inherent catalysis and resistance towards biodegradation [155, 163]. GQDs, rGO, and GOs are commonly used graphene-based NMs for preparing glucose biosensors. Functionalized graphene-chitosan electrode and studied the electrochemical behavior where direct transfer of electron takes place at the modified electrode and GOx with a limit of detection (LOD) of 20 μM [164]. Electrochemically reduced carboxyl graphene (ERCGr)-modified glassy carbon electrode (ERCGr-GOD/GCE) and electrochemically reduced GO-multiwalled CNT hybrid respectively where they studied the transfer of electron directly to the GOx that was self-assembled on the electrodes surface [165, 166].

FIGURE 4.12  Representation of graphene-based electrical biosensors.

Another significant attention gained by graphene-based electrical biosensor is in the detection of H2O2 as it is a by-product in several metabolic processes and a substrate of peroxidases. H2O2 is also an essential mediator in food environmental analyzes, clinical, pharmaceutical, and industrial; and hence its detection is very crucial in various fields, such as biology, chemistry, environmental protection, and food. The significant point while developing electrodes for H2O2 detection is to minimize the oxidation/reduction overpotentials [167]. Host-guest supramolecular interactions produces cyclodextrin functionalized graphene and adamantane-modified horseradish peroxidase was prepared by and it was found that CD-functionalized graphene sensor could detect very minimum concentration of H2O2 (0.1 μM) [168]. Platinum

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NPs on graphene hybrid electrode via microwave-assisted method, which had LOD of 80 nM [169]. Dihydronicotinamide adenine dinucleotide (NADH) is a vital coenzyme required for redox reactions in various metabolic processes where NADH gets oxidized to NAD+. Therefore, electrochemical enzymatic biosensors for the detection of NAD+/NADH has received considerable interest. However, oxidation of NADH requires very high potential due to which bare electrode of the biosensor suffers poor selectivity and sensitivity [170]. Thus, fabrication of dehydrogenase-based biosensors for electrochemical oxidation of NADH is required and graphene shows promising alternative in this field. Many graphene-based biosensors have already been developed with brilliant electrolytic activity towards NADH, though researches are still going on for their betterment [171–173]. Similarly, electrical biosensors for hemoglobin is used to detect hemoglobin (Hb) level in the living organisms is one of the most important detector in the healthcare sector. As Hb plays the vital role of transporting O2 throughout the body, hence its determination is very essential for various medical purposes. Graphene-based electrodes immobilized with Hb possess enhanced the rate of transfer of electrons in the active sites of Hb and the electrode; thereby making better electrochemical sensing of Hb. Synthesized an electrode which was modified by graphene chitosan, for electroanalysis of Hb where the electrode exhibited brilliant analytical performances such as low detection limit, good stability, wider linear range, etc. [174]. Similarly, many other works have been performed for graphene-based electrodes for Hb detection [175]. Cholesterol behaves as the precursors for the bio analytes such as steroid hormones and bile acids. Thus, with increase in the cholesterol level in the living body can lead to several problems related to health such as heart diseases, atherosclerosis, and cerebral thrombosis [177]. Hence, determination of cholesterol level in the body is medically very much important, and thus research areas on fabrication of biosensors for quantitative detection of cholesterol are also gaining importance. Platinum NPs decorated graphenebased biosensor for detection of cholesterol where cholesterol esterase and cholesterol oxidase were immobilized over the Platinum particles. The prepared biosensor possessed a high level of sensitivity and very low detection limit which is due to the synergistic effect of graphene and Pt nanoparticles (NPs) [178]. In cholesterol biosensor was fabricated using graphene-ionic liquid modified cholesterol oxidase as the sensing layer [179]. Fabricated a graphene-Pt-Pd hybrid NC where with cholesterol oxidase embedded in it for detection of cholesterol level in different food samples [180].

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DA is another vital biomolecule which behave as neurotransmitter found in serum sample and thereby is an essential part of the central nervous system. DA is present in very low concentration between 0.01 mM and 1 mM, and hence precise determination of such low DA levels in the body is very important in the medical field [181]. However, other essential biomolecules such as uric acid (UA) and AA present in a living body interferes the DA determination because all the three (DA, AA, and UA) have their oxidation peak potentials in the same voltage range, and are electroactive [182]. Thus, biosensors with higher selectivity and sensitivity are required for DA detection and this can be achieved by using graphene in the electrode materials. The introduction of graphene could amplify the output signal of DA detection which can be accredited to the pi-pi interaction between the graphene basal plane and the phenyl ring of DA [181]. Several works are done, and many are still going on developing graphene-based electrochemical biosensors for precise DA detection [183–185]. DNA biosensing is another significant field which is crucial for numerous applications required in healthcare and food quality monitoring [186]. In the healthcare field, such biosensors are basically used in the diagnosis of human genetic diseases, human pathogenic diseases and DNA damage caused by different chemicals and drugs. Graphene-based electrochemical biosensors plays a significant role in sensitive and selective DNA analysis, which proceeds via non-covalent π-π stacking of the graphene sheets over the DNA strands [187]. The difference of binding affinity between the single stranded and double stranded DNA to graphene make the biosensing selective. From different studies, it was found that single stranded DNA strongly binds to graphene sheets compared to double stranded DNA, and this can be accredited to its high structural flexibility and exposed nucleobases [188]. Further, graphene-based electrochemical biosensors for DNA sensing depends on two key factors, (a) hybridization between the target and the probe DNA; and (b) direct determination of DNA bases by monitoring their oxidation [189]. Among the different biosensors, the one which is based on direct oxidation of DNA following the second principle is the simplest [22, 176]. 4.6 SUMMARY In outlines, the carbon-based materials such as C-dots, Graphene, and their derivatives have a potential for application in real biosensing applications. The main advantageous factor of using such materials are that they are

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economical, easy to prepare, sustainable, and follows green approaches. Moreover, they have low toxicity level due to which they can be applicable for the use in real biosensing applications. Because of all these factors, they are far superior as compared to that of other counterparts. Continuous efforts have been made to commercialize this technology for the real use in diagnostic purposes. Shareholders and the other respective authorities should set some specifications for these materials, which will be used for nanoprobes development because of quality assurance and to help the public to accept this technology with reliability. This concern is not just for the safety purposes but, also for the sensitivity of cultural and religious points. This factor is very much crucial as their production can create endless possibilities by considering the selection of starting precursors, surface modification, and carbonization methods. Only those products which will meet the proposed requirements are allowed for real application stage from the research stage. Thus, the development of emerging carbon-based materials and their detailed study is paving a new direction of research in the field of biosensors in the near future. KEYWORDS • • • • • • •

carbon dots carbon nanofibers Fourier transform infrared spectroscopy multi-walled carbon nanotube quantum dots single-walled carbon nanotube ultra-violet

REFERENCES 1. Achadu, O. J., & Nyokong, T., (2017). Graphene quantum dots coordinated to mercaptopyridine-substituted phthalocyanines: Characterization and application as fluorescence “turn on” nanoprobes. Spectrochimica Acta: Part A, Molecular and Biomolecular Spectroscopy, 174, 339–347. https://doi.org/10.1016/j.saa.2016.11.043. 2. Achadu, O. J., & Nyokong, T., (2017). Application of graphene quantum dots functionalized with thymine and thymine-appended zinc phthalocyanine as Novel

116

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photoluminescent nanoprobes. New Journal of Chemistry, 41(4), 1447–1458. https:// doi.org/10.1039/C6NJ03285K. 3. Aiyer, S., Prasad, R., Kumar, M., Nirvikar, K., Jain, B., & Kushwaha, O. S., (2016). Fluorescent carbon nanodots for targeted in vitro cancer cell imaging. Applied Materials Today, 4, 71–77. https://doi.org/10.1016/j.apmt.2016.07.001. 4. Akca, S., Foroughi, A., Frochtzwajg, D., & Postma, H. W. C., (2011). Competing interactions in DNA assembly on graphene. Plos One, 6(4), e18442. https://doi. org/10.1371/journal.pone.0018442. 5. Anas, N. A. A., Fen, Y. W., Omar, N. A. S., Daniyal, W. M. E. M. M., Ramdzan, N. S. M., & Saleviter, S., (2019). Development of graphene quantum dots-based optical Sensor for toxic metal ion detection. Sensors, 19(18), 3850. https://doi.org/10.3390/s19183850. 6. Ananthanarayanan, A., Wang, X., Routh, P., Sana, B., Lim, S., Kim, D. H., Lim, K. H., Li, J., & Chen, P., (2014). Facile synthesis of graphene quantum dots from 3D graphene and their application for Fe3+ Sensing. Advanced Functional Materials, 24(20), 3021–3026. https://doi.org/10.1002/adfm.201303441. 7. Anh, N. T. N., Chowdhury, A. D., & Doong, R., (2017). Highly sensitive and selective detection of mercury ions using N, S-codoped graphene quantum dots and its paper strip based sensing application in wastewater. Sensors and Actuators. Part B, 252, 1169–1178. https://doi.org/10.1016/j.snb.2017.07.177. 8. Arvinte, A., Valentini, F., Radoi, A., Arduini, F., Tamburri, E., Rotariu, L., Palleschi, G., & Bala, C., (2007). The NADH electrochemical detection performed at carbon nanofibers modified glassy carbon electrode. Electroanalysis, 19(14), 1455–1459. https://doi.org/10.1002/elan.200703879. 9. Bagherzadeh, M., & Farahbakhsh, M., (2015). Chapter 2. Surface functionalization of grapheme. In: Tiwari, A., & Syvajarvi, M., (eds.), Graphene Materials: Fundamentals and Emerging Applications (pp. 25–65). John Wiley & Sons. 10. Bai, Y., Xu, T., & Zhang, X., (2020). Graphene-based biosensors for detection of biomarkers. Micromachines, 11(1), 60. https://doi.org/10.3390/mi11010060. 11. Bian, S., Shen, C., Hua, H., Zhou, L., Zhu, H., Xi, F., Liu, J., & Dong, X., (2016). One-pot synthesis of sulfur-doped graphene quantum dots as a novel fluorescent probe for highly selective and sensitive detection of lead(II). RSC Advances, 6(74), 69977–69983. https:// doi.org/10.1039/C6RA10836A. 12. Bian, S., Shen, C., Qian, Y., Liu, J., Xi, F., & Dong, X., (2017). Facile synthesis of sulfur-doped graphene quantum dots as fluorescent sensing probes for Ag+ ions detection. Sensors and Actuators Part B, 242, 231–237. https://doi.org/10.1016/j.snb. 2016.11.044. 13. Bottini, M., Balasubramanian, C., Dawson, M. I., Bergamaschi, A., Bellucci, S., & Mustelin, T., (2006). Isolation and characterization of fluorescent nanoparticles from pristine and oxidized electric arc-produced single-walled carbon nanotubes. Journal of Physical Chemistry B, 110(2), 831–836. https://doi.org/10.1021/jp055503b. 14. Bo, X., Bai, J., Qi, B., & Guo, L., (2011). Ultra-fine Pt nanoparticles supported on ionic liquid polymer-functionalized ordered mesoporous carbons for nonenzymatic hydrogen peroxide detection. Biosensors and Bioelectronics, 28(1), 77–83. https://doi. org/10.1016/j.bios.2011.07.001. 15. Britto, P. J., Santhanam, K. S. V., & Ajayan, P. M., (1996). Carbon nanotube electrode for oxidation of dopamine. Bioelectrochemistry and Bioenergetics, 41(1), 121–125. https://doi.org/10.1016/0302-4598(96)05078-7.

Carbon Nanomaterials for Optical and Electrical Biosensors 117 16. Brownson, D. A., & Banks, C. E., (2010). Graphene electrochemistry: An overview of potential applications. Analyst, 135(11), 2768–2778. https://doi.org/10.1039/c0an00590h. 17. Cao, S., Zhang, L., Chai, Y., & Yuan, R., (2013). An Integrated Sensing System for Detection of cholesterol based on TiO2-graphene–Pt–Pd hybridnanocomposites. Biosensors and Bioelectronics, 42, 532–538. https://doi.org/10.1016/j.bios.2012.10.048. 18. Chakraborti, H., Sinha, S., Ghosh, S., & Pal, S. K., (2013). Interfacing water soluble nanomaterials with fluorescence chemosensing: Graphene quantum dot to detect Hg2+ in 100% aqueous solution. Materials Letters, 97, 78–80. https://doi.org/10.1016/j.matlet. 2013.01.094. 19. Chang, H., Tang, L., Wang, Y., Jiang, J., & Li, J., (2010). Graphene fluorescence resonance energy transfer aptasensor for the thrombin detection. Analytical Chemistry, 82(6), 2341–2346. https://doi.org/10.1021/ac9025384. 20. Chang, J., Zhou, G., Christensen, E. R., Heideman, R., & Chen, J., (2014). Graphene-based sensors for detection of heavy metals in Water: A review. Analytical and Bioanalytical Chemistry, 406(16), 3957–3975. https://doi.org/10.1007/s00216-014-7804-x. 21. Chauhan, N., Maekawa, T., & Kumar, D. N. S., (2017). Graphene based biosensorsaccelerating medical diagnostics to new-dimensions. Journal of Materials Research, 32(15), 2860–2882. https://doi.org/10.1557/jmr.2017.91. 22. Zoski, C. G., (2006). Handbook of Electrochemistry (1st edn., p. 934). Elsevier. 23. Che, G., Lakshmi, B. B., Fisher, E. R., & Martin, C. R., (1998). Carbon nanotubule membranes for electrochemical energy storage and production. Nature, 393(6683), 346–349. https://doi.org/10.1038/30694. 24. Chen, H., Xie, Y., Kirillov, A. M., Liu, L., Yu, M., Liu, W., & Tang, Y., (2015). A ratiometric fluorescent nanoprobe based on terbium functionalized carbon dots for highly sensitive detection of an anthrax biomarker. Chemical Communications, 51(24), 5036–5039. https://doi.org/10.1039/c5cc00757g. 25. Chen, H., Li, W., Wang, Q., Jin, X., Nie, Z., & Yao, S., (2016). Nitrogen-doped graphene quantum dots based single-luminophor generated dual-potential electrochemiluminescence system for ratiometric sensing of Co2+. Electrochimica Acta, 214, 94–102. https:// doi.org/10.1016/j.electacta.2016.08.028. 26. Chen, J. L., Yan, X. P., Meng, K., & Wang, S. F., (2011). Graphene oxide based photoinduced charge transfer label-free near-infrared fluorescent biosensor for dopamine. Analytical Chemistry, 83(22), 8787–8793. https://doi.org/10.1021/ac2023537. 27. Chen, L., Wu, C., Du, P., Feng, X., Wu, P., & Cai, C., (2017). Electrolyzing synthesis of boron-doped graphene quantum dots for fluorescence determination of Fe3+ ions in water samples. Talanta, 164, 100–109. https://doi.org/10.1016/j.talanta.2016.11.019. 28. Cheng, H., Chen, X., Yu, H., Guo, M., Chang, Y., & Zhang, G., (2020). Hierarchically porous N, P-codoped carbon materials for high-performance supercapacitors. ACS Applied Energy Materials, 3(10), 10080–10088. https://doi.org/10.1021/acsaem.0c01771. 29. Chung, C., Kim, Y. K., Shin, D., Ryoo, S. R., Hong, B. H., & Min, D. H., (2013). Biomedical applications of graphene and graphene oxide. Accounts of Chemical Research, 46(10), 2211–2224. https://doi.org/10.1021/ar300159f. 30. Clark, L. C., & Lyons, C., (1962). Electrode systems for continuous monitoring in cardiovascular surgery. Annals of the New York Academy of Sciences, 102, 29–45. https://doi.org/10.1111/j.1749-6632.1962.tb13623.x. 31. Damborský, P., Švitel, J., & Katrlík, J., (2016). Optical biosensors. Essays in Biochemistry, 60(1), 91–100. https://doi.org/10.1042/EBC20150010.

118

Sustainable Nanomaterials for Biosystems Engineering

32. Das, R., Dhar, N., Bandyopadhyay, A., & Jana, D., (2016). Size dependent magnetic and optical properties in diamond shaped graphene quantum dots: A DFT study. Journal of Physics and Chemistry of Solids, 99, 34–42. https://doi.org/10.1016/j.jpcs.2016.08.004. 33. Deore, B. A., & Freund, M. S., (2005). Reactivity of poly(anilineboronic acid) with NAD+ and NADH. Chemistry of Materials, 17(11), 2918–2923. https://doi.org/10.1021/ cm050647o. 34. Dey, D., & Goswami, T., (2011). Optical biosensors: A revolution towards quantum nanoscale electronics device fabrication. Journal of Biomedicine and Biotechnology, 2011, 348218. https://doi.org/10.1155/2011/348218. 35. Dey, R. S., & Raj, C. R., (2013). Redox-functionalized graphene oxide architecture for the development of amperometric biosensing platform. ACS Applied Materials and Interfaces, 5(11), 4791–4798. https://doi.org/10.1021/am400280u. 36. Dey, R. S., & Raj, C. R., (2010). Development of an amperometric cholesterol biosensor based on graphene-Pt nanoparticle hybrid material. Journal of Physical Chemistry C, 114(49), 21427–21433. https://doi.org/10.1021/jp105895a. 37. Drummond, T. G., Hill, M. G., & Barton, J. K., (2003). Electrochemical DNA sensors. Nature Biotechnology, 21(10), 1192–1199. https://doi.org/10.1038/nbt873. 38. Fabiani, L., Saroglia, M., Galatà, G., De Santis, R., Fillo, S., Luca, V., Faggioni, G., et al., (2021). Magnetic beads combined with carbon black-based screen-printed electrodes for COVID-19: A reliable and miniaturized electrochemical immunosensor for SARS-CoV-2 detection in saliva. Biosensors and Bioelectronics, 171, 112686. https://doi.org/10.1016/j. bios.2020.112686. 39. Fang, B. Y., Li, C., Song, Y. Y., Tan, F., Cao, Y. C., & Zhao, Y. D., (2018). Nitrogendoped graphene quantum dot for direct fluorescence detection of Al3+ in aqueous media and living Cells. Biosensors and Bioelectronics, 100, 41–48. https://doi.org/10.1016/j. bios.2017.08.057. 40. Freire, R. M., Le, N. D. B., Jiang, Z., Kim, C. S., Rotello, V. M., & Fechine, P. B. A., (2018). NH2-rich carbon quantum dots: A protein-responsive probe for detection and identification. Sensors and Actuators. Part B, 255, 2725–2732. https://doi.org/10.1016/j. snb.2017.09.085. 41. Gao, L., Ju, L., & Cui, H., (2017). Chemiluminescent and fluorescent dual-signal graphene quantum dots and their application in pesticide sensing arrays. Journal of Materials Chemistry C, 5(31), 7753–7758. https://doi.org/10.1039/C7TC01658A. 42. Gasnier, A., Laura, P. M. L., Rubianes, M. D., & Rivas, G. A., (2013). Graphene paste electrode: Electrochemical behavior and analytical applications for the quantification of NADH. Sensors and Actuators. Part B, 176, 921–926. https://doi.org/10.1016/j. snb.2012.09.092. 43. Gholivand, M. B., & Khodadadian, M., (2014). Amperometric cholesterol biosensor based on the direct electrochemistry of cholesterol oxidase and catalase on a graphene/ ionic liquid-modified glassy carbon electrode. Biosensors and Bioelectronics, 53, 472–478. https://doi.org/10.1016/j.bios.2013.09.074. 44. Guo, R., Zhou, S., Li, Y., Li, X., Fan, L., & Voelcker, N. H., (2015). Rhodaminefunctionalized graphene quantum dots for detection of Fe3+ in cancer stem cells. ACS Applied Materials and Interfaces, 7(43), 23958–23966. https://doi.org/10.1021/acsami. 5b06523. 45. Guo, S., Dong, S., & Wang, E., (2010). Three-dimensional Pt-on-Pd bimetallic nanodendrites supported on graphene nanosheet: Facile synthesis and used as an

Carbon Nanomaterials for Optical and Electrical Biosensors 119 advanced nano-electrocatalyst for methanol oxidation. ACS Nano, 4(1), 547–555. https://doi.org/10.1021/nn9014483. 46. He, Y., Huang, G., & Cui, H., (2013). Quenching the chemiluminescence of acridinium ester by graphene oxide for label-free and homogeneous DNA detection. ACS Applied Materials and Interfaces, 5(21), 11336–11340. https://doi.org/10.1021/am404138x. 47. He, S., Qu, L., Tan, Y., Liu, F., Wang, Y., Zhang, W., Cai, Z., et al., (2017). A fluorescent aptasensor with product-triggered amplification by exonuclease III digestion for highly sensitive ATP detection. Analytical Methods, 9(33), 4837–4842. https://doi.org/10.1039/ C7AY01473B. 48. He, Y., Sheng, Q., Zheng, J., Wang, M., & Liu, B., (2011). Magnetite-graphene for the direct electrochemistry of hemoglobin and its biosensing application. Electrochimica Acta, 56(5), 2471–2476. https://doi.org/10.1016/j.electacta.2010.11.020. 49. Hua, M., Wang, C., Qian, J., Wang, K., Yang, Z., Liu, Q., Mao, H., & Wang, K., (2015). Preparation of graphene quantum dots based core-satellite hybrid spheres and their use as the ratiometric fluorescence probe for visual determination of mercury(II) ions. Analytica Chimica Acta, 888, 173–181. https://doi.org/10.1016/j.aca.2015.07.042. 50. Huang, H., Li, Z., She, J., & Wang, W., (2012). Oxygen density dependent band gap of reduced graphene oxide. Journal of Applied Physics, 111(5). https://doi.org/10.1063/ 1.3694665, PubMed: 054317. 51. Huang, H., Liao, L., Xu, X., Zou, M., Liu, F., & Li, N., (2013). The electron-transfer based interaction between transition metal ions and photoluminescent graphene quantum dots (Gqds): A platform for metal ion sensing. Talanta, 117, 152–157. https://doi.org/ 10.1016/j.talanta.2013.08.055. 52. Huang, J., Liu, Y., & You, T., (2010). Carbon nanofiber based electrochemical biosensors: A review. Analytical Methods, 2(3), 202–211. https://doi.org/10.1039/b9ay00312f. 53. Huang, J., Wang, D., Hou, H., & You, T., (2008). Electrospun palladium nanoparticleloaded carbon nanofibers and their electrocatalytic activities towards hydrogen peroxide and NADH. Advanced Functional Materials, 18(3), 441–448. https://doi.org/10.1002/ adfm.200700729. 54. Huang, P., Lin, J., Wang, X., Wang, Z., Zhang, C., He, M., Wang, K., et al., (2012). Light-triggered theranostics based on photosensitizer-conjugated carbon dots for simultaneous enhanced-fluorescence imaging and photodynamic therapy. Advanced Materials, 24(37), 5104–5110. https://doi.org/10.1002/adma.201200650. 55. Huang, Y., Liu, X., Zhang, L., Hu, K., Zhao, S., Fang, B., Chen, Z. F., & Liang, H., (2015). Nicking enzyme and graphene oxide-based dual signal amplification for ultrasensitive aptamer-based fluorescence polarization assays. Biosensors and Bioelectronics, 63, 178–184. https://doi.org/10.1016/j.bios.2014.07.036. 56. Ji, X., Banks, C. E., Crossley, A., & Compton, R. G., (2006). Oxygenated edge plane sites slow the electron transfer of the ferro-/Ferricyanide redox couple at graphite electrodes. ChemPhysChem, 7(6), 1337–1344. https://doi.org/10.1002/cphc.200600098. 57. Justino, C. I. L., Gomes, A. R., Freitas, A. C., Duarte, A. C., & Rocha-Santos, T. A. P., (2017). Graphene based sensors and biosensors. TrAC Trends in Analytical Chemistry, 91, 53–66. https://doi.org/10.1016/j.trac.2017.04.003. 58. Ju, J., & Chen, W., (2014). Synthesis of highly fluorescent nitrogen-doped graphene quantum dots for sensitive, label-free detection of Fe (III) in aqueous media, Label. Biosensors and Bioelectronics, 58, 219–225. https://doi.org/10.1016/j.bios.2014.02.061.

120

Sustainable Nanomaterials for Biosystems Engineering

59. Kaewprom, C., Sricharoen, P., Limchoowong, N., Nuengmatcha, P., & Chanthai, S., (2019). Resonance light scattering sensor of the metal complex nanoparticles using diethyl dithiocarbamate doped graphene quantum dots for Highly Pb(II)-sensitive detection in water sample. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy, 207, 79–87. https://doi.org/10.1016/j.saa.2018.09.002. 60. Kaewanan, P., Sricharoen, P., Limchoowong, N., Sripakdee, T., Nuengmatcha, P., & Chanthai, S., (2017). A fluorescence switching sensor based on graphene quantum dots decorated with Hg2+ and hydrolyzed thioacetamide for highly Ag+ sensitive and selective detection. RSC Advances, 7(76), 48058–48067. https://doi.org/10.1039/C7RA09126E. 61. Kang, X., Wang, J., Wu, H., Aksay, I. A., Liu, J., & Lin, Y., (2009). Glucose oxidase– graphene–chitosan modified electrode for direct electrochemistry and glucose sensing. Biosensors and Bioelectronics, 25(4), 901–905. https://doi.org/10.1016/j.bios. 2009.09.004. 62. Kaur, M., Mehta, S. K., & Kansal, S. K., (2017). A fluorescent probe based on nitrogen doped graphene quantum dots for turn off sensing of explosive and detrimental water pollutant, TNP in aqueous medium. Spectrochimica Acta: Part A, Molecular and Biomolecular Spectroscopy, 180, 37–43. https://doi.org/10.1016/j.saa.2017.02.035. 63. Kim, M., Iezzi, Jr. R., Shim, B. S., & Martin, D. C., (2019). Impedimetric biosensors for detecting vascular endothelial growth factor (VEGF) based on poly(3,4-ethylene dioxythiophene)(PEDOT)/gold nanoparticle (Au NP) composites. Frontiers in Chemistry, 7, 234. https://doi.org/10.3389/fchem.2019.00234. 64. Kushwaha, H. S., Sao, R., & Vaish, R., (2014). Label free selective detection of estriol using graphene oxide-based fluorescence sensor. Journal of Applied Physics, 116(3). https://doi.org/10.1063/1.4890024, PubMed: 034701. 65. Lan, G., Nong, J., Wei, W., Liu, X., Luo, P., Jin, W., et al., (2020). Highly-stable all-in-one photoelectrochemical electrodes based on carbon nanowall. Nanotechnology, 31(33), 335401. https://doi.org/10.1088/1361–6528/ab8cf5. 66. Li, H., Liu, J., Guo, S., Zhang, Y., Huang, H., Liu, Y., & Kang, Z., (2015). Carbon dots from PEG for highly sensitive detection of levodopa. Journal of Materials Chemistry. B, 3(11), 2378–2387. https://doi.org/10.1039/c4tb01983k. 67. Li, F., Chai, J., Yang, H., Han, D., & Niu, L., (2010). Synthesis of Pt/ionic liquid/ graphene nanocomposite and its simultaneous determination of ascorbic acid and dopamine. Talanta, 81(3), 1063–1068. https://doi.org/10.1016/j.talanta.2010.01.061. 68. Li, L., Li, L., Wang, C., Liu, K., Zhu, R., Qiang, H., & Lin, Y., (2015). Synthesis of nitrogen-doped and amino acid-functionalized graphene quantum dots from glycine, and their application to the fluorometric determination of ferric. Microchimica Acta, 182(3, 4), 763–770. https://doi.org/10.1007/s00604-014-1383-6. 69. Li, L. L., Ji, J., Fei, R., Wang, C. Z., Lu, Q., Zhang, J. R., Jiang, L. P., et al., (2012). A Facile Microwave avenue to electrochemiluminescent two-color graphene quantum dots. Advanced Functional Materials, 22(14), 2971–2979. https://doi.org/10.1002/ adfm.201200166. 70. Li, L., Lu, H., & Deng, L., (2013). A sensitive NADH and ethanol biosensor based on graphene-Au nanorods nanocomposites. Talanta, 113, 1–6. https://doi.org/10.1016/j. talanta.2013.03.074. 71. Li, M., Zhou, X., Ding, W., Guo, S., & Wu, N., (2013). Fluorescent aptamer functionalized graphene oxide biosensor for label-free detection of mercury(II). Biosensors and Bioelectronics, 41, 889–893. https://doi.org/10.1016/j.bios.2012.09.060.

Carbon Nanomaterials for Optical and Electrical Biosensors 121 72. Li, P., Chen, X., & Yang, W., (2013). Graphene-induced self-assembly of peptides into macroscopic-scale organized nanowire arrays for electrochemical NADH Sensing. Langmuir, 29(27), 8629–8635. https://doi.org/10.1021/la401881a. 73. Li, S. J., He, J. Z., Zhang, M. J., Zhang, R. X., Lv, X. L., Li, S. H., & Pang, H., (2013). Electrochemical detection of dopamine using water-soluble sulfonated graphene. Electrochimica Acta, 102, 58–65. https://doi.org/10.1016/j.electacta.2013.03.176. 74. Li, S., Li, Y., Cao, J., Zhu, J., Fan, L., & Li, X., (2014). Sulfur-doped graphene quantum dots as a novel fluorescent probe for highly selective and sensitive detection of Fe3+. Analytical Chemistry, 86(20), 10201–10207. https://doi.org/10.1021/ac503183y. 75. Li, Y., Chen, T., & Ma, Y., (2016). Nanosized carbon dots from organic matter and biomass. Journal of Wuhan University of Technology-Mater. Sci. Ed, 31(4), 823–826. https://doi.org/10.1007/s11595-016-1452-2. 76. Li, Y., Liu, X., Li, Q., Ge, J., Liu, H., Li, S., Wang, L., et al., (2016). Post-oxidation treated graphene quantum dots as a fluorescent probe for sensitive detection of copper ions. Chemical Physics Letters, 664, 127–132. https://doi.org/10.1016/j.cplett.2016.10.030. 77. Li, Z., Wang, Y., Ni, Y., & Kokot, S., (2015). A rapid and label-free dual detection of Hg (II) and cysteine with the use of fluorescence switching of graphene quantum dots. Sensors and Actuators. Part B, 207, 490–497. https://doi.org/10.1016/j.snb.2014.10.071. 78. Liang, B., Fang, L., Yang, G., Hu, Y., Guo, X., & Ye, X., (2013). Direct electron transfer glucose biosensor based on glucose oxidase self-assembled on electrochemically reduced carboxyl graphene. Biosensors and Bioelectronics, 43, 131–136. https://doi. org/10.1016/j.bios.2012.11.040. 79. Lin, L., Song, X., Chen, Y., Rong, M., Wang, Y., Zhao, L., Zhao, T., & Chen, X., (2015). Europium-decorated graphene quantum dots as a fluorescent probe for label-free, rapid, and sensitive detection of Cu2+ and L-cysteine. Analytica Chimica Acta, 891, 261–268. https://doi.org/10.1016/j.aca.2015.08.011. 80. Liu, C., Zhang, P., Zhai, X., Tian, F., Li, W., Yang, J., Liu, Y., et al., (2012). Nanocarrier for gene delivery and bioimaging based on carbon dots with PEI-passivation enhanced fluorescence. Biomaterials, 33(13), 3604–3613. https://doi.org/10.1016/j. biomaterials.2012.01.052. 81. Liu, Y., Hou, H., & You, T., (2008). Synthesis of carbon nanofibers for mediator less sensitive detection of NADH. Electroanalysis, 20(15), 1708–1713. https://doi.org/10.1002/ elan.200804242. 82. Liu, Z., Liu, B., Ding, J., & Liu, J., (2014). Fluorescent sensors using DNA-functionalized graphene oxide. Analytical and Bioanalytical Chemistry, 406(27), 6885–6902. https:// doi.org/10.1007/s00216-014-7888-3. 83. Loi, E., Ng, R. W. C., Chang, M. M. F., Fong, J. F. Y., Ng, Y. H., & Ng, S. M., (2017). One-pot synthesis of carbon dots using two different acids and their respective unique photoluminescence property. Luminescence, 32(1), 114–118. https://doi.org/10.1002/ bio.3157. 84. Lü, M., Li, J., Yang, X., Zhang, C., Yang, J., Hu, H., & Wang, X., (2013). Applications of graphene-based materials in environmental protection and detection. Chinese Science Bulletin, 58(22), 2698–2710. https://doi.org/10.1007/s11434-013-5887-y. 85. Lu, L. M., Qiu, X. L., Zhang, X. B., Shen, G. L., Tan, W., & Yu, R. Q., (2013). Supramolecular assembly of enzyme on functionalized graphene for electrochemical biosensing. Biosensors and Bioelectronics, 45, 102–107. https://doi.org/10.1016/j.bios. 2013.01.065.

122

Sustainable Nanomaterials for Biosystems Engineering

86. Luo, H., Shi, Z., Li, N., Gu, Z., & Zhuang, Q., (2001). Investigation of the electrochemical and electrocatalytic behavior of single-wall carbon nanotube film on a glassy carbon electrode. Analytical Chemistry, 73(5), 915–920. https://doi.org/10.1021/ac000967l. 87. Ma, Y., Cen, Y., Sohail, M., Xu, G., Wei, F., Shi, M., Xu, X., et al., (2017). A ratiometric fluorescence universal platform based on N, Cu codoped carbon dots to detect metabolites participating in H2O2-generation reactions. ACS Applied Materials and Interfaces, 9(38), 33011–33019. https://doi.org/10.1021/acsami.7b10548. 88. Maldonado, S., & Stevenson, K. J., (2005). Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes. Journal of Physical Chemistry B, 109(10), 4707–4716. https://doi.org/10.1021/jp044442z. 89. Mandal, M., Maitra, A., Das, T., & Das, C. K., (2015). Chapter 1. Graphene and related two-dimensional materials. In: Tiwari, A., & Syvajarvi, M., (eds.), Graphene Materials: Fundamentals and Emerging Applications (pp. 1–23). John Wiley & Sons. 90. Mani, V., Devadas, B., & Chen, S. M., (2013). Direct electrochemistry of glucose oxidase at electrochemically reduced graphene oxide-multiwalled carbon nanotubes hybrid material modified electrode for glucose biosensor. Biosensors and Bioelectronics, 41, 309–315. https://doi.org/10.1016/j.bios.2012.08.045. 91. Mansuriya, B. D., & Altintas, Z., (2019). Graphene quantum dot based electrochemical immunosensors for biomedical applications. Materials, 13(1), 96. https://doi.org/10.3390/ ma13010096. 92. McCreery, R. L., (2008). Advanced carbon electrode materials for molecular electrochemistry. Chemical Reviews, 108(7), 2646–2687. https://doi.org/10.1021/cr068076m. 93. Menon, S., Mathew, M. R., Sam, S., Keerthi, K., & Kumar, K. G., (2020). Recent advances and challenges in electrochemical biosensors for emerging and re-emerging infectious diseases. Journal of Electroanalytical Chemistry, 878, 114596. https://doi. org/10.1016/j.jelechem.2020.114596. 94. Morales-Narváez, E., Baptista-Pires, L., Zamora-Gálvez, A., & Merkoçi, A., (2017). Graphene-based biosensors: Going simple. Advanced Materials, 29(7). https://doi. org/10.1002/adma.201604905, PubMed: 27896856. 95. Mohammadi, Z., & Jafari, S. M., (2020). Detection of food spoilage and adulteration by Novel nanomaterial-based sensors. Advances in Colloid and Interface Science, 286, 102297. https://doi.org/10.1016/j.cis.2020.102297. 96. Motaghi, H., Mehrgardi, M. A., & Bouvet, P., (2017). Carbon dots-AS1411 aptamer nanoconjugate for ultrasensitive spectrofluorometric detection of cancer cells. Scientific Reports, 7(1), 10513. https://doi.org/10.1038/s41598-017-11087-2. 97. Castro, N. A. H., Guinea, F., Peres, N. M. R., Novoselov, K. S., & Geim, A. K., (2009). The electronic properties of graphene. Reviews of Modern Physics, 81(1), 109–162. https://doi.org/10.1103/RevModPhys.81.109. 98. Ng, S. M., (2019). Chapter 12. Carbon dots as optical nanoprobes for biosensors. In: Gobinath, S. C. B., & Lakshmipriya, T., (eds.), Nanobiosensors for biomolecular targeting (pp. 269–300). Elsevier Publishing. 99. Ngu, P. Z. Z., Chia, S. P. P., Fong, J. F. Y., & Ng, S. M., (2016). Synthesis of carbon nanoparticles from waste rice husk used for the optical sensing of metal ions. New Carbon Materials, 31(2), 135–143. https://doi.org/10.1016/S1872-5805(16)60008-2. 100. Niu, X., Zhong, Y., Chen, R., Wang, F., Liu, Y., & Luo, D. A., (2018). ‘Turn-on’ fluorescence sensor for Pb2+ detection based on graphene quantum dots and gold nanoparticles. Sensors and Actuators. Part B, 255, 1577–1581. https://doi.org/10.1016/j.snb.2017.08.167.

Carbon Nanomaterials for Optical and Electrical Biosensors 123 101. Niwa, O., Jia, J., Sato, Y., Kato, D., Kurita, R., Maruyama, K., Suzuki, K., & Hirono, S., (2006). Electrochemical performance of angstrom level flat sputtered carbon film consisting of sp2 and sp3 mixed bonds. Journal of the American Chemical Society, 128(22), 7144–7145. https://doi.org/10.1021/ja060609l. 102. Ou, X., Zhan, S., Sun, C., Cheng, Y., Wang, X., Liu, B., Zhai, T., et al., (2019). Simultaneous detection of telomerase and Mirna with graphene oxide-based fluorescent aptasensor in living Cells and tissue samples. Biosensors and Bioelectronics, 124–125, 199–204. https://doi.org/10.1016/j.bios.2018.10.009. 103. Park, C. S., Yoon, H., & Kwon, O. S., (2016). Graphene-based nano-electronic biosensors. Journal of Industrial and Engineering Chemistry, 38, 13–22. https://doi.org/10.1016/j. jiec.2016.04.021. 104. Park, S. Y., Lee, H. U., Park, E. S., Lee, S. C., Lee, J. W., Jeong, S. W., Kim, C. H., et al., (2014). Photoluminescent green carbon nanodots from food-waste-derived sources: Large-scale synthesis, properties, and biomedical applications. ACS Applied Materials and Interfaces, 6(5), 3365–3370. https://doi.org/10.1021/am500159p. 105. Pasinszki, T., Krebsz, M., Tung, T. T., & Losic, D., (2017). Carbon nanomaterial based biosensors for non-invasive detection of cancer and disease biomarkers for clinical diagnosis. Sensors, 17(8), 1919. https://doi.org/10.3390/s17081919. 106. Qaddare, S. H., & Salimi, A., (2017). Amplified fluorescent sensing of DNA using luminescent carbon dots and AuNPs/GO as a sensing platform: A novel coupling of FRET and DNA hybridization for homogeneous HIV-1 gene detection at femtomolar level. Biosensors and Bioelectronics, 89(2), 773–780. https://doi.org/10.1016/j.bios.2016.10.033. 107. Qi, Y. X., Zhang, M., Fu, Q. Q., Liu, R., & Shi, G. Y., (2013). Highly sensitive and selective fluorescent detection of cerebral lead(II) based on graphene quantum dot conjugates. Chemical Communications, 49(90), 10599–10601. https://doi.org/10.1039/c3cc46059b. 108. Qian, Z. S., Shan, X. Y., Chai, L. J., Chen, J. R., & Feng, H., (2015). A fluorescent nanosensor based on graphene quantum dots-aptamer probe and graphene oxide platform for detection of lead(II). Biosensors and Bioelectronics, 68, 225–231. https:// doi.org/10.1016/j.bios.2014.12.057. 109. Qian, Z. S., Shan, X. Y., Chai, L. J., Ma, J. J., Chen, J. R., & Feng, H., (2014). A universal fluorescence sensing strategy based on biocompatible graphene quantum dots and graphene oxide for the detection of DNA. Nanoscale, 6(11), 5671–5674. https://doi. org/10.1039/c3nr06583a. 110. Qu, C., Zhang, D., Yang, R., Hu, J., & Qu, L., (2019). Nitrogen and sulfur codoped graphene quantum dots for the highly sensitive and selective detection of mercury Ion in living cells. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 206, 588–596. https://doi.org/10.1016/j.saa.2018.07.097. 111. Ran, X., Sun, H., Pu, F., Ren, J., & Qu, X., (2013). Ag nanoparticle-decorated graphene quantum dots for label-free, rapid, and sensitive detection of Ag+ and biothiols. Chemical Communications, 49(11), 1079–1081. https://doi.org/10.1039/c2cc38403e. 112. Shang, N. G., Papakonstantinou, P., McMullan, M., Chu, M., Stamboulis, A., Potenza, A., Dhesi, S. S., & Marchetto, H., (2008). Catalyst-free efficient growth, orientation, and biosensing properties of multilayer graphene nanoflake films with sharp edge planes. Advanced Functional Materials, 18(21), 3506–3514. https://doi.org/10.1002/ adfm.200800951. 113. Shao, Y., Wang, J., Wu, H., Liu, J., Aksay, I., & Lin, Y., (2010). Graphene based electrochemical sensors and biosensors: A review. Electroanalysis, 22(10), 1027–1036. https://doi.org/10.1002/elan.200900571.

124

Sustainable Nanomaterials for Biosystems Engineering

114. Sharma, D., Kanchi, S., Sabela, M. I., & Bisetty, K., (2016). Insight into the biosensing of graphene oxide: Present and future prospects. Arabian Journal of Chemistry, 9(2), 238–261. https://doi.org/10.1016/j.arabjc.2015.07.015. 115. Shen, C., Ge, S., Pang, Y., Xi, F., Liu, J., Dong, X., & Chen, P., (2017). Facile and scalable preparation of highly luminescent N, S codoped graphene quantum dots and their application for parallel detection of multiple metal ions. Journal of Materials Chemistry. B, 5(32), 6593–6600. https://doi.org/10.1039/c7tb00506g. 116. Shen, P., & Xia, Y., (2014). Synthesis-modification integration: One-step fabrication of boronic acid functionalized carbon dots for fluorescent blood sugar sensing. Analytical Chemistry, 86(11), 5323–5329. https://doi.org/10.1021/ac5001338. 117. Shi, B., Zhang, L., Lan, C., Zhao, J., Su, Y., & Zhao, S., (2015). One-pot green synthesis of oxygen-rich nitrogen-doped graphene quantum dots and their potential application in pH-sensitive photoluminescence and detection of mercury(II) ions. Talanta, 142, 131–139. https://doi.org/10.1016/j.talanta.2015.04.059. 118. Shi, Y., Li, C., Liu, S., Liu, Z., Zhu, J., Yang, J., & Hu, X., (2015). Facile synthesis of fluorescent carbon dots for determination of curcumin based on fluorescence resonance energy transfer. RSC Advances, 5(79), 64790–64796. https://doi.org/10.1039/ C5RA13404H. 119. Shih, Y. W., Tseng, G. W., Hsieh, C. Y., Li, Y. Y., & Sakoda, A., (2014). Graphene quantum dots derived from platelet graphite nanofibers by liquid-phase exfoliation. Acta Materialia, 78, 314–319. https://doi.org/10.1016/j.actamat.2014.06.027. 120. Song, J., Xu, L., Zhou, C., Xing, R., Dai, Q., Liu, D., & Song, H., (2013). Synthesis of graphene oxide based Cuo nanoparticles composite electrode for highly enhanced nonenzymatic glucose detection. ACS Applied Materials and Interfaces, 5(24), 12928– 12934. https://doi.org/10.1021/am403508f. 121. Sternschulte, H., Thonke, K., Sauer, R., & Koizumi, S., (1999). Optical evidence for 630-meV phosphorus donor in synthetic diamond. Physical Review Part B, 59(20), 12924–12927. https://doi.org/10.1103/PhysRevB.59.12924. 122. Sun, H., Gao, N., Wu, L., Ren, J., Wei, W., & Qu, X., (2013). Highly photoluminescent amino-functionalized graphene quantum dots used for sensing copper ions. Chemistry, 19(40), 13362–13368. https://doi.org/10.1002/chem.201302268. 123. Sun, X., Peng, Y., Lin, Y., Cai, L., Li, F., & Liu, B., (2018). G-quadruplex formation enhancing energy transfer in self-assembled multilayers and fluorescence recognize for Pb2+ ions. Sensors and Actuators. Part B, 255, 2121–2125. https://doi.org/10.1016/j. snb.2017.09.004. 124. Suryawanshi, A., Biswal, M., Mhamane, D., Gokhale, R., Patil, S., Guin, D., & Ogale, S., (2014). Large scale synthesis of graphene quantum dots (GQDS) from waste biomass and their use as an efficient and selective photoluminescence on-off-on probe for Ag+ ions. Nanoscale, 6(20), 11664–11670. https://doi.org/10.1039/c4nr02494j. 125. Suvarnaphaet, P., & Pechprasarn, S., (2017). Graphene-based materials for biosensors: A review. Sensors, 17(10), 2161. https://doi.org/10.3390/s17102161. 126. Tabaraki, R., & Nateghi, A., (2016). Nitrogen-doped graphene quantum dots: “turn-off” fluorescent probe for detection of Ag+ ions. Journal of Fluorescence, 26(1), 297–305. https://doi.org/10.1007/s10895-015-1714-y. 127. Taer, E., Taslim, R., Aini, Z., Hartati, S. D., & Mustika, W. S., (2017). Activated carbon electrode from banana-peel waste for supercapacitor applications. AIP Conference Proceedings, 1801, 040004. https://doi.org/10.1063/1.4973093.

Carbon Nanomaterials for Optical and Electrical Biosensors 125 128. Takalkar, S., Baryeh, K., & Liu, G., (2017). Fluorescent carbon nanoparticle-based lateral flow biosensor for ultrasensitive detection of DNA. Biosensors and Bioelectronics, 98, 147–154. https://doi.org/10.1016/j.bios.2017.06.045. 129. Tan, X. W., Romainor, A. N. B., Chin, S. F., & Ng, S. M., (2014). Carbon dots production via pyrolysis of sago waste as potential probe for metal ions sensing. Journal of Analytical and Applied Pyrolysis, 105, 157–165. https://doi.org/10.1016/j.jaap.2013.11.001. 130. Tang, Y., Li, J., Guo, Q., & Nie, G., (2019). An ultrasensitive electrochemiluminescence assay for Hg2+ through graphene quantum dots and poly(5-Formylindole) nanocomposite. Sensors and Actuators. Part B, 282, 824–830. https://doi.org/10.1016/j.snb.2018.11.151. 131. Tang, J., Kong, B., Wu, H., Xu, M., Wang, Y., Wang, Y., Zhao, D., & Zheng, G., (2013). Carbon nanodots featuring efficient FRET for real-time monitoring of drug delivery and two-photon imaging. Advanced Materials, 25(45), 6569–6574. https://doi.org/10.1002/ adma.201303124. 132. Terse-Thakoor, T., Badhulika, S., & Mulchandani, A., (2017). Graphene based biosensors for healthcare. Journal of Materials Research, 32(15), 2905–2929. https:// doi.org/10.1557/jmr.2017.175. 133. Teymourian, H., Salimi, A., & Khezrian, S., (2013). Fe3O4 magnetic nanoparticles/ reduced graphene oxide nanosheets as a novel electrochemical and bio-eletrochemical sensing platform. Biosensors and Bioelectronics, 49, 1–8. https://doi.org/10.1016/j. bios.2013.04.034. 134. Thillaikkarasi, D., Karthikeyan, S., & Malarvizhi, M., (2020). Nanoporous activated carbon and multi-walled carbon nanotubes from renewable botanical hydrocarbons and their impact on efficiency of supercapacitor performance. Journal of Environmental Nanotechnology, 9(1), 01–04. https://doi.org/10.13074/jent.2020.03.194393. 135. Vamvakaki, V., & Chaniotakis, N. A., (2007). Carbon nanostructures as transducers in biosensors. Sensors and Actuators. Part B, 126(1), 193–197. https://doi.org/10.1016/j. snb.2006.11.042. 136. Vamvakaki, V., Hatzimarinaki, M., & Chaniotakis, N., (2008). Biomimetically synthesized silica carbon nanofiber architectures for the development of highly stable electrochemical biosensor systems. Analytical Chemistry, 80(15), 5970–5975. https:// doi.org/10.1021/ac800614j. 137. Vamvakaki, V., Tsagaraki, K., & Chaniotakis, N., (2006). Carbon nanofiber-based glucose biosensor. Analytical Chemistry, 78(15), 5538–5542. https://doi.org/10.1021/ac060551t. 138. Van, T. T. V., Trung, N. B., Kim, H. R., Chung, J. S., & Choi, W. M., (2014). One-pot synthesis of N-doped graphene quantum dots as a fluorescent sensing platform for Fe3+ ions detection. Sensors and Actuators. Part B, 202, 568–573. https://doi.org/10.1016/j. snb.2014.05.045. 139. Wang, C., Yang, F., Tang, Y., Yang, W., Zhong, H., Yu, C., Li, R., et al., (2018). Graphene quantum dots nanosensor derived from 3D nanomesh graphene frameworks and its application for fluorescent sensing of Cu2+ in rat brain. Sensors and Actuators. Part B, 258, 672–681. https://doi.org/10.1016/j.snb.2017.11.098. 140. Wang, F., Xie, Z., Zhang, H., Liu, C. Y., & Zhang, Y. G., (2011). Highly luminescent organosilane-functionalized carbon dots. Advanced Functional Materials, 21(6), 1027–1031. https://doi.org/10.1002/adfm.201002279. 141. Wang, J., Wang, C. F., & Chen, S., (2012). Amphiphilic egg-derived carbon dots: Rapid plasma fabrication, pyrolysis process, and multicolor printing patterns. Angewante Chemie international edition. Angewandte Chemie, 51(37), 9297–9301. https://doi.org/ 10.1002/anie.201204381.

126

Sustainable Nanomaterials for Biosystems Engineering

142. Wang, J., (2005). Carbon-nanotube based electrochemical biosensors: A review. Electroanalysis, 17(1), 7–14. https://doi.org/10.1002/elan.200403113. 143. Wang, J., Li, M., Shi, Z., Li, N., & Gu, Z., (2001). Electrocatalytic oxidation of 3,4-dihydroxyphenylacetic acid at a glassy carbon electrode modified with singlewall carbon nanotubes. Electrochimica Acta, 47(4), 651–657. https://doi.org/10.1016/ s0013-4686(01)00795-2. 144. Wang, L., Zhang, X., Xiong, H., & Wang, S., (2010). A novel nitromethane biosensor based on biocompatible conductive redox graphene-chitosan/hemoglobin/graphene/ room temperature ionic liquid matrix. Biosensors and Bioelectronics, 26(3), 991–995. https://doi.org/10.1016/j.bios.2010.08.027. 145. Wang, Q., Zhang, C., Shen, G., Liu, H., Fu, H., & Cui, D., (2014). Fluorescent carbon dots as an efficient siRNA nanocarrier for its interference therapy in gastric cancer cells. Journal of Nanobiotechnology, 12(1), 58. https://doi.org/10.1186/s12951-014-0058-0. 146. Wang, R., Fan, H., Jiang, W., Ni, G., & Qu, S., (2019). Amino-functionalized graphene quantum dots prepared using high-softening point asphalt and their application in Fe3+ detection. Applied Surface Science, 467, 468, 446–455. https://doi.org/10.1016/j. apsusc.2018.10.104. 147. Wang, S. E., & Si, S., (2013). A fluorescent nanoprobe based on graphene oxide fluorescence resonance energy transfer for the rapid determination of oncoprotein vascular endothelial growth factor (VEGF). Applied Spectroscopy, 67(11), 1270–1274. https://doi. org/10.1366/13-07071. 148. Wang, W., Wang, Z., Liu, J., Peng, Y., Yu, X., Wang, W., Zhang, Z., & Sun, L., (2018). One-pot facile synthesis of graphene quantum dots from rice husks for Fe3+ sensing. Industrial and Engineering Chemistry Research, 57(28), 9144–9150. https://doi.org/ 10.1021/acs.iecr.8b00913. 149. Wang, Y., Li, Y., Tang, L., Lu, J., & Li, J., (2009). Application of graphene-modified electrode for selective detection of dopamine. Electrochemistry Communications, 11(4), 889–892. https://doi.org/10.1016/j.elecom.2009.02.013. 150. Wang, Z., Huang, P., Bhirde, A., Jin, A., Ma, Y., Niu, G., Neamati, N., & Chen, X., (2012). A nanoscale graphene oxide-peptide biosensor for real-time specific biomarker detection on the cell surface. Chemical Communications, 48(78), 9768–9770. https:// doi.org/10.1039/c2cc31974h. 151. Wang, Z., Xu, C., Lu, Y., Chen, X., Yuan, H., Wei, G., Ye, G., & Chen, J., (2017). Fluorescence sensor array based on amino acid derived carbon dots for pattern-based detection of toxic metal ions. Sensors and Actuators. Part B, 241, 1324–1330. https:// doi.org/10.1016/j.snb.2016.09.186. 152. Wu, L., Zhang, X., & Ju, H., (2007). Highly sensitive flow injection detection of hydrogen peroxide with high throughput using a carbon nanofiber modified electrode. Analyst, 132(5), 406–408. https://doi.org/10.1039/b701933e. 153. Wu, L., Yan, F., & Ju, H., (2007). An amperometric immunosensor for separation-free immunoassay of CA125 based on its covalent immobilization coupled with thionine on carbon nanofiber. Journal of Immunological Methods, 322(1, 2), 12–19. https://doi. org/10.1016/j.jim.2007.01.026. 154. Wu, S., He, Q., Tan, C., Wang, Y., & Zhang, H., (2013). Graphene-based electrochemical sensors. Small, 9(8), 1160–1172. https://doi.org/10.1002/smll.201202896. 155. Xia, N., Wang, X., & Liu, L., (2016). A graphene oxide-based fluorescent method for the detection of human chorionic gonadotropin. Sensors, 16(10), 1699. https://doi.org/ 10.3390/s16101699.

Carbon Nanomaterials for Optical and Electrical Biosensors 127 156. Xiaoyan, Z., Zhangyi, L., & Zaijun, L., (2017). Fabrication of valine-functionalized graphene quantum dots and its use as a novel optical Probe for sensitive and selective detection of Hg2+. Spectrochimica Acta: Part A, Molecular and Biomolecular Spectroscopy, 171, 415–424. https://doi.org/10.1016/j.saa.2016.08.037. 157. Xie, R., Wang, Z., Zhou, W., Liu, Y., Fan, L., Li, Y., & Li, X., (2016). Graphene quantum dots as smart Probes for biosensing. Analytical Methods, 8(20), 4001–4016. https://doi. org/10.1039/C6AY00289G. 158. Xu, F., Shi, H., He, X., Wang, K., He, D., Ye, X., Tang, J., et al., (2015). Masking agent-free and channel-switch-mode simultaneous sensing of Fe3+ and Hg2+ using dualexcitation graphene quantum dots. Analyst, 140(12), 3925–3928. 159. Xu, H., Dai, H., & Chen, G., (2010). Direct electrochemistry and electrocatalysis of hemoglobin protein entrapped in graphene and chitosan composite film. Talanta, 81(1, 2), 334–338. https://doi.org/10.1016/j.talanta.2009.12.006. 160. Xu, H., Zhou, S., Xiao, L., Wang, H., Li, S., & Yuan, Q., (2015). Fabrication of a nitrogendoped graphene quantum dot from MOF-derived porous carbon and its application for highly selective fluorescence detection of Fe3+. Journal of Materials Chemistry C, 3(2), 291–297. https://doi.org/10.1039/C4TC01991A. 161. Xu, H., Zhou, S., Xiao, L., Li, S., Song, T., Wang, Y., & Yuan, Q., (2015). Nanoreactorconfined synthesis and separation of yellow-luminescent graphene quantum dots with a recyclable SBA-15 template and their application for Fe(III) sensing. Carbon, 87, 215–225. https://doi.org/10.1016/j.carbon.2015.02.036. 162. Xu, Q., Pu, P., Zhao, J., Dong, C., Gao, C., Chen, Y., Chen, J., et al., (2015). Preparation of highly photoluminescent sulfur-doped carbon dots for Fe(III) detection. Journal of Materials Chemistry A, 3(2), 542–546. https://doi.org/10.1039/C4TA05483K. 163. Xu, Y., Wang, S., Hou, X., Sun, Z., Jiang, Y., Dong, Z., Tao, Q., Man, J., & Cao, Y., (2018). Coal-derived nitrogen, phosphorus, and sulfur codoped graphene quantum dots: A promising ion fluorescent Probe. Applied Surface Science, 445, 519–526. https://doi. org/10.1016/j.apsusc.2018.03.156. 164. Xu, Y., Wu, M., Liu, Y., Feng, X. Z., Yin, X. B., He, X. W., & Zhang, Y. K., (2013). Nitrogen-doped carbon dots: A facile and general preparation method, photoluminescence investigation, and imaging applications. Chemistry: A European Journal, 19(7), 2276– 2283. https://doi.org/10.1002/chem.201203641. 165. Yan, X., Song, Y., Zhu, C., Song, J., Du, D., Su, X., & Lin, Y., (2016). Graphene quantum Dot–MnO2 nanosheet based optical sensing platform: A sensitive fluorescence “turn off-on” nanosensor for glutathione detection and intracellular imaging. ACS Applied Materials and Interfaces, 8(34), 21990–21996. https://doi.org/10.1021/acsami.6b05465. 166. Mohd, Y. S. N. A. M., Chin, S. F., Pang, S. C., & Ng, S. M., (2013). Detection of Sn(II) ions via quenching of the fluorescence of carbon nanodots. Microchimica Acta, 180(1, 2), 137–143. https://doi.org/10.1007/s00604-012-0908-0. 167. Ye, W., Guo, J., Bao, X., Chen, T., Weng, W., Chen, S., & Yang, M., (2017). Rapid and sensitive detection of bacteria response to antibiotics using nanoporous membrane and graphene quantum dot (GQDS) based electrochemical biosensors. Materials, 10(6), 603. https://doi.org/10.3390/ma10060603. 168. Liu, Y., & Kim, D. Y., (2015). Ultraviolet and blue emitting graphene quantum dots synthesized from carbon nano-onions and their comparison for metal ion sensing. Chemical Communications, 51(20), 4176–4179. https://doi.org/10.1039/c4cc07618d.

128

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169. Yu, Y., Liu, Y., Zhen, S. J., & Huang, C. Z., (2013). A graphene oxide enhanced fluorescence anisotropy strategy for DNAzyme-based assay of metal ions. Chemical Communications, 49(19), 1942–1944. https://doi.org/10.1039/c3cc38129c. 170. Zhang, C., Cui, Y., Song, L., Liu, X., & Hu, Z., (2016). Microwave assisted one-pot synthesis of graphene quantum dots as highly sensitive fluorescent probes for detection of iron ions and pH value. Talanta, 150, 54–60. https://doi.org/10.1016/j.talanta.2015.12.015. 171. Zhang, J., & Yu, S. H., (2016). Carbon dots: Large-scale synthesis, sensing, and bioimaging. Materials Today, 19(7), 382–393. https://doi.org/10.1016/j.mattod.2015.11.008. 172. Zhang, J., Yuan, Y., Liang, G., & Yu, S. H., (2015). Scale-up synthesis of fragrant nitrogen-doped carbon dots from bee pollens for bioimaging and catalysis. Advanced Science, 2(4), 1500002. https://doi.org/10.1002/advs.201500002. 173. Zhang, L., Peng, D., Liang, R. P., & Qiu, J. D., (2015). Nitrogen-doped graphene quantum dots as a new catalyst accelerating the coordination reaction between cadmium(II) and 5,10,15,20-tetrakis(1-methyl-4-pyridinio) porphyrin for cadmium(II) sensing. Analytical Chemistry, 87(21), 10894–10901. https://doi.org/10.1021/acs.analchem.5b02450. 174. Zhu, X., Sun, L., Chen, Y., Ye, Z., Shen, Z., & Li, G., (2013). Combination of cascade chemical reactions with graphene–DNA interaction to develop new strategy for biosensor fabrication. Biosensors and Bioelectronics, 47, 32–37. https://doi.org/10.1016/j.bios. 2013.02.039. 175. Zhang, Y., Shen, J., Li, H., Wang, L., Cao, D., Feng, X., Liu, Y., et al., (2016). Recent progress on graphene-based electrochemical biosensors. Chemical Record, 16(1), 273–294. https://doi.org/10.1002/tcr.201500236. 176. Zhu, L., Cui, X., Wu, J., Wang, Z., Wang, P., Hou, Y., & Yang, M., (2014). Fluorescence immunoassay based on carbon dots as labels for the detection of human immunoglobulin G. Anal. Methods, 6(12), 4430–4436. https://doi.org/10.1039/C4AY00717D. 177. Zhang, Y. Q., Ma, D. K., Zhuang, Y., Zhang, X., Chen, W., Hong, L. L., Yan, Q. X., et al., (2012). One-pot synthesis of N-doped carbon dots with tunable luminescence properties. Journal of Materials Chemistry, 22(33), 16714–16718. https://doi.org/10.1039/ c2jm32973e. 178. Zhao, C., Jiao, Y., Hu, F., & Yang, Y., (2018). Green synthesis of carbon dots from pork and application as nanosensors for uric acid detection. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy, 190, 360–367. https://doi.org/10.1016/j. saa.2017.09.037. 179. Zhao, X., Gao, J., He, X., Cong, L., Zhao, H., Li, X., & Tan, F., (2015). DNA-modified graphene quantum dots as a sensing platform for detection of Hg2+ in living cells. RSC Advances, 5(49), 39587–39591. https://doi.org/10.1039/C5RA06984J. 180. Zhao, X. E., Lei, C., Gao, Y., Gao, H., Zhu, S., Yang, X., You, J., & Wang, H., (2017). A ratiometric fluorescent nanosensor for the detection of silver ions using graphene quantum dots. Sensors and Actuators. Part B, 253, 239–246. https://doi.org/10.1016/j. snb.2017.06.086. 181. Zhao, Y., Zuo, S., & Miao, M., (2017). The effect of oxygen on the microwave-assisted synthesis of carbon quantum dots from polyethylene glycol. RSC Advances, 7(27), 16637–16643. https://doi.org/10.1039/C7RA01804E. 182. Zheng, P., & Wu, N., (2017). Fluorescence and sensing applications of graphene oxide and graphene quantum dots: A review. Chemistry, an Asian Journal, 12(18), 2343–2353. https://doi.org/10.1002/asia.201700814.

Carbon Nanomaterials for Optical and Electrical Biosensors 129 183. Zhou, J., Shan, X., Ma, J., Gu, Y., Qian, Z., Chen, J., & Feng, H., (2014). Facile synthesis of P-doped carbon quantum dots with highly efficient photoluminescence. RSC Advances, 4(11), 5465–5468. https://doi.org/10.1039/c3ra45294h. 184. Zhang, J., Tong, T., Zhang, L., Li, X., Zou, H., & Yu, J., (2018). Enhanced performance of planar perovskite solar cell by graphene quantum dot modification. ACS Sustainable Chemistry and Engineering, 6(7), 8631–8640. https://doi.org/10.1021/acssuschemeng. 8b00938. 185. Zhao, X., Zhang, J., Shi, L., Xian, M., Dong, C., & Shuang, S., (2017). Folic acidconjugated carbon dots as green fluorescent probes based on cellular Targeting imaging for recognizing cancer cells. RSC Advances, 7(67), 42159–42167. https://doi.org/10.1039/ C7RA07002K. 186. Zhou, L., Geng, J., & Liu, B., (2013). Graphene quantum dots from polycyclic aromatic hydrocarbon for bioimaging and sensing of Fe3+ and hydrogen peroxide. Particle and Particle Systems Characterization, 30(12), 1086–1092. https://doi.org/10.1002/ ppsc.201300170. 187. Zhou, M., Zhai, Y., & Dong, S., (2009). Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide. Analytical Chemistry, 81(14), 5603–5613. https://doi.org/10.1021/ac900136z. 188. Zhou, Y., Fang, Y., & Ramasamy, R. P., (2019). Non-covalent functionalization of carbon nanotubes for electrochemical biosensor development. Sensors, 19(2), 392. https://doi. org/10.3390/s19020392. 189. Zhu, L., Xu, G., Song, Q., Tang, T., Wang, X., Wei, F., & Hu, Q., (2016). Highly sensitive determination of dopamine by a turn-on fluorescent biosensor based on aptamer labeled carbon dots and nano-graphite. Sensors and Actuators. Part B, 231, 506–512. https:// doi.org/10.1016/j.snb.2016.03.084.

CHAPTER 5

RECENT TRENDS IN GRAPHENEDERIVED APPLICATIONS FOR ENERGY HARVESTING AND BIOSENSING VEDANT A. JOSHI and GIRISH M. JOSHI

ABSTRACT Energy storage has potential applications in diverse fields. It has significantly allured the meticulous attention of numerous researchers. Present energyrelated devices are suffered with many issues like their poor performance and damage to the environment. Therefore, the value-added research on elements focused an improved performance and yielding green energy resources has taken a boom. Various advancements in this domain eventually proved that graphene due to higher electrical conductivity (EC), low production cost, unique heterogeneous charge carriers and electron transfer rates, large surface area and wide range of applicability in turn possess the potential to be used as a reliable alternate electrode material in numerous applications to encounter the problems related to energy storage. Similarly, Biosensors are also one of the important and necessary elements in the present tech-savvy era, as they possess a very crucial role in detecting various life-threatening diseases. Substantial research is being carried out in the domain of sensing elements used in biosensors in order to enhance their performance in terms of their selectivity, sensitivity, stability, response time, etc. The inclusion of carbon nanomaterials (CNMs) in this domain has significantly increased their performance. Graphene, due to its outstanding and unique properties act as an “electron wire” between the electrode surface and redox centers of an enzyme or protein molecule. Similarly, the rapid electron transfer that occurs in turn allows achieving a very precise, accurate, and selective discernment Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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of biomolecules. However, in this chapter, we consolidated a brief overview of various graphene derived materials having diverse energy harvesting and biosensing applications followed by their future prospectus. In addition to this, we also present the current progress in electrochemical biosensors that use graphene, carbon nanotubes (CNTs) and various other CNMs as their sensing elements. 5.1 INTRODUCTION Energy storage and biosensing are the most important and challenging research domains and due to its potential application in diverse fields they have attracted the attention of scientific community. The conventional energy-elated devices are extensively suffered with many issues like their poor performance, damage to environment, etc. In the same way the existing biosensors posses comparatively low selectivity and sensitivity, high production cost, low stability, fouling of sensing area, etc. [20, 30, 60, 125]. Therefore the research on value-addition elements for enhancing performance and yielding green energy resources has taken a boom. Among various nanomaterials (NMs), graphene due to its extraordinary properties, including large surface area, unique morphological properties, low production cost, unique heterogeneous charge carriers and electron transfer rates, high mechanical strength, high electrical, thermal, optical conductivity, etc., possess the potential to be used as a reliable alternate electrode material in numerous applications to encounter the problems related to energy storage and biosensing [19, 20, 93, 139, 152]. Graphene is thick (a one atom) planar sheet that consists of sp2 hybridized bonded carbon atoms that are packed densely in a honeycomb crystal lattice and is considered as the paramount foundation for all the fullerene allotropic dimensionalities [20, 24, 98, 121]. It is considered as the “Mother of all Carbon atoms” – as a building block as it can be rolled to form one dimensional CNT, can be converted to zero-dimensional ball and can be stacked over one another to form three-dimensional graphite [20, 24, 98, 121, 133]. It is reported that the properties of graphene may vary depending upon the type of method by which it is synthesized [20, 24, 98, 121]. A larger number of methods are used for the synthesis of graphene, namely exfoliation and cleavage, plasma enhanced CVD techniques, thermal CVD techniques, various chemical methods, thermal decomposition of SiC, thermal decomposition on another substrate, unzipping CNTs and various other methods [29]. Due to the extraordinary and unique physical and chemical properties of graphene, it has a wide range

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of applications in diverse fields. The theoretical surface area of graphene is divulged to be ~2,630 m2/g which is significantly greater than SWCNTs and graphite and is shown in Figure 5.1. Similarly, the EC of graphene is also ~60 times greater than SWCNTs. These distinctive properties of graphene make it more compatible electrode material for various energy storage and biosensing applications [20, 30, 76, 98, 142].

FIGURE 5.1  Comparison between surface area of graphene, graphite, and SWCNTs allotropes.

In addition to this, it is reported that graphene possesses half-integer quantum hall effect with fermi velocity 106 m/s [20, 49, 115]. In graphene, even in the presence of metallic impurities, charge carriers can cover thousands of interatomic distances without any scattering [121]. The existence of oxygen-containing group on the edges or on the surface of graphene has a huge impact on heterogeneous electron transfer and thus on electrochemical performance. However, these groups may change its chemical and electrical properties [98]. Due to its high conductivity, high mobility of electron, large surface area and unique electrical qualities and characteristics it has a broad

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range of applications in biosensing and energy generation and harvesting devices [20]. 5.2  APPLICATIONS OF GRAPHENE DERIVED MATERIALS IN ENERGY HARVESTING DEVICES Due to the incredible growth and advancement in technology, the existing energy storage devices are becoming unsuitable to meet the stipulation. Thus, the need for enhancing the storage capacity has come into limelight for numerous researchers and scientists. Graphene due to its exceptional properties has paved the path in this domain. 5.2.1 SUPERCAPACITORS Supercapacitors are one of the important devices that are widely used for storage of energy. Due to their various advantages as shown in Figure 5.2, they have prominence in this field [20].

FIGURE 5.2  Advantages of supercapacitors.

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In supercapacitors, Faradic Redox Reaction (FRR) causes electron transfer between the electrolyte and the electrode, thus enabling the storage of energy (Pseudo Capacitors) [20, 132]. Similarly, the storage of energy also occurs due to the development of an electrical double layer at the interface of the electrode (Electrical Double Layer Capacitor) [20, 35]. In supercapacitor unit cell a porous separator infused with an electrolyte is used to isolate two carbon electrodes which are also impregnated with the electrolyte. The imbued electrode in turn allows the ionic current to flow between the electrode and thwarting the electric current from the discharge cell [20, 117]. The electric current from each electrode is conducted through the current collectors or carbon impregnated polymers. Figure 5.3 shows the schematic of a supercapacitor unit cell.

FIGURE 5.3  Schematic of supercapacitor unit cell.

The performance of supercapacitors is highly influenced by the electrode material used for its fabrication. Various materials, namely GNS, Graphene, GNS-ZnO, polyaniline (PANI), PANI/GOS, GNS/PANI, CNT/PANI having unique performance parameters are used as electrode materials in supercapacitor. Figures 5.4 and 5.5 shows the comparison between the performance parameters of various electrode materials reported in literature [20, 26, 28, 35, 78, 143, 146, 149].

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FIGURE 5.4  Variation in specific capacitance of various graphene derived electrode materials.

The main advantages of graphene derived material include their excellent EC, outstanding capacitive power, large surface area and low production cost [20]. All these factors have significantly contributed in emphasizing the role of graphene derived materials in the domain of energy harvesting. From Figure 5.4, it can be inferred that the specific capacitance reported for graphene is not up to the mark, while those reported for graphene-based hybrid materials is quite notable. The highest reported specific capacitance is 1,335 Fg–1 for Nickle (II) hydroxide nanocrystals deposited in GNS [20], while the least reported specific capacitance is 38.9 Fg–1 [78] reported for GNS. Similarly, from Figure 5.5 it can be inferred that the power density of graphene doped materials is quite notable as compared to virgin graphene. The highest reported power density is 70 kWkg–1 for GNS/PANI composite, while the least reported power density is 2.5 kWkg–1 for GNS [20]. Thus, the research in the domain for fabrication of economical and environment friendly graphene-based hybrid material has taken a boom.

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FIGURE 5.5  Variation in power density of various graphene derived electrode materials.

5.2.2  BATTERIES/LI-ION STORAGE Li-ion storage batteries are another class of energy storage device. Due to their longer cycle life-time and high energy capacities they have wide range of application in energy storage domain [73, 91]. The performance of the battery is highly dependent on the type of electrode material used in its fabrication [75]. However, due to high columbic efficiency of graphite, its employed as an electrode in lithium-ion battery [75]. However, research in the domain for employing new electrode materials in Li-ion battery for improving its performance has taken a boom. Various materials namely GNS, GNS/Fe2O3, GNS/SnO2, GNS with CNT spacer, etc., having unique performance parameters are used as an electrode in Lithium-ion Battery [18, 73, 88, 138, 151]. Figure 5.6 shows the comparison of various graphene derived materials that can be employed as an electrode in Lithium-ion battery. However, it is worth noting that the synthesis method used for the fabrication of electrode material alters its specific capacitance. From Figure 5.6, it can be inferred that the specific capacitance of graphite is not up to the mark. In addition, graphite also possesses comparatively low cyclic stability [88, 151].

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However, these loopholes can be overcome using graphene-based materials. However, the specific capacitance reported for oxidized GNSs is the maximum with the value of ~1,400 mAhg–1 [18], however it is the least for GNS/with CNT spacer with the value of 730 mAhg–1 [88, 151]. Thus, the results discussed above indicate that the replacement of graphite electrode with graphene electrode can significantly alter the specific capacitance and thus the performance of lithium-ion battery [20].

FIGURE 5.6  Comparison between the specific capacitance of various graphene-based electrode materials.

5.2.3  FUEL CELL Fuel cell mainly refers to an electrochemical cell that produces electric energy by converting the chemical energy of fuel through a redox reaction in the presence of oxidizing agent [1, 83]. The main drawback associated with fuel cell is constricted obtainability of Platinum [77]. However, graphene due to its extraordinary properties has application in fuel cells. Extended

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surface area of graphene allows more efficient dispersion of Pt NPs than carbon black. Thus, the better surface morphology along with more active catalytic sites are been reported by using Pt/Graphene catalyst in Direct Methanol Fuel Cell [147]. However, as the performance of fuel cell is also dependent on the type of electrode used, therefore the research in the domain for enhancing the properties of electrode material in terms of increasing EC, improving catalytic binding, emergence towards metal free electrodes, etc., has taken a pace in last few years [20, 29, 101]. Figure 5.7 shows the comparison between various types of substrates (graphene substrates) in terms of power density at maximum power that can be used in Fuel Cells [4, 55, 107]. Thus, we can infer from Figure 5.7 that nitrogen doped GNS-Pt substrate possess maximum power density at maximum power (440 mWcm–2). Thus, GNSs act as a potential material for overcoming the current issues related to fuel cells and thus enhancing its power [4, 55, 107].

FIGURE 5.7  Comparison between power densities at maximum power of various types of graphene substrates.

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5.3  APPLICATION OF GRAPHENE BASED MATERIALS IN BIOSENSING A recent study shows that there has been a notable growth in the domain of synthesis, characterization, and applications of NMs that are being employed to design the biosensors with improved sensitivity [30]. Modified biosensors with improved performance in terms of high selectivity, low detection limit, high sensitivity, ability to detect Pico and nanomolar concentrations, high stability. It possesses special importance in the field of medical science for quantitative and qualitative estimation of metabolic and physiological parameters [68]. Specificity, selectivity, sensitivity, and reusability are the most important parameters for designing biosensors and hence research in the domain to alter the performance of electrode in order to enhance their analytical performance is carried out thoroughly in the past few years by using various NMs with tunable physicochemical properties [30, 60, 125]. Among various NMs, graphene due to its extraordinary properties including large surface area, unique morphological properties, high mechanical strength, high electrical, thermal, optical conductivity, etc., possess the potential to be used as an excellent NM for sensing applications [19, 93, 139]. Amongst all graphene derived materials, reduced graphene oxide (rGOx) and graphene oxide (GOx) has significantly attracted the attention of the scientific community and are on the verge of becoming one of the crucial class of NMs in the field of electrochemical and biosensors [68]. Graphene derived materials, especially rGO and GO can be easily doped with various metal oxides (MO), metals, QDs, NPs, organic molecules, etc., for developing a diverse range of graphene derived NCs that can be extensively used for enhancing the performance of conventional biosensors [68]. Biosensors and Electrochemical sensors have a broad range of sensing applications in environmental sciences, biomedical applications, food science, clinical diagnosis, etc. [30, 59, 127]. They possess the capability for sensing a wide range of components including lipids, sugars, antioxidants, cancer biomarkers, neurotransmitters, toxins in food, toxins in drinking water, etc. [14, 16, 45, 86, 103, 120, 126]. A large collection of various research and review articles by various eminent researchers and scientists is widely available in this domain which in turn highlights the importance of this topic.

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5.3.1  BIOSENSORS AND ELECTROCHEMICAL SENSORS FOR DETECTION OF CHOLESTEROL AND GLUCOSE The detection and control of the fluctuation levels of cholesterol and glucose in the human body are very essential as they may lead to severe diseases like cardiovascular diseases, atherosclerosis, hypertension, cardiopathy, myocardial infraction, diabetes, etc. [3, 51]. Diabetes is one of the most common disease that has affected extensively large number of people worldwide. In one of the reports of 2019 published by International Diabetes Federation, it is reported that 463 million adults were suffering from diabetes. However, they consolidated that this number will significantly rise upto 700 million by 2045 [54]. However, the physiological level of glucose in blood after a time span of at least 8 hrs of fasting also called pre-meal in turn detects the prevalence of diabetes [68]. Biosensors plays a very crucial role in clinical diagnosis as they provide the real-time data preparing, which is important for prediction of possible health related issues in short order of time [30, 42, 85, 153]. Enzymatic reaction between the oxidase enzyme and the analyte detection of cholesterol and glucose confirmed by electrochemical method. Direct electrocatalytic oxidation of the analyte on the modified electrode surface is used to discern the non-enzymatic detection of cholesterol and glucose. However, the recent study shows that there is a need of a very highly selective, stable, and sensitive electrochemical sensor for the detection of cholesterol and glucose [30]. There has been a notable growth in the domain of research on graphene derived biosensors and electrochemical sensors for the detection of cholesterol and glucose. To develop a miniaturized electrochemical glucose biosensor consisting of a hybrid electrode (Au/rGOx/AuPtNPs/GOx/Nafion) that was extensively used for determining the glucose concentration in human sweat by amperometric analysis. The developed sensor in this work was reported to have a sensitivity of 82 μAmM–1cm–2 along with the linear range of 0.1–2.3 mM towards the oxidation of glucose (in 0.005M PBS) with the response time of 12 sec. In addition to this, the developed sensor also possessed an adequate stability, interference effect and reproducibility [148]. Similarly, work developed a specific non-enzymatic glucose biosensor using CNT (activated) GO doped nickel hydroxide-Nafion hybrid composite. The sensor developed in this study was reported to have a sensitivity of 40 nA, along with the detection range of 5–1,000 μM and LOD of 0.75 μM. The sensor developed revealed excellent results in terms of performance when compared with commercialized glucose monitoring meters that are used for

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analyzing the standard artificial and whole blood samples [84]. In the same way, developed a low cost, portable glucose biosensor by using graphene that was modified with a conducting polymer capped with PFLO, glucose oxidase and Au-NPs. Then sensor developed in this study was reported to have a sensitivity of 7.357 μAmM–1cm–2, along with the detection range of 0.1–1.5 mM and LOD of 0.081 mM. Excellent results were obtained in terms of performance when glucose levels in commercial beverages were measured using developed sensor and compared to the results provided by the manufacturer [44]. On the other hand, developed a cholesterol biosensor using AuNPs/rGOx-PAMAM-Fc. The developed sensor in this work was reported to have the detection range of 0.0004–15.36 mM along with the LOD of 2 nM. The developed sensor exhibited a huge probability of for its potential application in clinical diagnosis for cholesterol detection [156]. Similarly, developed a GOx-molecular imprinted polymer derived material for sensing of cholesterol. The material developed in this study possessed the detection limit of 0.1 nM towards the cholesterol at pH 5.0 [5]. In addition to the above-mentioned sensors, various other biosensors and electrochemical sensors are developed for detection of cholesterol and glucose [5, 11, 12, 31–33, 36, 43, 48, 50, 53, 61, 62, 72, 79, 82, 90, 94, 105, 108, 122, 130, 135, 140, 154]. Figures 5.8–5.11 show the graphical comparison in terms of analytical parameters of various graphene derived NCs used for detection of cholesterol and glucose. However, extensive research in the domain of selectivity, sensitivity, low-cost production, miniaturization, stability, and fouling of sensing area can lead to the practical applications of graphene-based biosensors and electrochemical sensors for detection of cholesterol and glucose [30]. 5.3.2  BIOSENSORS AND ELECTROCHEMICAL SENSORS FOR DISCERNMENT OF BISPHENOL A 4-4’-(propane-2,2-diyl) diphenol, [(CH3)2C(C6H4OH)2] commonly known as Bisphenol A (BPA) or BPA is an endocrine disruptor that has the potential to imitate estrogen and can significantly lead to deterioration in health of human being and animals [7]. BPA is widely used to manufacture phenol, polycarbonate (PC) plastic, epoxy resins, etc. [7, 30]. Various electrochemical sensors due to their low production cost, acceptable sensitivity, etc., are being extensively used for detection of BPA. A notable research has been carried out in this domain to develop graphene-based sensors for accurate and precise detection of bisphenol. Various graphene based modified electrodes

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FIGURE 5.8  Comparison between detection limit of various types of graphene derived NCs used for detection of cholesterol.

FIGURE 5.9  Comparison between sensitivity of various types of graphene derived NCs used for detection of cholesterol.

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FIGURE 5.10  Comparison between detection limit of various types of graphene derived NCs used for detection of glucose.

FIGURE 5.11  Comparison between sensitivity of various types of graphene derived NCs used for detection of glucose.

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loaded with NPs are reported to have the linear range of 1×10–2 to 10 μmol/L. In addition to this they also possess the capability to detect significantly low BPA concentration upto 8 nM [118]. Graphene based modified sensors are reported to have enhanced sensitivity, stability, accuracy, and selectivity [47, 81, 118]. To develop an electrochemical sensor used for detecting BPA using rGOx-Ag/PLL/GCE. The developed sensor possessed a remarkable linear range of 1 to 80 μM, along with the detection limit 0.54 μM. The sensor developed is reported to have excellent reproducibility, selectivity, and sensitivity [71]. Similarly, work developed a sensitive and a simple electrochemical sensor using IL-GNP altered glassy carbon paste electrodes (GCPEs) for detection of BPA. The sensor developed by Butmee et al. [20] possessed low detection range along with high sensitivity and broad linear range. In addition to this, it also possessed acceptable stability, reproducibility, repeatability, and selectivity. The quantitative BPA data of water and plastic samples obtained from the developed sensors showed significantly less error as compared to the data obtained from high performance liquid chromatography [21]. Likewise, developed an electrochemical sensor using porous graphene-black phosphorous composite. The sensor developed was used for quantitative detection of BPA in biological and food packaging samples. The developed sensor was reported to have the linear range of 4.3×10–8 to 5.5×10–5 mol/L along with the LOD of 7.8×10–9 mol/L [22]. Similarly, a brief review on quantitative determination of BPA in real samples by using electrochemical and biosensors has been explicitly, that in turn provides a brief insight about this topic [129]. In spite of satisfactory results discussed above, thorough research in the domain of selectivity, sensitivity, time consumption, etc., can lead to practical application of graphene-derived biosensors and electrochemical sensors for detection of BPA [30, 37]. 5.3.3  BIOSENSORS AND ELECTROCHEMICAL SENSORS FOR DETECTION OF ASCORBIC ACID, URIC ACID, AND DOPAMINE Ascorbic acid (AA), uric acid (UA) and dopamine (DA) are important compounds having notable function in human metabolism. AA is an antioxidant, while DA is one of the most crucial catecholamine neurotransmitters, on the other hand, UA is the key outcome of purine metabolism. The fluctuation in the level of these compounds in the human body may lead to various chronic diseases including Gout, Parkinson’s, Schizophrenia, etc. [30, 96]. However, precise, and accurate quantitative detection of these compounds may lead to diagnosis and further treatment of disease [30].

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In the past few years, there has been a notable growth in the domain of research on fabrication and application of graphene based modified electrodes for detecting AA, UA, and DA [13, 64, 65, 116]. To developed a electrochemical sensor based on GF/CNTs/AuNPs composite electrode used for detecting UA and DA. The sensor developed was reported to possess the linear range of 5×10–1 to 60 μM and 0.1 to 48 μM for UA and DA respectively. In addition to this, it posses the detection limit of 33.03 nM and 1.36 nM for detection of UA and DA respectively [52]. Similarly, work developed a very sensitive electrochemical sensor using rGOx/F doped SnO2 modified electrode for detecting DA and UA. The sensor developed in this study possesses the detection range of 0.07 μM and 0.39 μM for DA and UA, respectively. Further, it posses the linear range of 5 to 300 μM and 0.5 to 50 μM for detection of UA and DA, respectively [2]. In addition to the above-mentioned sensors, various other biosensors and electrochemical sensors are developed for detection of AA, UA, and DA [17, 41, 67, 69, 74, 97, 99, 111, 119, 131, 134, 145, 158]. Figures 5.12–5.14 show the graphical comparison in terms of analytical parameters of various graphene derived NCs used for detecting of AA, DA, and UA, respectively.

FIGURE 5.12  Comparison between detection limits of various types of graphene derived NCs used for detection of AA.

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FIGURE 5.13  Comparison between detection limits of various types of graphene derived NCs used for detection of dopamine.

FIGURE 5.14  Comparison between detection limits of various types of graphene derived NCs used for detection of UA.

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From the above-mentioned results, it can be inferred that graphene-based materials possess the potential to be used simultaneously or individually for accurate and precise discernment of AA, UA, and DA [30]. However, rigorous research in the domain of selectivity, sensitivity, and stability can result in practical application of the developed graphene-based biosensors and electrochemical sensors for discernment of AA, UA, and DA [30]. 5.3.4  BIOSENSORS AND ELECTROCHEMICAL SENSORS FOR DETECTION OF HEAVY METAL IONS Heavy metal ions cause adverse effects not only on human health but also on ecosystem when their amount exceeds the acceptable value/range. Hence, precise, and accurate quantitative estimation of heavy metal ions in the human body as well as in the water/soil environment is essential [30]. It is reported that, in comparison to the other heavy metal ions Pb+2 and Cd+2 ions cause grievous threat to the health of human beings in terms of respiratory disorders, imbalanced metabolism, deterioration of the immune system, reproductive toxicity, etc., hence their precise and accurate detection is very important for safeguarding the human health [87]. In comparison to the customary methods that are employed for detecting ions of heavy metal, graphene-derived biosensors and electrochemical sensors posses more enhanced performance in respect of stability, selectivity, sensitivity, precision, etc., and hence large number of various research and review articles are widely available in this domain [30]. To developed a highly selective, precise, and sensitive fluorescence sensor using graphene-QDs along with Au-NPs for detection of Pb+2 ions [87]. Similarly, modified GCE by reinforcing it with nitrogen-doped graphene along with chitosan for detecting Pb+2 ions in aqueous solution [80]. In addition to this, modified the glassy carbon electrode using nitrogen-doped rGOx along with MnO2. The developed sensor was extensively used for the detection of Hg+2 ions. It is reported that the developed sensor possessed a sensitivity of 72.16 mA/mM along with the detection limit of 0.0414 mM [144]. Similarly, modified the glassy carbon electrode by using electrochemically reduced GOx for simultaneous detection of Hg+2 and Pb+2 ions. The developed sensor possessed the detection limit of 1 ng/mL and 0.2 ng/mL for Hg+2 and Pb+2 ions respectively along with the linear range of 1~1,000 ng/mL for both ions. It is also reported that the application of the developed sensor can be extended for quantitative and qualitative analysis of different kinds of real samples [141].

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Furthermore, to the above-mentioned modified sensors, various other biosensors and electrochemical sensors are developed for detection of heavy metal ions [39, 70, 87, 100, 112, 136, 137, 157]. Figure 5.15 shows the graphical comparison in terms of analytical parameters of various graphene derived NCs used for detecting Ions of Heavy Metals.

FIGURE 5.15  Comparison between detection limits of various types of graphene derived NCs used for detecting ions of heavy metals.

However, the high production cost and troublesome fabrication methods, in turn, restrict the practical application of these sensors. 5.3.5  BIOSENSORS AND ELECTROCHEMICAL SENSORS FOR DETECTION OF CANCER BIOMARKERS Cancer is considered as one of the deadliest diseases globally, with increasing mortality rate. As stated by World Health Organization (WHO), it is the second largest disease spread across the globe. However, detection, diagnosis, and treatment in the early stage can significantly reduce the mortality rate

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[30]. Modified biosensors due to their extraordinary properties including excellent sensitivity, selectivity, fast response, etc., possess the potential to be employed for detecting cancer biomarkers. Various graphene-based biosensors are designed for precise and accurate detection of cancer biomarkers. However, nanobiosensors have significantly attracted the attention of numerous researchers and scientists because of their highly enhanced properties, including high precision, excellent sensitivity and selectivity, etc. [9, 46, 102, 104]. A wide collection of research and review articles on this topic in turn highlights the importance and necessity of this topic. Various graphene based modified biosensors loaded with NPs are designed for detection of cancer biomarkers. To developed a biosensor using GOx doped with Fe2N NPs. The developed sensor possessed high sensitivity, selectivity, and stability towards detection of 4-nitroquinoline N-oxide (4-NQO) markers. The sensor developed possessed the LOD of 0.0092 μM along with the linear range of 0.05 to 574.2 μM towards 4-NQO markers [102]. Similarly, developed a label-free immunosensor using graphene NCs/P-phenylenediamine that was extensively used for detection of (NSE) antigen. The developed sensor showed satisfactory results for NSE antigen detection in human serum [9]. Furthermore, developed an electrochemical multiplexed immunosensor using rGOx doped Thionine/AuNPs composite for detection of Carcinoembryonic Antigen. The developed sensor possessed the detection limit of 650×10–3 pg/ml, along with the linear range of 0.01 to 300 ng/ml [58]. In addition to the above-mentioned sensors, various other biosensors and electrochemical sensors are developed for detection of cancer biomarkers [6, 15, 23, 25, 56, 89, 109, 110, 128]. However, the modified sensors due to their enhanced performance along with high stability, sensitivity, accuracy, easy fabrication, fast response, etc., towards the cancer biomarkers possess the potential for diagnosis of cancer at an early stage [30]. 5.3.6  BIOSENSORS AND ELECTROCHEMICAL SENSORS FOR DETECTION OF PATHOGENS Pathogens are one of the major contaminants in water that includes various types of fungi, viruses, bacteria, etc., and are duly responsible for different types of water-borne diseases. Their presence in food and water products adversely affects the human health [8, 38, 68, 95]. Similarly, the presence of pathogenic microorganisms, namely viroid, nematodes, fungi, phytoplasma, etc., leads to various infectious and hazardous diseases, that

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in turn decreases the productivity of agricultural field worldwide [66, 68]. Amongst all pathogen, bacterial strains of enterohemorrhagic Escherichia Coli are the most dangerous and life hazardous strains. Hence, the detection of these strains along with others is of utmost importance in food safety in order to avert various critical life-threatening diseases in human beings [150]. However, various graphene modified electrochemical biosensors with enhanced properties and performance are extensively explored for detection of pathogens and their progress has been reported previously [10, 106]. To development of graphene derived label-free biosensor that was extensively used for detecting Escherichia Coli O157:H7. A sensor developed in this study was reported to have 10 to 1,000 cells/mL as it’s linear range [92]. Similarly, the development of graphene modified electrochemical sensor using GO/Fe2O3/CS composite for detecting Escherichia Coli O157:H7. A sensor developed in this study was reported to have a linear range of 1μM to 10 fM along with the detection limit of 10 fM [124]. Furthermore, the development of impedimetric aptasensor using rGOx/AuNPs NC that was extensively used for detection of Staphylococcus aureus. The sensor developed in this study was reported to have the detection limit of 10 CFU/ mL along with the linear range of 10–106 cells/mL [57]. However, in addition to the above-mentioned sensors, various other graphene derived biosensors and electrochemical sensors are extensively developed for detection of pathogens [27, 34, 40, 63, 113, 114, 123, 155]. Figure 5.16 shows the graphical comparison in terms of analytical parameters of various graphene derived NCs used for detection of pathogens. 5.4 SUMMARY Graphene due to its outstanding and unique properties has wide range of application in Energy harvesting and Biosensing domain. However, in the present review, we briefly consolidated the advance applications of graphene derived/doped materials in the key area of energy harvesting, mainly in fuel cell, Li-ion batteries and supercapacitors. On the other hand, we extensively reviewed the diverse applications of graphene derived/doped materials in biosensing domain mainly for detection of Cancer Biomarkers, AA, DA, UA, Pathogens, Cholesterol, Glucose, BPA, and Heavy Metal Ions. However, more extensive research can be carried out in the domain of enhancing the analytical parameters and performance of electrodes to a more precise level along with profound research in the field of development of more convenient and economical fabrication method. This in turn will lead to wider practical

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applications of the developed graphene derived materials in the domain of energy harvesting and biosensing.

FIGURE 5.16  Comparison between detection limits of various types of graphene derived NCs used for detection of pathogens.

KEYWORDS • • • • • •

electrochemical faradic redox reaction graphene oxide morphological nanomaterials reduced graphene oxide

REFERENCES 1. Ahammad, A. J. S., Islam, T., Hasan, M. M., Mozumder, M. N. I., Karim, R., Odhikari, N., Pal, P. R., et al., (2018). Reduced graphene oxide screen-printed FTO as highly

Recent Trends in Graphene-Derived Applications 153 sensitive electrodes for simultaneous determination of dopamine and uric acid. Journal of the Electrochemical Society, 165(5), B174–B183. https://doi.org/10.1149/2.0121805jes. 2. Ahmadalinezhad, A., & Chen, A., (2011). High-performance electrochemical biosensor for the detection of total cholesterol. Biosensors and Bioelectronics, 26(11), 4508–4513. https://doi.org/10.1016/j.bios.2011.05.011. 3. Aïssa, B., Memon, N. K., Ali, A., & Khraisheh, M. K., (2015). Recent progress in the growth and applications of graphene as a smart material: A review. Frontiers in Materials, 2, 58. https://doi.org/10.3389/fmats.2015.00058. 4. Alexander, S., Baraneedharan, P., Balasubrahmanyan, S., & Ramaprabhu, S., (2017). Modified graphene based molecular imprinted polymer for electrochemical non-enzymatic cholesterol biosensor. European Polymer Journal, 86, 106–116. https:// doi.org/10.1016/j.eurpolymj.2016.11.024. 5. Ali, M. A., Singh, C., Srivastava, S., Admane, P., Agrawal, V. V., Sumana, G., John, R., et al., (2017). Graphene oxide-metal nanocomposites for cancer biomarker detection. RSC Advances, 7(57), 35982–35991. https://doi.org/10.1039/C7RA05491B. 6. Almeida, S., Raposo, A., Almeida-Gonzalez, M., Carrascosa, C., & Bisphenol, A., (2018). Bisphenol A: Food exposure and impact on human health. Comprehensive Reviews in Food Science and Food Safety, 17(6), 1503–1517. https://doi.org/10.1111/1541-4337.12388. 7. Alocilja, E. C., & Radke, S. M., (2003). Market analysis of biosensors for food safety. Biosensors and Bioelectronics, 18(5, 6), 841–846. https://doi.org/10.1016/s0956-5663 (03)00009-5. 8. Amani, J., Maleki, M., Khoshroo, A., Sobhani-Nasab, A., & Rahimi-Nasrabadi, M., (2018). An electrochemical immunosensor based on poly P-phenylenediamine and graphene nanocomposite for detection of neuron-specific enolase via electrochemically amplified detection. Analytical Biochemistry, 548, 53–59. https://doi.org/10.1016/j.ab.2018.02.024. 9. Amiri, M., Bezaatpour, A., Jafari, H., Boukherroub, R., & Szunerits, S., (2018). Electrochemical methodologies for the detection of pathogens. ACS Sensors, 3(6), 1069–1086. https://doi.org/10.1021/acssensors.8b00239. 10. Amouzadeh, T. M., & Varkani, J. N., (2014). Green synthesis of reduced graphene oxide decorated with gold nanoparticles and its glucose sensing application. Sensors and Actuators. Part B, 202, 475–482. https://doi.org/10.1016/j.snb.2014.05.099. 11. Anirudhan, T. S., Deepa, J. R., & Binussreejayan, (2018). Electrochemical sensing of cholesterol by molecularly imprinted polymer of silylated graphene oxide and chemically modified nanocellulose polymer. Materials Science and Engineering. C, Materials for Biological Applications, 92, 942–956. https://doi.org/10.1016/j.msec.2018.07.041. 12. Ben, A. S. B. S., (2017). Nanostructured carbon electrode modified with N-doped graphene quantum dots-chitosan nanocomposite: A sensitive electrochemical dopamine sensor. Royal Society Open Science, 4(11), 171199. https://doi.org/10.1098/rsos.171199. 13. Apak, R., Demirci, Ç. S. D., Üzer, A., Çelik, S. E., Bener, M., Bekdeşer, B., Can, Z., et al., (2018). Novel spectroscopic and electrochemical sensors and nanoprobes for the characterization of food and biological antioxidants. Sensors, 18(1), 186. https://doi. org/10.3390/s18010186. 14. Azimzadeh, M., Rahaie, M., Nasirizadeh, N., Ashtari, K., & Naderi-Manesh, H., (2016). An electrochemical nanobiosensor for plasma Mirna-155, based on graphene oxide and gold nanorod, for early detection of breast cancer. Biosensors and Bioelectronics, 77, 99–106. https://doi.org/10.1016/j.bios.2015.09.020.

154

Sustainable Nanomaterials for Biosystems Engineering

15. Batool, R., Rhouati, A., Nawaz, M. H., Hayat, A., & Marty, J. L., (2019). A review of the construction of nano-hybrids for electrochemical biosensing of glucose. Biosensors, 9(1), 46. https://doi.org/10.3390/bios9010046. 16. Begum, H., Ahmed, M. S., & Jeon, S., (2017). New approach for porous chitosan-graphene matrix preparation through enhanced amidation for synergic detection of dopamine and uric acid. ACS Omega, 2(6), 3043–3054. https://doi.org/10.1021/acsomega.7b00331. 17. Bhardwaj, T., Antic, A., Pavan, B., Barone, V., & Fahlman, B. D., (2010). Enhanced electrochemical lithium storage by graphene nanoribbons. Journal of the American Chemical Society, 132(36), 12556–12558. https://doi.org/10.1021/ja106162f. 18. Bo, X., Zhou, M., & Guo, L., (2017). Electrochemical sensors and biosensors based on less aggregated graphene. Biosensors and Bioelectronics, 89(1), 167–186. https://doi. org/10.1016/j.bios.2016.05.002. 19. Brownson, D. A. C., Kampouris, D. K., & Banks, C. E., (2011). An overview of graphene in energy production and storage applications. Journal of Power Sources, 196(11), 4873–4885. https://doi.org/10.1016/j.jpowsour.2011.02.022. 20. Butmee, P., Tumcharern, G., Saejueng, P., Stankovic, D., Ortner, A., Jitcharoen, J., Kalcher, K., & Samphao, A., (2019). A direct and sensitive electrochemical sensing platform based on ionic liquid functionalized graphene nanoplatelets for the detection of bisphenol A. Journal of Electroanalytical Chemistry, 833, 370–379. https://doi. org/10.1016/j.jelechem.2018.12.014. 21. Cai, J., Sun, B., Li, W., Gou, X., Gou, Y., Li, D., & Hu, F., (2019). Novel nanomaterial of porous graphene functionalized black phosphorus as electrochemical sensor platform for bisphenol A detection. Journal of Electroanalytical Chemistry, 835, 1–9. https://doi. org/10.1016/j.jelechem.2019.01.003. 22. Cao, J. T., Yang, J. J., Zhao, L. Z., Wang, Y. L., Wang, H., Liu, Y. M., & Ma, S. H., (2018). Graphene oxide@gold nanorods-based multiple-assisted electrochemiluminescence signal amplification strategy for sensitive detection of prostate specific antigen. Biosensors and Bioelectronics, 99, 92–98. https://doi.org/10.1016/j.bios.2017.07.050. 23. Chen, D., Tang, L., & Li, J., (2010). Graphene-based materials in electrochemistry. Chemical Society Reviews, 39(8), 3157–3180. https://doi.org/10.1039/b923596e. 24. Chen, M., Wang, Y., Su, H., Mao, L., Jiang, X., Zhang, T., & Dai, X., (2018). Threedimensional electrochemical DNA biosensor based on 3D graphene-Ag nanoparticles for sensitive detection of CYFRA21-1 in non-small cell lung cancer. Sensors and Actuators. Part B, 255, 2910–2918. https://doi.org/10.1016/j.snb.2017.09.111. 25. Chen, S., Zhu, J., & Wang, X., (2010). One-step synthesis of graphene-cobalt hydroxide nanocomposites and their electrochemical properties. Journal of Physical Chemistry C, 114(27), 11829–11834. https://doi.org/10.1021/jp1048474. 26. Chen, S., Frank, C. Y., & Voordouw, G., (2018). Three-dimensional graphene nanosheet doped with gold nanoparticles as electrochemical DNA biosensor for bacterial detection. Sensors and Actuators. Part B, 262, 860–868. https://doi.org/10.1016/j. snb.2018.02.093. 27. Chen, Y., Zhang, X., Yu, P., & Ma, Y., (2010). Electrophoretic deposition of graphene nanosheets on nickel foams for electrochemical capacitors. Journal of Power Sources, 195(9), 3031–3035. https://doi.org/10.1016/j.jpowsour.2009.11.057. 28. Choi, W., Lahiri, I., Seelaboyina, R., & Kang, Y. S., (2010). Synthesis of graphene and its applications: A review. Critical Reviews in Solid State and Materials Sciences, 35(1), 52–71. https://doi.org/10.1080/10408430903505036.

Recent Trends in Graphene-Derived Applications 155 29. Coroş, M., Pruneanu, S., Stefan-Van, S. R. I., & Progress, R. R., (2020). In the graphenebased electrochemical sensors and biosensors. Journal of the Electrochemical Society, 167(3). https://doi.org/10.1149/2.0282003JES, PubMed: 037528. 30. Cui, M., Xu, B., Hu, C., Shao, H. B., & Qu, L., (2013). Direct electrochemistry and electrocatalysis of glucose oxidase on three-dimensional interpenetrating, porous graphene modified electrode. Electrochimica Acta, 98, 48–53. https://doi.org/10.1016/j. electacta.2013.03.040. 31. Dey, R. S., & Raj, C. R., (2010). Development of an amperometric cholesterol biosensor based on graphene-Pt nanoparticle hybrid material. Journal of Physical Chemistry C, 114(49), 21427–21433. https://doi.org/10.1021/jp105895a. 32. Dhara, K., Ramachandran, T., Nair, B. G., & Satheesh, B. T. G., (2015). Single step synthesis of Au–CuO nanoparticles decorated reduced graphene oxide for high performance disposable nonenzymatic glucose sensor. Journal of Electroanalytical Chemistry, 743, 1–9. https://doi.org/10.1016/j.jelechem.2015.02.005. 33. Dinshaw, I. J., Muniandy, S., Teh, S. J., Ibrahim, F., Leo, B. F., & Thong, K. L., (2017). Development of an aptasensor using reduced graphene oxide chitosan complex to detect salmonella. Journal of Electroanalytical Chemistry, 806, 88–96. https://doi. org/10.1016/j.jelechem.2017.10.054. 34. Du, X., Guo, P., Song, H., & Chen, X., (2010). Graphene nanosheets as electrode material for electric double-layer capacitors. Electrochimica Acta, 55(16), 4812–4819. https://doi.org/10.1016/j.electacta.2010.03.047. 35. Du, X., Jiang, D., Chen, S., Dai, L., Zhou, L., Hao, N., You, T., et al., (2017). CeO2 nanocrystallines ensemble-on-nitrogen-doped graphene nanocomposites: One-pot, rapid synthesis and excellent electrocatalytic activity for enzymatic biosensing. Biosensors and Bioelectronics, 89(1), 681–688. https://doi.org/10.1016/j.bios.2015.11.054. 36. Duan, Y., Li, S., Lei, S., Qiao, J., Zou, L., & Ye, B., (2018). Highly sensitive determination of bisphenol A based on MoCuSe nanoparticles decorated reduced graphene oxide modified electrode. Journal of Electroanalytical Chemistry, 827, 137–144. https://doi. org/10.1016/j.jelechem.2018.08.011. 37. Dye, C., (2014). After 2015: Infectious diseases in a new era of health and development. Philosophical Transactions of the Royal Society of London: Series B, Biological Sciences, 369(1645), 20130426. https://doi.org/10.1098/rstb.2013.0426. 38. Fang, B. Y., Li, C., Song, Y. Y., Tan, F., Cao, Y. C., & Zhao, Y. D., (2018). Nitrogendoped graphene quantum dot for direct fluorescence detection of Al(3+) in aqueous media and living cells. Biosensors and Bioelectronics, 100, 41–48. https://doi.org/10.1016/j. bios.2017.08.057. 39. Fei, J., Dou, W., & Zhao, G., (2016). Amperometric immunoassay for the detection of Salmonella pullorum using a screen—Printed carbon electrode modified with gold nanoparticle-coated reduced graphene oxide and immunomagnetic beads. Microchimica Acta, 183(2), 757–764. https://doi.org/10.1007/s00604-015-1721-3. 40. Fu, L., Wang, A., Lai, G., Su, W., Malherbe, F., Yu, J., Lin, C. T., & Yu, A., (2018). Defects regulating of graphene ink for electrochemical determination of ascorbic acid, dopamine, and uric acid. Talanta, 180, 248–253. https://doi.org/10.1016/j.talanta.2017.12.058. 41. Gahlaut, A., Hooda, V., Dhull, V., & Hooda, V., (2018). Recent approaches to ameliorate selectivity and sensitivity of enzyme based cholesterol biosensors: A review. Artificial Cells, Nanomedicine, and Biotechnology, 46(3), 472–481. https://doi.org/10.1080/2169 1401.2017.1337028.

156

Sustainable Nanomaterials for Biosystems Engineering

42. Geim, A. K., & Novoselov, K. S., (2007). The rise of graphene. Nature Materials, 6(3), 183–191. https://doi.org/10.1038/nmat1849. 43. Gholivand, M. B., & Khodadadian, M., (2014). Amperometric cholesterol biosensor based on the direct electrochemistry of cholesterol oxidase and catalase on a graphene/ ionic liquid-modified glassy carbon electrode. Biosensors and Bioelectronics, 53, 472–478. https://doi.org/10.1016/j.bios.2013.09.074. 44. Gokoglan, T. C., Kesik, M., Soylemez, S., Yuksel, R., Unalan, H. E., & Toppare, L., (2017). Paper based glucose biosensor using graphene modified with a conducting polymer and gold nanoparticles. Journal of the Electrochemical Society, 164(6), G59– G64. https://doi.org/10.1149/2.0791706jes. 45. Gu, H., Tang, H., Xiong, P., & Zhou, Z., (2019). Biomarkers-based biosensing and bioimaging with graphene for cancer diagnosis. Nanomaterials, 9(1), 130. https://doi. org/10.3390/nano9010130. 46. Gugoasa, L. A., Stefan-Van, S. R. I., Al-Ogaidi, A. J. M., Stanciu-Gavan, C., Van, S. J. F., Rosu, M. C., & Pruneanu, S., (2017). Molecular recognition of colon cancer biomarkers: P53, KRAS, and CEA in whole blood samples. Journal of the Electrochemical Society, 164(9), B443–B447. 47. Yu, H., Feng, X., Chen, X., Qiao, J., Gao, X., Xu, N., & Gao, L., (2017). Electrochemical determination of bisphenol A on a glassy carbon electrode modified with gold nanoparticles loaded on reduced graphene oxide-multi walled carbon nanotubes composite. Chinese Journal of Analytical Chemistry, 45(5), 713–720. https://doi.org/10.1016/S1872-2040 (17)61014-4. 48. He, Y., & Zheng, J., (2013). One-pot ultrasonic-electrodeposition of copper–graphene nanoflowers in ethaline for glucose sensing. Anal. Methods, 5(3), 767–772. https://doi. org/10.1039/C2AY26213D. 49. Heersche, H. B., Jarillo-Herrero, P., Oostinga, J. B., Vandersypen, L. M. K., & Morpurgo, A. F., (2007). Bipolar supercurrent in graphene. Nature, 446(7131), 56–59. https://doi. org/10.1038/nature05555. 50. Hemanth, S., Halder, A., Caviglia, C., Chi, Q., & Keller, S. S., (2018). 3D carbon microelectrodes with bio-functionalized graphene for electrochemical biosensing. Biosensors, 8(3), 70. https://doi.org/10.3390/bios8030070. 51. Hong, K. N., Fuster, V., Rosenson, R. S., Rosendorff, C., & Bhatt, D. L., (2017). How low to go with glucose, cholesterol, and blood pressure in primary prevention of CVD. Journal of the American College of Cardiology, 70(17), 2171–2185. https://doi. org/10.1016/j.jacc.2017.09.001. 52. Huang, B., Liu, J., Lai, L., Yu, F., Ying, X., Ye, B. C., Li, Y., & Free-Standing, A., (2017). A free-standing electrochemical sensor based on graphene foam-carbon nanotube composite coupled with gold nanoparticles and its sensing application for electrochemical determination of dopamine and uric acid. Journal of Electroanalytical Chemistry, 801, 129–134. https://doi.org/10.1016/j.jelechem.2017.07.029. 53. Huang, Y., Tan, J., Cui, L., Zhou, Z., Zhou, S., Zhang, Z., Zheng, R., et al., (2018). Graphene and Au Nps co-mediated enzymatic silver deposition for the ultrasensitive electrochemical detection of cholesterol. Biosensors and Bioelectronics, 102, 560–567. https://doi.org/10.1016/j.bios.2017.11.037. 54. International Diabetes Federation, (n.d.). Facts and Figures. https://www.idf.org/ aboutdiabetes/what-is-diabetes/facts-figures.html (accessed on 9 July 2022).

Recent Trends in Graphene-Derived Applications 157 55. Imran, J. R. I., Rajalakshmi, N., & Ramaprabhu, S., (2010). Nitrogen doped graphene nanoplatelets as catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell. Journal of Materials Chemistry, 20(34), 7114–7117. https://doi. org/10.1039/c0jm00467g. 56. Jang, H. D., Kim, S. K., Chang, H., & Choi, J. W., (2015). 3D label-free prostate specific antigen (PSA) immunosensor based on graphene-gold composites. Biosensors and Bioelectronics, 63, 546–551. https://doi.org/10.1016/j.bios.2014.08.008. 57. Jia, F., Duan, N., Wu, S., Ma, X., Xia, Y., Wang, Z., & Wei, X., (2014). Impedimetric aptasensor for Staphylococcus aureus based on nanocomposite prepared from reduced graphene oxide and gold nanoparticles. Microchimica Acta, 181(9, 10), 967–974. https://doi.org/10.1007/s00604-014-1195-8. 58. Jia, X., Liu, Z., Liu, N., & Ma, Z., (2014). A label-free immunosensor based on graphene nanocomposites for simultaneous multiplexed electrochemical determination of tumor markers. Biosensors and Bioelectronics, 53, 160–166. https://doi.org/10.1016/j.bios. 2013.09.050. 59. Justino, C. I. L., Gomes, A. R., Freitas, A. C., Duarte, A. C., & Rocha-Santos, T. A. P., (2017). Graphene based sensors and biosensors. TrAC Trends in Analytical Chemistry, 91, 53–66. https://doi.org/10.1016/j.trac.2017.04.003. 60. Kalambate, P. K., Dhanjai, Huang, Z., Li, Y., Shen, Y., Xie, M., Huang, Y., & Srivastava, A. K., (2019). Core@Shell nanomaterials based sensing devices: A review. TrAC Trends in Analytical Chemistry, 115, 147–161. 61. Kang, X., Wang, J., Wu, H., Aksay, I. A., Liu, J., & Lin, Y., (2009). Glucose oxidasegraphene-chitosan modified electrode for direct electrochemistry and glucose sensing. Biosensors and Bioelectronics, 25(4), 901–905. https://doi.org/10.1016/j.bios.2009.09.004. 62. Karikalan, N., Karthik, R., Chen, S. M., Karuppiah, C., & Elangovan, A., (2017). Sonochemical synthesis of sulfur doped reduced graphene oxide supported CuS nanoparticles for the non-enzymatic glucose sensor applications. Scientific Reports, 7(1), 2494. https://doi.org/10.1038/s41598-017-02479-5. 63. Kaur, H., Shorie, M., Sharma, M., Ganguli, A. K., Sabherwal, P., & Rebar, B., (2017). Graphene functionalized aptasensor for pathogenic E. coli O78:K80:H11 detection. Biosensors and Bioelectronics, 98, 486–493. 64. Kaya, S. I., Kurbanoglu, S., & Ozkan, S. A., (2019). Nanomaterials-based nanosensors for the simultaneous electrochemical determination of biologically important compounds: Ascorbic acid, uric acid, and dopamine. Critical Reviews in Analytical Chemistry, 49(2), 101–125. https://doi.org/10.1080/10408347.2018.1489217. 65. Keteklahijani, Y. Z., Sharif, F., Roberts, E. P. L., & Sundararaj, U., (2019). Enhanced sensitivity of dopamine biosensors: An electrochemical approach based on nanocomposite electrodes comprising polyaniline, nitrogen-doped graphene, and DNA-functionalized carbon nanotubes. Journal of the Electrochemical Society, 166(15), B1415–B1425. https://doi.org/10.1149/2.0361915jes. 66. Khater, M., De La Escosura-Muñiz, A., & Merkoçi, A., (2017). Biosensors for plant pathogen detection. Biosensors and Bioelectronics, 93, 72–86. https://doi.org/10.1016/j. bios.2016.09.091. 67. Kim, Y. R., Bong, S., Kang, Y. J., Yang, Y., Mahajan, R. K., Kim, J. S., & Kim, H., (2010). Electrochemical detection of dopamine in the presence of ascorbic acid using graphene modified electrodes. Biosensors and Bioelectronics, 25(10), 2366–2369. https://doi.org/ 10.1016/j.bios.2010.02.031.

158

Sustainable Nanomaterials for Biosystems Engineering

68. Krishnan, S. K., Singh, E., Singh, P., Meyyappan, M., & Nalwa, H. S., (2019). A review on graphene-based nanocomposites for electrochemical and fluorescent biosensors. RSC Advances, 9(16), 8778–8881. https://doi.org/10.1039/C8RA09577A. 69. Kucukkolbasi, S., Erdogan, Z. O., Baslak, C., Sogut, D., Kus, M., & Highly, A., (2019). A Highly Sensitive ascorbic acid sensor based on graphene oxide/CdTe quantum dotsmodified glassy carbon electrode. Russian Journal of Electrochemistry, 55(2), 107–114. https://doi.org/10.1134/S1023193519010051. 70. Li, M., Zhou, X., Ding, W., Guo, S., & Wu, N., (2013). Fluorescent aptamer-functionalized graphene oxide biosensor for label-free detection of mercury(II). Biosensors and Bioelectronics, 41, 889–893. https://doi.org/10.1016/j.bios.2012.09.060. 71. Li, Y., Wang, H., Yan, B., & Zhang, H., (2017). An electrochemical sensor for the determination of bisphenol A using glassy carbon electrode modified with reduced graphene oxide-silver/poly-L-lysine nanocomposites. Journal of Electroanalytical Chemistry, 805, 39–46. https://doi.org/10.1016/j.jelechem.2017.10.022. 72. Li, Z., Xie, C., Wang, J., Meng, A., & Zhang, F., (2015). Direct electrochemistry of cholesterol oxidase immobilized on chitosan–graphene and cholesterol sensing. Sensors and Actuators. Part B, 208, 505–511. https://doi.org/10.1016/j.snb.2014.11.054. 73. Lian, P., Zhu, X., Liang, S., Li, Z., Yang, W., & Wang, H., (2010). Electrochimica acta large reversible capacity of high-quality graphene sheets as an anode material for lithium-ion batteries. Electrochimica Acta, 55(12), 3909–3914. https://doi.org/10.1016/j. electacta.2010.02.025. 74. Lian, Q., He, Z., He, Q., Luo, A., Yan, K., Zhang, D., Lu, X., & Zhou, X., (2014). Simultaneous determination of ascorbic acid, dopamine, and uric acid based on tryptophan functionalized graphene. Analytica Chimica Acta, 823, 32–39. https://doi. org/10.1016/j.aca.2014.03.032. 75. Liang, M., & Zhi, L., (2009). Graphene-based electrode materials for rechargeable lithium batteries. Journal of Materials Chemistry, 19(33), 5871–5878. https://doi.org/10.1039/ b901551e. 76. Liu, C., Alwarappan, S., Chen, Z., Kong, X., & Li, C. Z., (2010). Membraneless enzymatic biofuel cells based on graphene nanosheets. Biosensors and Bioelectronics, 25(7), 1829–1833. https://doi.org/10.1016/j.bios.2009.12.012. 77. Grande, L., Chundi, V. T., Wei, D., Bower, C., Andrew, P., & Ryhänen, T., (2012). Graphene for energy harvesting/storage devices and printed electronics. Particuology, 10(1), 1–8. https://doi.org/10.1016/j.partic.2011.12.001. 78. Lu, T., Zhang, Y., Li, H., Pan, L., Li, Y., & Sun, Z., (2010). Electrochemical behaviors of graphene-ZnO and graphene-SnO2 composite films for supercapacitors. Electrochimica Acta, 55(13), 4170–4173. https://doi.org/10.1016/j.electacta.2010.02.095. 79. Ma, G., Yang, M., Li, C., Tan, H., Deng, L., Xie, S., Xu, F., et al., (2016). Preparation of spinel nickel-cobalt oxide nanowrinkles/reduced graphene oxide hybrid for nonenzymatic glucose detection at physiological level. Electrochimica Acta, 220, 545–553. https://doi. org/10.1016/j.electacta.2016.10.163. 80. Magerusan, L., Socaci, C., Coros, M., Pogacean, F., Rosu, M. C., Gergely, S., Pruneanu, S., et al., (2017). Electrochemical platform based on nitrogen-doped graphene/chitosan nanocomposite for selective Pb2+ detection. Nanotechnology, 28(11), 114001. https:// doi.org/10.1088/1361-6528/aa56cb. 81. Mahmoudi, E., Hajian, A., Rezaei, M., Afkhami, A., Amine, A., & Bagheri, H., (2019). A novel platform based on graphene nanoribbons/protein capped Au-Cu bimetallic

Recent Trends in Graphene-Derived Applications 159 nanoclusters: Application to the sensitive electrochemical determination of bisphenol A. Microchemical Journal, 145, 242–251. https://doi.org/10.1016/j.microc.2018.10.044. 82. Mascagni, D. B. T., Miyazaki, C. M., Da Cruz, N. C., De Moraes, M. L., Riul, A. Jr., & Ferreira, M., (2016). Layer-by-layer assembly of functionalized reduced graphene oxide for direct electrochemistry and glucose detection. Materials Science and Engineering. C, Materials for Biological Applications, 68, 739–745. https://doi.org/10.1016/j.msec. 2016.06.001. 83. Farooqui, U. R., Ahmad, A. L., & Hamid, N. A., (2018). Graphene oxide: A promising membrane material for fuel cells. Renewable and Sustainable Energy Reviews, 82, 714–733. https://doi.org/10.1016/j.rser.2017.09.081. 84. Mohammadi, S., Taheri, A., & Rezayati-Zadorcid, Z., (2018). Ultrasensitive and selective non-enzymatic glucose detection based on Pt electrode modified by carbon nanotubes@ graphene oxide/ nickel hydroxide-nafion hybrid composite in alkaline media. Progress in Chemical and Biochemical Research, 1(1), 1–10. https://doi.org/10.29088/SAMI/ PCBR.2018.1.110. 85. Narwal, V., Deswal, R., Batra, B., Kalra, V., Hooda, R., Sharma, M., & Rana, J. S., (2019). Cholesterol biosensors: A review. Steroids, 143, 6–17. https://doi.org/10.1016/j. steroids.2018.12.003. 86. Nikoleli, G. P., Siontorou, C., Nikolelis, D., Bratakou, S., Karapetis, S., & Tzamtzis, N., (2017). Biosensors based on lipid modified graphene microelectrodes. C, 3(4), 9. https:// doi.org/10.3390/c3010009. 87. Niu, X., Zhong, Y., Chen, R., Wang, F., Liu, Y., & Luo, D. A., (2018). ‘Turn-on’ fluorescence sensor for Pb2+ detection based on graphene quantum dots and gold nanoparticles. Sensors and Actuators. Part B, 255, 1577–1581. https://doi.org/10.1016/j.snb.2017.08.167. 88. Paek, S. M., Yoo, E., & Honma, I., (2009). Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. Nano-Letters, 9(1), 72–75. https://doi.org/10.1021/nl802484w. 89. Pal, M., & Khan, R., (2017). Graphene oxide layer decorated gold nanoparticles based immunosensor for the detection of prostate cancer risk factor. Analytical Biochemistry, 536, 51–58. https://doi.org/10.1016/j.ab.2017.08.001. 90. Palanisamy, S., Karuppiah, C., & Chen, S. M., (2014). Direct electrochemistry and electrocatalysis of glucose oxidase immobilized on reduced graphene oxide and silver nanoparticles nanocomposite modified electrode. Colloids and Surfaces B: Biointerfaces, 114, 164–169. https://doi.org/10.1016/j.colsurfb.2013.10.006. 91. Pan, D., Wang, S., Zhao, B., Wu, M., Zhang, H., Wang, Y., & Jiao, Z., (2009). Li storage properties of disordered graphene nanosheets. Chemistry of Materials, 21(14), 3136–3142. https://doi.org/10.1021/cm900395k. 92. Pandey, A., Gurbuz, Y., Ozguz, V., Niazi, J. H., & Qureshi, A., (2017). Grapheneinterfaced electrical biosensor for label-free and sensitive detection of foodborne pathogenic E. coli O157:H7. Biosensors and Bioelectronics, 91, 225–231. https://doi. org/10.1016/j.bios.2016.12.041. 93. Papageorgiou, D. G., Kinloch, I. A., & Young, R. J., (2017). Mechanical properties of graphene and graphene-based nanocomposites. Progress in Materials Science, 90, 75–127. https://doi.org/10.1016/j.pmatsci.2017.07.004. 94. Parlak, O., Tiwari, A., Turner, A. P., & Tiwari, A., (2013). Template-directed hierarchical self-assembly of graphene based hybrid structure for electrochemical biosensing. Biosensors and Bioelectronics, 49, 53–62. https://doi.org/10.1016/j.bios.2013.04.004.

160

Sustainable Nanomaterials for Biosystems Engineering

95. Paulitz, T. C., & Bélanger, R. R., (2001). Biological control in greenhouse systems. Annual Review of Phytopathology, 39(1), 103–133. https://doi.org/10.1146/annurev. phyto.39.1.103. 96. Pérez-Ruiz, F., Jansen, T., Tausche, A. K., Juárez-Campo, M., Gurunath, R. K., & Richette, P., (2019). Efficacy and safety of lesinurad for the treatment of hyperuricemia in gout. Drugs in Context, 8, 212581. https://doi.org/10.7573/dic.212581. 97. Ping, J., Wu, J., Wang, Y., & Ying, Y., (2012). Simultaneous determination of ascorbic acid, dopamine, and uric acid using high-performance screen-printed graphene electrode. Biosensors and Bioelectronics, 34(1), 70–76. https://doi.org/10.1016/j.bios.2012.01.016. 98. Pumera, M., (2009). Electrochemistry of graphene: New horizons for sensing and energy storage. Chemical Record, 9(4), 211–223. https://doi.org/10.1002/tcr.200900008. 99. Qi, S., Zhao, B., Tang, H., & Jiang, X., (2015). Determination of ascorbic acid, dopamine, and uric acid by a novel electrochemical sensor based on pristine graphene. Electrochimica Acta, 161, 395–402. https://doi.org/10.1016/j.electacta.2015.02.116. 100. Qian, Z. S., Shan, X. Y., Chai, L. J., Chen, J. R., & Feng, H., (2015). A fluorescent nanosensor based on graphene quantum dots-aptamer probe and graphene oxide platform for detection of lead(II). Biosensors and Bioelectronics, 68, 225–231. https:// doi.org/10.1016/j.bios.2014.12.057. 101. Raccichini, R., Varzi, A., Passerini, S., & Scrosati, B., (2015). The role of graphene for electrochemical energy storage. Nature Materials, 14(3), 271–279. https://doi.org/ 10.1038/nmat4170. 102. Rajaji, U., Muthumariyappan, A., Chen, S. M., Chen, T. W., & Ramalingam, R. J., (2019). A novel electrochemical sensor for the detection of oxidative stress and cancer biomarker (4-nitroquinoline N-oxide) based on iron nitride nanoparticles with multilayer reduced graphene nanosheets modified electrode. Sensors and Actuators. Part B, 291, 120–129. https://doi.org/10.1016/j.snb.2019.04.041. 103. Rapini, R., & Marrazza, G., (2017). Electrochemical aptasensors for contaminants detection in food and environment: Recent advances. Bioelectrochemistry, 118, 47–61. https://doi.org/10.1016/j.bioelechem.2017.07.004. 104. Rauf, S., Mishra, G. K., Azhar, J., Mishra, R. K., Goud, K. Y., Nawaz, M. A. H., Marty, J. L., & Hayat, A., (2018). Carboxylic group riched graphene oxide based disposable electrochemical immunosensor for cancer biomarker detection. Analytical Biochemistry, 545, 13–19. https://doi.org/10.1016/j.ab.2018.01.007. 105. Razmi, H., & Mohammad-Rezaei, R., (2013). Graphene quantum dots as a new substrate for immobilization and direct electrochemistry of glucose oxidase: Application to sensitive glucose determination. Biosensors and Bioelectronics, 41, 498–504. https:// doi.org/10.1016/j.bios.2012.09.009. 106. Reta, N., Saint, C. P., Michelmore, A., Prieto-Simon, B., & Voelcker, N. H., (2018). Nanostructured electrochemical biosensors for label-free detection of water-and foodborne pathogens. ACS Applied Materials and Interfaces, 10(7), 6055–6072. https://doi. org/10.1021/acsami.7b13943. 107. Saikia, K., Kakati, B. K., Boro, B., & Verma, A., (2018). Chapter 13. Current advances and applications of fuel cell technologies. In: Sarangi, P., Nanda, S., & P. Mohanty, P., (eds.), Recent Advancements in Biofuels and Bioenergy Utilization (pp. 303–337). Springer. 108. Seger, B., & Kamat, P. V., (2009). Electrocatalytically active graphene-platinum nanocomposites. Role of 2-D carbon support in PEM fuel cells. Journal of Physical Chemistry C, 113(19), 7990–7995. https://doi.org/10.1021/jp900360k.

Recent Trends in Graphene-Derived Applications 161 109. Semwal, V., & Gupta, B. D., (2018). LSPR-and SPR-based fiber-optic cholesterol sensor using immobilization of cholesterol oxidase over silver nanoparticles coated graphene oxide nanosheets. IEEE Sensors Journal, 18(3), 1039–1046. https://doi.org/10.1109/ JSEN.2017.2779519. 110. Shahrokhian, S., & Salimian, R., (2018). Ultrasensitive detection of cancer biomarkers using conducting polymer/electrochemically reduced graphene oxide-based biosensor: Application toward BRCA1 sensing. Sensors and Actuators. Part B, 266, 160–169. https://doi.org/10.1016/j.snb.2018.03.120. 111. Shahzad, F., Zaidi, S. A., & Koo, C. M., (2017). Highly sensitive electrochemical sensor based on environmentally friendly biomass-derived sulfur-doped graphene for cancer biomarker detection. Sensors and Actuators. Part B, 241, 716–724. https://doi. org/10.1016/j.snb.2016.10.144. 112. Sheng, Z. H., Zheng, X. Q., Xu, J. Y., Bao, W. J., Wang, F. B., & Xia, X. H., (2012). Electrochemical sensor based on nitrogen doped graphene: Simultaneous determination of ascorbic acid, dopamine, and uric acid. Biosensors and Bioelectronics, 34(1), 125–131. https://doi.org/10.1016/j.bios.2012.01.030. 113. Shi, X., Gu, W., Peng, W., Li, B., Chen, N., Zhao, K., & Xian, Y., (2014). Sensitive Pb(2+) probe based on the fluorescence quenching by graphene oxide and enhancement of the leaching of gold nanoparticles. ACS Applied Materials and Interfaces, 6(4), 2568–2575. https://doi.org/10.1021/am405012k. 114. Shukla, S., Haldorai, Y., Bajpai, V. K., Rengaraj, A., Hwang, S. K., Song, X., Kim, M., et al., (2018). Electrochemical coupled immunosensing platform based on graphene oxide/gold nanocomposite for sensitive detection of Cronobacter sakazakii in powdered infant formula. Biosensors and Bioelectronics, 109, 139–149. https://doi.org/10.1016/j. bios.2018.03.010. 115. Singh, A., Sinsinbar, G., Choudhary, M., Kumar, V., Pasricha, R., Verma, H. N., Singh, S. P., & Arora, K., (2013). Graphene oxide-chitosan nanocomposite based electrochemical DNA biosensor for detection of typhoid. Sensors and Actuators. Part B, 185, 675–684. https://doi.org/10.1016/j.snb.2013.05.014. 116. Soodchomshom, B., (2010). Switching effect in a gapped graphene D-WAVE superconductor structure. Physica B, 405(5), 1383–1387. https://doi.org/10.1016/j.physb. 2009.12.004. 117. Staden, R. S., Balahura, L., Oprisanu-Vulpe, A., Gugoasa, L. A., Staden, J. F. V., Ungureanu, E., Socaci, C., & Porav, A., (2017). Nanostructured materials detect dopamine in biological fluids. Journal of the Electrochemical Society, 164(12), B561–B566. 118. Stoller, M. D., Park, S., Zhu, Y., An, J., Ruoff, R. S., & Ultracapacitors, G. B., (2008). Graphene-based ultracapacitors. Nano-Letters, 8(10), 3498–3502. https://doi.org/10.1021/ nl802558y. 119. Su, B., Shao, H., Li, N., Chen, X., Cai, Z., & Chen, X., (2017). A sensitive bisphenol A voltammetric sensor relying on Au-Pd nanoparticles/graphene composites modified glassy carbon electrode. Talanta, 166, 126–132. https://doi.org/10.1016/j.talanta.2017.01.049. 120. Sun, C. L., Lee, H. H., Yang, J. M., & Wu, C. C., (2011). The simultaneous electrochemical detection of ascorbic acid, dopamine, and uric acid using graphene/size-selected Pt nanocomposites. Biosensors and Bioelectronics, 26(8), 3450–3455. https://doi.org/10.1016/j. bios.2011.01.023. 121. Tavakolian-Ardakani, Z., Hosu, O., Cristea, C., Mazloum-Ardakani, M., & Marrazza, G., (2019). Latest trends in electrochemical sensors for neurotransmitters: A review. Sensors, 19(9), 2037. https://doi.org/10.3390/s19092037.

162

Sustainable Nanomaterials for Biosystems Engineering

122. Thirumalraj, B., Palanisamy, S., Chen, S. M., Yang, C. Y., Periakaruppan, P., & Lou, B. S., (2015). Direct electrochemistry of glucose oxidase and sensing of glucose at a glassy carbon electrode modified with a reduced graphene oxide/fullerene-C60 composite. RSC Advances, 5(95), 77651–77657. https://doi.org/10.1039/C5RA12018G. 123. Tiwari, I., Singh, M., Pandey, C. M., & Sumana, G., (2015). Electrochemical detection of a pathogenic Escherichia coli specific DNA sequence based on a graphene oxidechitosan composite decorated with nickel ferrite nanoparticles. RSC Advances, 5(82), 67115–67124. https://doi.org/10.1039/C5RA07298K. 124. Tiwari, I., Singh, M., Pandey, C. M., & Sumana, G., (2015). Electrochemical genosensor based on graphene oxide modified iron oxide-chitosan hybrid nanocomposite for pathogen detection. Sensors and Actuators. Part B, 206, 276–283. https://doi.org/10.1016/j.snb. 2014.09.056. 125. Tonelli, D., Scavetta, E., & Gualandi, I., (2019). Electrochemical deposition of nanomaterials for electrochemical sensing. Sensors, 19(5), 1186. https://doi.org/10.3390/ s19051186. 126. Tukimin, N., Abdullah, J., & Sulaiman, Y., (2018). Review-electrochemical detection of uric acid, dopamine, and ascorbic acid. Journal of the Electrochemical Society, 165(7), B258–B267. https://doi.org/10.1149/2.0201807jes. 127. Tung, T. T., Nine, M. J., Krebsz, M., Pasinszki, T., Coghlan, C. J., Tran, D. N. H., & Losic, D., (2017). Recent advances in sensing applications of graphene assemblies and their composites. Advanced Functional Materials, 27(46). https://doi.org/10.1002/ adfm.201702891, PubMed: 1702891. 128. Tuteja, S. K., Duffield, T., & Neethirajan, S., (2017). Graphene-based multiplexed disposable electrochemical biosensor for rapid on-farm monitoring of NEFA and βHBA dairy biomarkers. Journal of Materials Chemistry. B, 5(33), 6930–6940. https://doi. org/10.1039/c7tb01382e. 129. Varmira, K., Saed-Mocheshi, M., & Jalalvand, A. R., (2017). Electrochemical sensing and bio-sensing of bisphenol A and detection of its damage to DNA: A comprehensive review. Sensing and Bio-Sensing Research, 15, 17–33. https://doi.org/10.1016/j. sbsr.2017.07.002. 130. Vijayaraj, K., Hong, S. W., Jin, S. H., Chang, S. C., & Park, D. S., (2016). Fabrication of a novel disposable glucose biosensor using an electrochemically reduced graphene oxide-glucose oxidase biocomposite. Analytical Methods, 8(38), 6974–6981. https:// doi.org/10.1039/C6AY02032A. 131. Vinoth, V., Wu, J. J., & Anandan, S., (2016). Sensitive electrochemical determination of dopamine and uric acid using AuNps(EDAS)-rGO nanocomposites. Analytical Methods, 8(22), 4379–4390. https://doi.org/10.1039/C6AY00335D. 132. Vivekchand, S. R. C., Rout, C. S., Subrahmanyam, K. S., Govindaraj, A., & Rao, C. N. R., (2008). Graphene-based electrochemical supercapacitors. Journal of Chemical Sciences, 120(1), 9–13. https://doi.org/10.1007/s12039-008-0002-7. 133. Wallace, G. G., Chen, J., Li, D., Moulton, S. E., & Razal, J. M., (2010). Nanostructured carbon electrodes. Journal of Materials Chemistry, 20(18), 3553–3562. https://doi. org/10.1039/b918672g. 134. Wan, X., Yang, S., Cai, Z., He, Q., Ye, Y., Xia, Y., Li, G., & Liu, J., (2019). Facile synthesis of MnO2 nanoflowers/N-doped reduced graphene oxide composite and its application for simultaneous determination of dopamine and uric acid. Nanomaterials, 9(6), 1–16. https://doi.org/10.3390/nano9060847.

Recent Trends in Graphene-Derived Applications 163 135. Wang, B., (2019). Direct electrochemistry of glucose oxidase on a graphene-graphene oxide nanocomposite-modified electrode for a glucose biosensor. International Journal of Electrochemical Science, 14, 7495–7506. https://doi.org/10.20964/2019.08.34. 136. Wang, C., Yang, F., Tang, Y., Yang, W., Zhong, H., Yu, C., Li, R., et al., (2018). Graphene quantum dots nanosensor derived from 3D nanomesh graphene frameworks and its application for fluorescent sensing of Cu2+ in rat brain. Sensors and Actuators. Part B, 258, 672–681. https://doi.org/10.1016/j.snb.2017.11.098. 137. Wang, F., Gu, Z., Lei, W., Wang, W., Xia, X., & Hao, Q., (2014). Graphene quantum dots as a fluorescent sensing platform for highly efficient detection of copper(II) ions. Sensors and Actuators. Part B, 190, 516–522. https://doi.org/10.1016/j.snb.2013.09.009. 138. Wang, H., Cui, L. F., Yang, Y., Sanchez, C. H. S., Robinson, J. T., Liang, Y., Cui, Y., & Dai, H., (2010). Mn3O4-graphene hybrid as a high-capacity anode material for lithium-ion batteries. Journal of the American Chemical Society, 132(40), 13978–13980. https://doi. org/10.1021/ja105296a. 139. Wang, J., Mu, X., & Sun, M., (2019). The thermal, electrical, and thermoelectric properties of graphene nanomaterials. Nanomaterials, 9(2), 218. https://doi.org/10.3390/ nano9020218. 140. Wang, Q., Wang, Q., Li, M., Szunerits, S., & Boukherroub, R., (2015). Preparation of reduced graphene oxide/Cu nanoparticle composites through electrophoretic deposition: Application for nonenzymatic glucose sensing. RSC Advances, 5(21), 15861–15869. https://doi.org/10.1039/C4RA14132F. 141. Wang, S., Zhai, S., Li, Y., Zhang, C., Han, Z., Peng, R., Wang, X., et al., (2018). Simultaneously detection of Pb2+ and Hg2+ using electrochemically reduced graphene oxide. International Journal of Electrochemical Science, 13(1), 785–796. https://doi. org/10.20964/2018.01.84. 142. Wang, X., Zhi, L., & Müllen, K., (2008). Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano-Letters, 8(1), 323–327. https://doi.org/10.1021/ nl072838r. 143. Wang, Y., Shi, Z., Huang, Y., Ma, Y., Wang, C., Chen, M., & Chen, Y., (2009). Supercapacitor devices based on graphene materials. Journal of Physical Chemistry C, 113(30), 13103–13107. https://doi.org/10.1021/jp902214f. 144. Wen, G. L., Zhao, W., Chen, X., Liu, J. Q., Wang, Y., Zhang, Y., Huang, Z. J., & Wu, Y. C., (2018). N-doped reduced graphene oxide /MnO2 nanocomposite for electrochemical detection of Hg2+ by square wave stripping voltammetry. Electrochimica Acta, 291, 95–102. https://doi.org/10.1016/j.electacta.2018.08.121. 145. Weng, X., Cao, Q., Liang, L., Chen, J., You, C., Ruan, Y., Lin, H., & Wu, L., (2013). Simultaneous determination of dopamine and uric acid using layer-by-layer graphene and chitosan assembled multilayer films. Talanta, 117, 359–365. https://doi.org/10.1016/j. talanta.2013.09.023. 146. Wu, Z., Wang, D., Ren, W., Zhao, J., Zhou, G., Li, F., & Cheng, H., (2010). Anchoring hydrous RuO2 on graphene sheets for high-performance electrochemical capacitors. Advanced Functional Materials, 20(20), 3595–3602. https://doi.org/10.1002/adfm. 201001054. 147. Xin, Y., Liu, J., Zhou, Y., Liu, W., Gao, J., Xie, Y., Yin, Y., & Zou, Z., (2011). Preparation and characterization of Pt supported on graphene with enhanced electrocatalytic activity in fuel cell. Journal of Power Sources, 196(3), 1012–1018. https://doi.org/10.1016/j. jpowsour.2010.08.051.

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148. Xuan, X., Yoon, H. S., & Park, J. Y., (2018). A wearable electrochemical glucose sensor based on simple and low-cost fabrication supported micro-patterned reduced graphene oxide nanocomposite electrode on flexible substrate. Biosensors and Bioelectronics, 109, 75–82. https://doi.org/10.1016/j.bios.2018.02.054. 149. Yan, J., Wei, T., Shao, B., Fan, Z., Qian, W., Zhang, M., & Wei, F., (2010). Preparation of a graphene nanosheet/polyaniline composite with high specific capacitance. Carbon, 48(2), 487–493. https://doi.org/10.1016/j.carbon.2009.09.066. 150. Yang, L., & Bashir, R., (2008). Electrical/electrochemical impedance for rapid detection of foodborne pathogenic bacteria. Biotechnology Advances, 26(2), 135–150. https://doi. org/10.1016/j.biotechadv.2007.10.003. 151. Yoo, E., Kim, J., Hosono, E., Zhou, H. S., Kudo, T., & Honma, I., (2008). Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium-ion batteries. Nano-Letters, 8(8), 2277–2282. https://doi.org/10.1021/nl800957b. 152. Yu, X., Zhang, W., Zhang, P., & Su, Z., (2017). Fabrication technologies and sensing applications of graphene-based composite Fi LMS: Advances and challenges. Biosensors and Bioelectronics, 89, 72–84. https://doi.org/10.1016/j.bios.2016.01.081. 153. Zhang, C., Zhang, Z., Yang, Q., & Chen, W., (2018). Graphene-based electrochemical glucose sensors: Fabrication and sensing properties. Electroanalysis, 30(11), 2504–2524. https://doi.org/10.1002/elan.201800522. 154. Zhang, M., Yuan, R., Chai, Y., Wang, C., & Wu, X., (2013). Cerium oxide-graphene as the matrix for cholesterol sensor. Analytical Biochemistry, 436(2), 69–74. https://doi. org/10.1016/j.ab.2013.01.022. 155. Zhou, Q., Li, G., Zhang, Y., Zhu, M., Wan, Y., & Shen, Y., (2016). Highly selective and sensitive electrochemical immunoassay of Cry1C using nanobody and Π-Π stacked graphene oxide/thionine assembly. Analytical Chemistry, 88(19), 9830–9836. https:// doi.org/10.1021/acs.analchem.6b02945. 156. Zhu, J., Ye, Z., Fan, X., Wang, H., Wang, Z., Chen, B., & Highly, A., (2019). A highly Sensitive biosensor based on Au Nps/Rgo-PAMAM-Fc nanomaterials for detection of cholesterol. International Journal of Nanomedicine, 14, 835–849. https://doi. org/10.2147/IJN.S184013. 157. Zhu, X., Zhang, Z., Xue, Z., Huang, C., Shan, Y., Liu, C., Qin, X., et al., (2017). Understanding the selective detection of Fe3+ based on graphene quantum dots as fluorescent probes: The Ksp of a metal hydroxide-assisted mechanism. Analytical Chemistry, 89(22), 12054–12058. https://doi.org/10.1021/acs.analchem.7b02499. 158. Zou, H. L., Li, B. L., Luo, H. Q., & Li, N. B., (2015). A novel electrochemical biosensor based on hemin functionalized graphene oxide sheets for simultaneous determination of ascorbic acid, dopamine, and uric acid. Sensors and Actuators B, 207, 535–541. https:// doi.org/10.1016/j.snb.2014.10.121.

CHAPTER 6

NANOMATERIALS FOR BIOSENSING APPLICATIONS: CONCEPTS AND RECENT ADVANCEMENTS JNANRAJ BORAH and ANUPAM CHETIA

ABSTRACT Biosensor is one of the appealing topics drawing the interest of the scientific community due to the complexity of biological entities that are directly connected to the preservation of a sound environment. To improve the sensitivity and performance of biosensors, their designs have changed significantly during the past few years. Nanotechnology (NT) provides technologies to study and manufacture materials in the nanoscale range (1–100 nm). Nanomaterials (NMs), including nanoparticles (NPs), nanorods, nanotubes, and nanowires have been introduced into this area which has significantly improved the sensing performance of biosensors. NT-based biosensors or nanobiosensors utilize the novel NM properties such as electrical, optical, chemical, magnetic, etc., for efficient sensing of a target molecule. NM-based biosensors are in general fast, highly sensitive, and small in size, which provide versatility to the sensing technology. Focusing on this theme, this chapter includes a discussion on the basic concept of NT-based biosensors along with different types of nanobiosensors and its implementation in various applications. This chapter highlights the advances in nanomaterials (NMs) and their roles in the biosensing field.

Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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6.1 INTRODUCTION In the present situation of ever-changing environmental advancements and subsequent altered homeostatic activities that occur both in vivo and ex vivo stages, the sensing of biological responses or the biosensors has been accepted considerable importance. In fields such as biomedical, diagnosis, agriculture, food safety screening, fermentations, biodefense, plant biology and in different applications for environmental protection, the study of the actions or behavior of ever evolving materials has taken on considerable significance. Biosensing plays a vital role in biomedical treatment and diagnostic. In contrast to traditional detection methods, including spectroscopy or chromatography, biosensing technology has significant merits [23, 41]. One of the leading causes of death worldwide is a lack of early, affordable treatment, and successful early detection technology of diseases like lung cancer, ischemic heart disease, cirrhosis, and related contagious diseases [48, 63]. Thus, the development of good biosensors that could analyze the slightest features of natural interactions, even on an extremely tiny scale and maximal possible sensitivities, with extreme specificity, deserves immediate focus. The biosensing process constitutes with three processes binding of bioanalytes to the receptor, generation of a signal or transduction and detection [40]. The transduction mechanisms in charge of converting the reactions of bioanalyte interactions in a reproducible and recognizable approach, making use of the transformation of complicated biochemical response energy into electrical type by the usage of transduction mechanisms, are an important component of biosensing [27, 41]. NT deals with the study and manufacture of materials, termed as NMs at the nanodimension (1–100 nm) [8, 41]. In this particular dimension, NMs are exceptional incumbents since they have exceptionally high ratios of the area of surface to the volume which provide the area to be utilized in a useful manner that is way more effective. As in several other technical fields, NMs have proven their suitability for applications for biosensing [34]. The majority of the constituent atoms of theirs or the particles are found over the surface area of this kind of substance due to the small size of theirs, providing rise to a remarkable differentiation in the basic physicochemical properties of theirs coming from the bulk of exact same materials. A further considerations are the quantum consequences of discontinuous behavior, which result in large changes in NM qualities because of the quantum containment of delocalized électrons. [48]. In addition, the great strengths of biosensor science are their electromechanical properties. Biosensors primarily based on NMs which

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mirror the amalgamation of chemistry, material science, biotechnology, and molecular biology, will significantly improve biomolecule detection sensitivity plus specificity, protecting the biomolecule detection sensitivity and specificity [41, 48]. These biosensors can recognize or alter atoms and molecules, and they have a lot of room to grow for applications including biomolecular recognition, disease detection, and environmental protection [2, 43, 62]. NT-provided nanostructural miracles have revolutionized the events in the field of molecular biology that have allowed atoms and molecules to be controlled and have tracked the biological phenomena with much greater specificity at the physiological level. The concept of biosensors has to be soundly gathered to really understand what this technology is actually about [27, 41]. This chapter describes the basic concept of NT based biosensors, suitable selection, and optimization for the development of NMs for sensing applications, various types of nanobiosensors, and their application in biomedical, diagnostic, and other fields. The chapter also highlights the biosensors recently built to detect the COVID-19 virus. 6.2  CONCEPT OF BIOSENSORS Using biological interactions, a biosensor is usually referred to as a sensing unit or even a measuring technique explicitly created to estimate a substance and, after that, evaluate these interactions in a readable type utilizing electromechanical interpretation and transduction [41]. The very first biosensor was created in the year 1950 by American biochemist “L, Clark” [5]. This particular biosensor is utilized to evaluate oxygen in the bloodstream, so the electrode applied to this particular sensor is named as Clark electrode or oxygen electrode. As for the basic and conceptual system of operation, these components are the bioreceptor, transducer, and detector. The receptor distinctly combine to an analyte, the transducer converts biochemical reaction energy to electrical energy, and a framework for sensing and transforming the signal into useful information [41]. These detection processes might be optical, electrochemical, or perhaps piezoelectric in character. In comparison to standard assessment strategies, like enzymelinked immunosorbent assays (ELISA), Biosensors have the potential to be completely automated, exhibit improved reproducibility, permit rapid and real-time evaluation, and often display a chance for re-utilize as an outcome of surface area regeneration [46].

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A biosensor’s primary aim or role is to detect biologically distinct materials. In most cases, these compounds are immunological molecules, antibodies, enzymes, proteins, etc. It is accomplished with an additional biologically delicate substance which participate during the making of bioreceptor. A bioreceptor thus appears to be the part of a biosensor that can serve as a template for recognizing the material. There may be various materials which may be utilized as bioreceptors. For example, antigen is being used to screen an antibody and vice versa [41, 66]. The fundamental function of the next element, i.e., the transducer, is converting the corresponding biochemical energy that has been arising because of the interaction between bioreceptor and bioanalyte, into electric energy. Transducer essentially converts one type of power into another. The nature of the very first type is biochemical, and the basic association between the bioreceptor and the bioanalyte generates it, even though the nature of the second type is normally electrical. The detector device would be the third part. This captures the electrical signal directed by the transducer element and amplifies it appropriately; hence it is possible to interpret and evaluate the resulting reaction. Along with these components, an extremely important necessity of the nanobiosensors will be the accessibility of immobilization systems, which may be utilized to bioreceptor immobilization to create the reaction of its with bioanalyte a lot more feasible and economical. Immobilization can make the general practice of biological detection less expensive; also, the functionality of the methods depending on this concept can also be influenced by changes in pH, temperature, interference by pollutants, along with any other physical and chemical variations [37, 41]. 6.3  NANOTECHNOLOGY-BASED BIOSENSORS: NANOBIOSENSORS Nanotechnology is a quickly expanding arena involving NMs. NT-based detection methods hold the possibility for offering a selection of advantages over conventional lab methodologies. Over the last 10 years, there are already the amount of promising measures towards the growth as well as the use of novel NT. The understanding of the principle of biosensing lays the basis for learning and the construction of nanobiosensors. Nanobiosensors are fundamentally sensors constituted of NMs and, surprisingly, they are not the special sensors that could detect all nanoscale events in addition to occurrences. A number of new platforms on the basis of NT have recently been developed to detect an extensive range of targets, such as infectious agents,

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medicines, nucleic acids, protein biomarkers, and cancer cells. The question that remains a concern from the explanation above is the fact that NMs are expected to be applied in the manufacture of biosensors or perhaps they are intending to have a significant effect on the whole technology. NMs are a distinctive contribution to mankind from NT; these are the substances that happen to have between one and 100 nanometers of one of their measurements. The size limitations of these materials make it possible for them to be very unusual since most of their constituent atoms concentrated at or very near to their surface and often have virtually all substantial physical and chemical properties that vary significantly from those of the same compounds at the bulk scale. An additional aspect leading to considerable variations in the qualities of NMs it is noted that, because of the quantum containment of delocalized electrons, the quantum effects toward discontinuous behavior arise. Since the amount of nanoparticular atoms in the surface is much greater than in bulk, their binding energy is smaller, and thus their melting points are decreased. The structure of the particles is critical to their properties. Nanorods, for example, can have significantly different properties than nanospheres made of the same substance. The boosted surface area per unit mass additionally results to 1,000-fold enhance in the chemical reactivity [41, 44]. Thus, these NMs are able to perform really effective roles as a sensor in the biosensor technologies. Numerous NMs are assessed for improved biological signaling as well as transduction pathways based on their mechanical and electronic properties. Many of the widely-used materials contain nanotubes, NPs, nanorods, nanowires, and nanocrystalline films. Nanobiosensors have become highly effective inputs in biosensor technology that has been achievable just as a result of the marvels of nanotechnological ramifications of the issue. A wide selection of biosensing products which use NPs or maybe nanostructures are being investigated. These are studied globally and may be as specific as the use of amperometric products for sugar enzyme recognition in order to use QDs as representatives of fluorescence when it comes to binding detection and for some biomolecular detection using bioconjugated NMs. In addition, these components can be used to facilitate electron microscopic detection. NMs like magnetic nanoparticles (MNPs), nanosensors, nanowires, carbon nanotubes (CNTs), and QDs, including giant magnetoresistance (GMR) sensors, are utilized to quantitatively identify biomolecules with, experimentally, fairly good precision. More details are provided in the text on the several bio-sensors produced by using different nano-scale materials. The content reveals the implications and results in the use of multiple NMs and their

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intrinsic advantages, as well as the key parameters where they may have major consequences and achieve dramatically improved results [41]. 6.4  DEVELOPMENT OF NANOMATERIALS FOR NANOBIOSENSING: SELECTION AND OPTIMIZATION There is a wide range, elements which regulate or even determine the usage of a specific type of NMs for biosensors. These elements will be the essential components of the chemical and physical qualities together with the energy very sensitive and also picky responses. Until deploying the sensing programs accurately and using a NM; We should start with their preferred manufacturing. The manufacturing process is a form of experimental design known as “Nanofabrication.” The nanofabrication approach focuses on two main operations: the manufacture and architecture of nanoscale adhesive surfaces using integrated circuit science, and NM surface engineering using micromachining. This biosensing approach thus developed employs variations of four main procedures: specifically photolithography, etching/growth, thin film, surface etching techniques, and chemical bonding parameters [41]. Electrodes within nanorange or nanoscale electrodes emerge as a result of the lithography process have increased biosensing precision by having larger and better surface areas, allowing for more precise immobilization [58]. These advances are being used to build glucose biosensors using the enzyme glucose oxidase. The techniques for the use of proven platinum NPs above CNTs sheets have dramatically improved the immobilization of the enzyme methods required to detect analytic substances. These techniques have significantly broader applications for biosensing technologies, allowing glucose from many sources other than blood to be detected. Similarly, pairs of immunosensors have been established that responds the covering of thin films with a sensing surface, allowing the related analytes to be detected better and faster [47]. Extremely sensitive electric as well as electromechanical characteristics, are integrated into a few substances by building them with nanoelectromechanical methods (NEMS). NEMS technology has so provided a bunch of materials with great qualities due to the nanoscale functionality of theirs. MEMS and NEMS systems have allowed the mechanical substances to work even more and more advanced because their physical properties are of vital importance to the size of the object. Furthermore, these tools have been integrated with biological molecules and systems to progress their bioadhesion characteristics, as well as their reaction to a broad range of stimuli. Surface forces such as friction, unified forces, adhesion, plus it is

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possible to regulate viscous drag forces in an incredibly detailed way with both the application of MEMS and NEMS, enabling the best simulation of the biochemical interactions involved in technologies for biosensing [6]. The control and enhancement of their optical attributes would be another important aspect seen that use NMs for implementations for sensing. In order to maximize the sensing components’ reliable and efficient optical reaction along with the incoming light, the phenomena are particularly intriguing as surface plasm resonances and especially anticipated from NPs. Surface plasmon resonance (SPR) is an event that relies on the excitation of the surface field of particles alongside the charged particles and ionic species that generate ions and as a consequence, creates excitation of charged particles’ fluidic status. As a result of their peculiar optical properties that give them photonic character and the significant and positive effect of using fluorophores., this particular property is favorably suitable for NPs. This unique phenomenon uses absolute internal reflection that exists above a critical value for the angle of incidence. In this case, the reflection of light is improved by the subsequent modification of the critical angle of reflection by a thin, surface-coated film of metal-based NPs. This particular tendency is highly logical in the case of NMs, and it is explicitly referred to as localized plasmon surface resonance [41, 67]. The surface plasm resonance effect depends largely on the media’s refractive index and possibly the most significant property that regulates light flow through a medium. A nanobiosensor is a little more equipped to classify perhaps the tiniest interacting phenomena because of the existence of SPR, which makes a superior and considerably more effective degree of biological interaction assessment through a nanobiosensor compared to a biosensor [29, 35, 45]. This way, NMs, regardless of the nature of theirs, prior to being used for biosensing, they must be improved for their impact and efficiency in accordance with the desired purpose. Nanostructured semiconductor crystals are often used in practical applications by coupling with the sensing molecule of biological origin to increase the identification of neuronal responses. These may be merged with peptide assembly of various NMs to ensure that a self-assembly can lead to good interaction, which saves a significant amount of time compared to currently available methods and technology. Moreover, the tuning as well as surface design by high-tech inroads called collectively micromachine processes involves a key technique in the shaping of NMs for ideal application. For use in biosensing applications of NMs, components as aspect proportions, functionalization with different substances, and compatibility problems with regard to the substrate being studied are rather important [41].

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6.5  NANOMATERIAL-BASED NANOBIOSENSORS An incredibly complex field is the classification of nanobiosensors. Therefore, this is because it is focused on the dynamics of NMs integrated into the operation of biosensing. Furthermore, the meaning is not as straightforward as it seems as for the biosensors. In the case of biosensors, the receptors are categorized according to two parameters, specifically the substrate form to be investigated and the other is based on the signal transduction system used. Taking the differentiation of nanobiosensors into account, we note that the classification criteria are undoubtedly the characteristics of NMs that are required to enhance the sensing mechanism. For example, all sensors that use metal NPs to improve the sensing of biochemical signals are consist of NP-based biosensors. Similarly, in addition to performance, nanobiosensors are classified as nanotube sensors if they use CNTs as reaction specificity enhancers, whereas biosensors utilizing nanowires as charge transfer as well as carriers are referred to as nanowire biosensors. In addition, there are receptors focused on QDs that use QDs as contrast agents to improve optical responsivity. Several of the main groups of nanobiosensors developed so far and those in use are included in the forthcoming text [18, 41]. 6.5.1  NANOPARTICLE-BASED BIOSENSORS NPs have a number of likely biosensor applications. For example, biological molecules (e.g., peptides, proteins, nuclear acids) have also been used in biosensors to detect and amplify various markers, with functional NPs (electronic, magnet, and optical). Several of the NP-based sensors are the acoustic wave biosensors, optical biosensors, electrochemical, and magnetic biosensors, as described subsequent [34]. Biosensors based on acoustic waves have been built to greatly increase sensitivity and identification limitations as well. In order to get biophysical, biochemical, and medical knowledge about the analyte of interest, Mechanical or acoustic waves are used as a measurement tool in an acoustic wave biosensor [22, 41]. From electrical or mechanical differences, It detects variations in density, conductivity, elasticity, and also dielectric qualities. The piezoelectric effect is often used in these units to electrically trigger acoustic waves at an input transducer and to obtain the waves at the output transducer. Acoustic biosensors could be manufactured with piezoelectric crystals like quartz, niobite, lithium, or maybe lithium tantalate as they’re robust also ecologically steady [19, 32]. Furthermore, such sensors are adaptable and

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may potentially recognize a wide variety of biomolecules. Acoustic wave sensors may be divided on the basis of the waves they emit, such as bulk or even acoustic surface waves. All these wave mechanisms have different positives and negatives based on their specific applications. Bulk acoustic wave (BAW) biosensors employ both longitudinal and shear waves, with the latter typically selected to reduce acoustic radiation in the platform of interest. A parallel electrode is placed on either side of the thin crystal portion in BAW systems. Almost any piezoelectric part can be used in a BAW sensor, and generally, quartz is utilized, since it is a cheap substance, abundant, and abundantly synthesizable in a short amount of time. Thin quartz disks are much more steady at high temperatures than other piezoelectric components. Surface acoustic wave (SAW) sensors are utilized for a long time in computing temperature, concentration, acceleration, viscosity, pressure, and then chemical/biological entities. They are often used to conduct signal processing tasks, but they are very sensitive to their surroundings. This particular sort of acoustic wave sensors includes fundamental elements such as for instance piezoelectric substrate, micrometallization patterns, interdigital transducers (IDT), and also active thin films. Unlike BAW, which only communicates with the surroundings by traversing through the reverse surface region of the substance, SAW moves along and near the piezoelectric material’s surface [22]. The mass-based version of these sensors requires antibody-modified sol particle conjugation that attach themselves to the electrode top, which seems to have been complexed together with analyte particles attached in a fashion that immobilizes antibody molecules with the electrode surface, among a variety of stimulus-based effects in such type of sensors. The greater mass of the antibody’s bound sol molecules corresponds to a difference in the vibrational frequency on the quartz grounded sensing platform, that shift serves as the detecting basis. Most sol-based antibody particles have an optimal diameter of 5–100 nanometers. Cadmium sulfide, Au, platinum, and TiO2 crystals are commonly favored [40, 41, 56]. In the diversifying and growing technologies employed monitoring biological interactions, magnetic substances have special properties that may be exploited for the improvement of biosensors for quick measurements at the point of test. Magnetic biosensors employ magnetic particles, or maybe crystals, as a technique of detecting biological interactions by computing modifications in magnetic qualities or maybe magnetically caused consequences like changes in coil inductance, resistance or maybe magneto-optical qualities. Magnetic biosensors, which make use of specially architectured MNPs, are often made of ferrite, are often used individually or in combination. In reference to biomedical applications, these types of sensors are

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highly helpful. For many analytical uses, magnetic materials allow for a huge amount of diversity. This is essentially because the screening-related magnetic elements compose of iron that comes with certain other transition metals that have distinct characteristics. Since MNPs are integrated, conventionally used biodetection systems have become more responsive and stronger. In their magnetic behavior, transition metal alloys with other materials and iron having their unpaired electrons in the d-orbitals have been significantly flexible. Magnetic bioassay techniques are applied for the precise separation of magnetically marked targeted molecule with the aid of a magnetometer in a very common type of substances that have come to the fore in these respects. To quickly identify biological entities with superparamagnetic dynamics of MNPs as targets, exclusive products, for instance, superconducting quantum interference devices (SQUID) were used. In this particular method, On the microscope, a mylar film with attached targets is put. A suspension of MNPs containing anti-bodies is mixed in a well, and 1-s magnetic area pulses are used in parallel on the SQUID. The NPs generate a complete magnetization in the presence of the aligning field, which relax when the field is off. Unbound NPs relax easily due to Brownian rotation and contribute no perceivable signal. NPs bound to the target are captured and also undergo Neel relaxation, resulting in a slowly decaying magnetic flux that the SQUID recognizes. By using antibodies attached to MNPs, the exact antigens from the mixtures are screened with these kinds of sensors. These take advantage of the extremely paramagnetic impact of magnetic components that is especially found in the nanoscale particles [10, 41, 51]. Electrochemical biosensors sensors generally function facilitating or even evaluate the biochemical responses with the assistance of enhanced electric means. These biosensors are manufactured mainly from metallic NPs. By the use of metal NPs, biomolecule-to-biomolecule chemical reactions could be successfully and conveniently carried out, which significantly helps to achieve immobilization of one of the reactants. This unique skill really specifies these reactions and prevents the risk of obtaining unwanted side products. Colloidal Au-based NPs were applied in the unique reference to boost the immobilization of DNA on electrodes made with Au has greatly enhanced the output of a general biosensor by additionally reducing the maximum detection [9, 41]. Metal NPs are already utilized to avail the electron transfer within nanoelectronic products. Gold NPs (Au NPs) may greatly improve electron transport throughout the self-assembled monolayer molecules on the electrode surfaces. This observation might be especially useful in the improvement of electroluminescence based biosensors. For the recognition of xanthine, glucose, and H2O2, biosensors are built using

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enzyme-conjugated Au NPs [12, 41, 64, 68]. The assessment of the enzyme electrochemistry units comprising reddish horse peroxidase, immobilized on yellow electrodes filled with carbon NPs. The study suggests a much faster amperometric response and much better electrocatalytic reduction potential for horse reddish peroxidase [64]. As a result, when in contrast with the one minus having NPs, the biosensor produced exhibit enhanced sensitivity and a much lower LOD. Nanosized semiconductor crystals could be used in a similar fashion to increase the potency of photochemical responses, and biological organisms, including those of precursors and enzymes, can also be labeled to establish novel PEC methods. In this particular study, Curri et al. [16] attempted to apply self-assembly strategy to immobilized nanocrystalline CdS to allow an immobilized formaldehyde-based enzymatic detection system dehydrogenase on the gold (Au) electrodes to be able to tackle formaldehyde catalytic oxidation. Metal-based NPs have also been used in other experiments to combine with biological probes, then cope with beneficial identification of a mixture’s particular molecules. Bioassays focused on the specificity of biotin-streptavidin were produced in this regard [26]. Resonance enhancement through biorecognitive interactions with metallic nanoclusters bound to a surface was found to be useful to be used in bio-optical sensory devices. In these assays, the interaction of lectin sugar, antigen antibodies and protein receptor is introduced [4]. The analytes caused metal nanoclusters to bind and may dissociate from a reflective substrate that preferably conducts electron. The dissociation or binding may be converted into a clearly observable optical signal by resonant amplification of clusters meeting their mirror dipoles. Au nanoparticulars are used to build an optical biosensor for the identification and detection as typical fluorescence quenchers of such DNA sequences. The binding of target molecules resulted in a conformation shift and the fluorescence of the quenched fluorophore was especially restored. On this specific basis, the biosensor has identified single base mutations in a homogeneous structure [34, 42]. 6.5.2  NANOTUBE-BASED BIOSENSORS CNTs are now commonly recognized in the field of optoelectronic and material sciences as a favorite NM. Because the discovery of theirs in the year 1990’s, they’ve drawn interest globally due to their remarkable qualities, most important of which would be the electric conductivity, adaptable physical structural or geometrical features, along with the actually compelling physico-mechanical properties which range from increased aspect ratios

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to really great functionalization capabilities as well as higher mechanical stability plus flexible abilities. As a result of these features, each single-walled nanotube and multiwalled nanotubes are used to build even better and better performing biosensors [17, 41, 53]. The advancements in the architecture of biosensors made for glucose sensing, concerning the use of immobilizing surfaces made of nanotubes for the enzyme, namely glucose oxidase, are probably the most familiar advances in sensing which have arrived at the fore; this particular enzyme is used to determine glucose from many body fluids. The sensors with enzymes predicted the existence of glucose from significant body tissues, in convention, while the application of nanotubes as immobilization assemblies culminated in the measurement of glucose from currently restricted body fluids, including tears and saliva. Single-walled nanotubes were brilliantly used for enzymatic glucose detection in one specific configuration, and this discovery also resulted in a major improvement in enzyme activity [3]. The increased biosensor functionality was investigated and also discovered, primarily as a result of the higher enzyme loading and the nanotubes’ much better electrical conductivity (EC). Because of their smoother and improved electron transfer flow properties, CNTs are frequently used to increase the electronic identification of the sensing phenomena, not just for their structural stability. In a few studies, and also in one specific analysis, this development produced greater oxidoreductase efficacy in each glucose oxidase in addition to flavin adenine dinucleotide precursor fastening to the substrates better, and in a more controllable way, the substantial changes in catalytic biosensors are generally exploited [28]. In addition, by combining CNTs s on the sensing particles of a sensor by greater charge carriers conductance and regulating their needed flow attributes, the chemo electroluminescence effect continues to be enhanced. In a systematic and relevant study, biosensors mainly focused on CNTs are extensively outlined through the use of both CNTs and nanostructured arrays the associated frame-sensitive assemblies for the key benefits and breakthroughs they obtain. This assessment highlights the ability of CNTs for functionalization and their rapid friendliness to be merged in a great way with biomolecules such as DNA, oligonucleotide probes, proteins, and also their associated benefits [59]. 6.5.3  NANOWIRE-BASED BIOSENSORS Nanowires, like those of CNTs, are basically cylindrical arrangements, with lengths within the nanorange spectrum of a few micrometers to centimeters in

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diameters. Nanowires are single-dimensional nanostructures with excellent transference properties for electrons [41]. Considerably, inside the nanowires, the behavior of charge carriers is vigorously made stronger and completely apart from all other bulk products. Sensors that rely primarily on nanowires are much less common, but a variety of intriguing instances are documented in literature where nanowire usage has greatly enhanced the functionality and identification of biological elements. In one important study, the Cui and Lieber group (2001) biosensors based on boron-doped silicon nanowires were studied for their effectiveness, and they were also used to track chemical and biological elements [13]. Semiconductor nanowires are now used in-depth and a variety of biomolecules are often used for coupling to establish their exclusively related substrates. Coated silicon nanowires with biotin were used in an experiment to identify and removal of streptavidin molecules out of the mixture. The nanowires’ small size and abilities would qualify them as ideal pathogen biodetection candidates including several other real-time assessments of biological species and chemical compounds, thus, the current accuracies of widely used in vivo testing techniques can be significantly improved. Since these sensing things run on incredibly extremely precise scales, they may also be seen in in-vivo situations, as well as to function in the littlest spaces inside life cells. Wang et al. [60] used optical fibers with nanosize diameters as well as coated with antibodies in one basic study to identify the existence of toxicants inside individual cells. Cullum et al. [15] proclaimed the development of ZnO nanowires one more extremely strongly associated analysis, coated them through yellow-colored electrodes, after which utilized them to identify hydrazine utilizing amperometric responses. They indicated an amazing sensitivity, lower detection threshold, and greatly reduced response times than all those recorded in the commonly claimed sensor methods used conventionally. Nanofire has a wide variety of uses and is much superior to nanotubes in terms of efficiency in two significant respects. Initially, during the synthesis of theirs, They make a variety of changes to their design by commanding operating variables. Second, because of the availability of sufficient compounds on their surfaces, they have a much wider variety of improvements in functionalized assemblies. Despite the incredibly well-known synthesis method for nanowire synthesis, a few difficulties have been achieved by using theirs to develop sensing tools [57]. Several related experiments have shown that it’s tough to add nanowires in to the sensing methods to obtain a general boost in their electric conductivity. In an extremely advanced review, Cui, and Lieber group (2001) have meticulously labored on semiconductor nanowires besides they were also

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synthesized using a combination of previously existing approaches [13]. They also created a complex one-dimensional structure that included more than 200 distinct nanowire electrical assemblies and used them to detect serum bone cancer antigens at a minimum level. Yang et al. [65] gave an invaluable perspective by strictly conversing about nanobelts and nanowires in addition to their structural properties and aspects that they may be utilized within sensing uses for the very best assessment of the reasoning behind the utilization of nanowires or also recognizing the attributes of theirs that will strengthen the realization process. Cui et al. [14]; and Huang et al. [33] examined the striking characteristics of nanowires in a few of the related developments and identified their effectiveness in enhancing biological stimulus conduction and detection. In particular, Huang et al. [33] concentrated on the plasmon resonance potential of nanowires in the field, which can be integrated with and significantly incorporated with sensor probes increase the sensing function’s sensitivity. Stern et al. [55] created nanowires using the complementary metal oxide semiconductor (CMOS) technique work on making the process a little more efficient. This methodology has demonstrated to be really simple in a manner of managing as well as modifying nanowire synthesis approaches which has long been employed for evaluation of serum fluids to allow the separation of numerous proteins and pathogens in their natural or crude form. NMs have thus proven to be exceptionally effective in brightening sensing technologies and have also expanded the methods of measurement and detection by bounds and leaps. The quicker and faster inspection allowed by faster analysis and assessment protocols with the NMs only revolutionized the process of biosensing. There are several other NMs that have been capitalized on and used in biosensing programs, with the exception of those previously described. To improve the traditional sensing techniques, nanodots are used close to the morphology of nanosheets, QDs along with various other buildings with modified geometries like nanocombs, nanobelts, at the same time as nanoribbons. Combining piezoelectric and cantilever units has contributed much more to this technology’s brand new appeal. As QDs, NMs are included as labels that come with sensitive dyes, photochromic, and thermochromic, as well as electrochromic components are already improved that may reveal highly fine detections which could easily be tracked. They also significantly contributed to the advancement of electron transfer mechanisms and to the improvement of even more robust actuating mechanisms in order to force on a device a precise state of observation. Any effect on the usage of nanobiosensors in different walks of life is stated in the textual material ahead [41].

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6.6  APPLICATIONS OF NANOBIOSENSORS 6.6.1 BIOMEDICAL The main aim to be addressed through healthcare promotion as well as testing and delivery is undoubtedly the opportunity to determine overall health status, illness onset and development, then monitor treatment outcomes in a non-invasive approach. To accomplish the goal, there are three prerequisites: those biomarkers that indicate a diseased or stable state; a non-invasive approach for detecting and keeping track of biomarkers; and solutions for discriminating against biomarkers. For patient survival and good disease prognosis, early detection of the disease is important, so precise and responsive techniques are necessary. In an interdisciplinary combination of tactics from NT, medical science and chemistry, biosensor innovations have the ability to meet these requirements [41]. Since time immemorial, biosensors have been able to biologically diagnose serum antigens as well as carcinogens, as well as causative elements of various metabolic issues. The usage of biosensors in the identification of problems such as diabetes, allergic reactions, cancer, and also several different problems on the basis of serum assessment are being identified in the everyday uses of diagnosis. There are many medical applications that are mainly made possible by the regular use of biosensors to address the bulk of the researched and successful uses of nanobiosensors from a medical point of view [41]. Such uses include the identification of sugar in diabetic persons [7, 55], the diagnosis of bacterial urinary tract diseases [21, 60], the detection of HIV AIDS [1, 24] also the evaluation of cancer [25, 30]. Certainly, entirely these are very important health concerns that actually concern humanity around the world. Before the use of biosensors, identifying, and analyzing these pathogens and diseases was extremely complex, time-consuming, and expensive. Indeed, biosensors have improved the identification of both of these pathogens and their associated malfunctions. This unique diagnosis is far more advantageous and even more accurate with all the inclusion of nanoscale interventions. The inclusion of NMs has made it easier to immobilize the recognition of enzyme devices, allowing costly enzymes to be recycled as well as reused. In addition, they have enriched the sensitivity and accuracy which make them perfect candidates for tapping on. The advent of new technologies such as MEMS and NEMS at the nanoscale has made it possible to take advantage of a number of the entire test methods. Intelligent sensing nanoscale substances are now used primarily to create highly delicate inroads, such as those for lab-on-a-chip assays. Biochips as well as

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microarray based assessment have allowed the assessment of many diseases is maybe no time. With regulated synthesis, MNPs can now be synthesized and used to isolate and balance heavy metals with iron characteristics from living organisms’ blood serum. Study of biochemical responses is unbelievably adaptable, and utilization of MNPs gives a high level of selectivity. This is why hemoglobin metal protein activity has been considered for blood-associative diseases. These invasions are widely known as magnetic diagnostic resonance because they optimize the magnetic binding of body antigens in vivo [31]. There have been even more sophisticated responses for the detection of nanobiosensors using diverse methods of their incorporation into sensing systems. 6.6.2 ENVIRONMENTAL This is a comparatively larger field of application. This is because nearly every second the atmosphere undergoes so many sudden shifts of magnitude. Extremely specific and systematic activities include contaminants, heavy metals from waste sources, toxic intermediates, and control of environmental factors such as humidity calculation and many other critical characteristics. In terms of NM-based sensors, they have a lot of flexibility in detector and monitor application. Utilizing the technology such as electronic samples on a cantilever and the provisions involving a very small volume of analyte are very effective technological invaders. NM sensor techniques may be used to detect the particular type of damaging range of an ambient substance. A fluorescent reporting method was used in one study in combination with the Chinese hamster ovary cell line to detect numerous toxicants present in significantly differing waters. Carcinogens as well as harmful intermediates are isolated from the use of very advanced as well as certain components, especially called endocrine disrupting agents, resulting in the destruction of appropriate hormonal processes in living beings [36]. Similarly, Purohit et al. [49] have tried biosensors in one specific study to keep track of abiotic problems that are critical for biological recovery optimization purposes, such as bioremediation. The method of bioremediation can thus be extended and used both for the enhancement of atmospheric efficiency and for the decontamination of toxic contaminants. Such applications may be much more useful and efficient when designed by the use of NMs. Biosensors are already produced as information for the substrate-specific detection system for the detection of nitrates [39], inorganic phosphates [38, 61], along with natural oxygen requirement, which have already been shown to be eco-restoring in

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their working pathways. These systems can be combined and the use of NMs allows a single sensor that could detect the different pollutants similarly well with only one functioning. There are infinite environmental variables and to study them nanobiosensors can constructed in this way and could be employed. These applications are efficient and save considerably energy, and valuable time [41]. 6.6.3 OTHERS Additionally, to optimize other detections, nanobiosensors can be used. For several programs, nutrient media and substrate mixtures can be managed in industrial functions using these sensors. Many factory preparations as well as separations on an industrial scale may be improved by utilizing such sensors. For example, nanobiosensors may be used to selectively remove the impurities in metallurgical activities involving the isolation of impurities found in a complex shape blended in the type of ores by measuring different configurations of the sensing enzymes. The acquisition of biochemical and microbiological experiments that come with developments focused on bioengineering are pretty useful functions of these components of sensing [41]. 6.7  NANOBIOSENSORS FOR DETECTION OF COVID-19 VIRUS We are presently dealing with the COVID 19 pandemic, the outcome of serious acute respiratory syndrome coronavirus (SARS-CoV-2). Because no proper vaccinations or medications is established when it comes to the treatment or remedy of SARS-CoV-2 disease to date, early detection is important to help fight this pandemic. In this case, the most important priority is the safe, quick, and cheap SARS-CoV-2 diagnostic technique. The reference technique currently being used for the identification of SARS-CoV-2 infection is the reverse transcription polymerase chain reaction (RT-PCR). In a variety of cases, however, incorrect findings have been found in the diagnosis of COVID-19. Researchers are actively working to improve innovative techniques, and in a series of constant rigorous efforts, NMs-assisted biosensing methods may be a way to develop new strategies to meet the current need for fast and accurate COVID-19 diagnosis [54]. In order to develop innovative techniques, NMs like Au nanostructures, graphene, lanthanide-doped polystyrene NPs, plus metal oxide NPs can possibly be used. Au-based nanostructures, due to excellent physicochemical properties in biomedical

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applications it has been extensively employed [54]. Au nanostructures are specifically used to produce virus detection biosensors in terms of optical signal enhancement, current amplifier and resonance light dispersion [20]. The unique plasmonic effect-based dual-functional biosensing framework for SARS-CoV-2 sensing was developed [50]. The manufactured biosensor utilizes the blend of plasmonic photothermal as well as Local SPR. In addition, 2D-Au nanoislands (AuNI) was regulated with additional DNA receptors for responsive SARS-CoV-2 recognition made possible by nucleic acid hybridization [54]. Lanthanides have special electronic configuration, allowing lanthanide-doped NPs many fascinating optical properties, including long-life luminescence, large, and sharp bandsm [54]. Chen et al. [11] produced a lateral flow immunoassay (LFIA)-based biosensing for SARS-CoV-2 diagnosis. The developed LFIA is based on the concept of identification in human serum samples for anti-SARS-CoV-2 IgG. In addition, these authors examined the observations of anti-SARS coV-2 IgG identification by means of the RT-PCR technique to verify the clinical application of LIFA. It was observed that, except for a study that displayed the other findings, the results obtained using LIFA were same to those found using the RT-PCR technique [11]. Graphene has proved its value for the creation of advanced biosensing platforms, 2D hexagonally organized carbon single thick atomic layers [54]. Seo et al. [52] designed a field-effect biosensing platform for the identification of SARS-CoV-2 in human nasopharyngeal swabs, by utilizing exceptional graphene properties. In order to eventually prepare the FET Biosensing Unit, the graphene surface had been coated with a particular SARS-CoV-2 spike protein antibody. Different sample analysis, such as antigenic protein, cultivated virus, and COVID 19 nasopharyngeal swab, were analyzed in the clinical function of the FET-based biosensing system. This graphene-based FET sensor performs well in SARS-CoV-2 spiked culture and clinical tests, values of LOD 1.6 × 101 pfu/mL, and 2.42 × 102 copies/mL, respectively [52]. 6.8  NEED FOR RESEARCH For the identification, testing, and analysis of biological diseases and molecules in medicine, there is a huge requirement for quick, cheap, and effective processes. In the fields of environmental pollutant control, the identification of foodborne pathogens and even the future danger of bioterrorism, this specific need is present. One of the key scientific and technological questions of this century is the invention of highly sensitive

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biological and chemical sensors. In order to fulfilled its needs in various fields such as in vitro-medical diagnostics, pharmaceutical development, and the identification of pathogens, the next generation biosensor systems require major improvements in precision and sensitivity. Developments of health strategies have been critical for drug improvement. By identifying associated protein-rich foods, nucleic acid sequences, organelles, cellular receptors, enzymes, along with other markers, the ability to identify pathogens and diseases will provide biomedical healthcare practitioners and researchers with detailed knowledge on disease mechanisms as well as victim issues. However, several of the commonly available traditional methods are slower and require many samples, and can also yield false positive or potentially negative findings. Therefore, fast, cheap, effective, and multiplexed testing to find a variety of biomaterials is necessary. The analyzer of nanobioelectronics and biosensors aims to integrate reliable, easy-to-use, and efficient sensors and biosensors with a number of uses like diagnostics and food analysis, other industries, and environmental monitoring. 6.9  FUTURE PROSPECTS The enormous development in sensor technology is because of the strong technical requirement for quick, responsive, and reasonable price biosensing systems in key areas of human life, such as health care, food, and beverage, genome analysis, process industries, environmental monitoring, protection, and safety. Biosensors based on NT are currently in the early stages of growth. NT’s widespread use in a wide range of fields as semiconductors, biological, and medical instruments, polymeric materials, optical sensors, dispersions, and coatings are amazing. The term nanotoxicity refers to the human health risk raised from the use of the novel NMs. Therefore, the study of adverse effect in human health causing from these NMs is very important. The chief goal is to maintain the correlation of surface properties with cytotoxicity, stability, and biological distribution for different in vivo applications. 6.10 SUMMARY Nanobiosensor research emphasis on the advancement of new technologies which have the capability to create major participation to the detection of animal and human disease markers, encouraging discovery of therapeutic compounds as well as tests, characterization of nano- and bio-materials,

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and then development of biocatalysts. In the production of biosensors, NT has really proven to be a very important blessing. It has revolutionized the biological detection process. The overall processes have been faster, more intelligent, less expensive, And helpful to consumers. Through the use of different NMs as well as nanostructures such as those of QDs, enzyme immobilization NPs, and hybrid nanostructures of several functionalities, the mechanisms of transduction have been greatly enhanced. In view of their multidimensional capacity, the future argues wonderfully for these complex, modular, and fast recognition systems. Those materials are now currently, towards the coupling of biological and chemical sensors is increasingly being considered to create the complete practice quick and simple to implement and in terms of efficiency, they are also a step forward. The application has been stimulated by growing advances in miniaturization and many key pathways and regulatory activities of these components can be detected using NMs technology. Sensing technology has become more robust, and flexible as NM exploration continues to evolve and undergo extensive testing. No doubt, because of its technological complexity, biosensor production for different applications is still cumbersome and costly, but the NMs integration has established to be a major blessing for this technology, largely because of its pleasant experimental assistance with the results. KEYWORDS • • • • • •

bulk acoustic wave enzyme linked immunosorbent assays giant magnetoresistance interdigital transducers nanoelectromechanical methods surface acoustic wave

REFERENCES 1. Alterman, M., Sjöbom, H., Säfsten, P., Markgren, P. O., Danielson, U. H., Hämäläinen, M., Löfås, S., et al., (2001). P1/P1’ modified HIV protease inhibitors as tools in two new sensitive surface plasmon resonance biosensor screening assays. European Journal of Pharmaceutical Sciences, 13(2), 203–212. https://doi.org/10.1016/s0928-0987(01)00109-9.

Nanomaterials for Biosensing Applications 185 2. Altintas, Z., (2017). Biosensors and Nanotechnology: Applications in Health Care Diagnostics (1st edn, p. 367). John Wiley & Sons. 3. Azamian, B. R., Davis, J. J., Coleman, K. S., Bagshaw, C. B., Green, M. L. H., & Carbon, B. S. W., (2002). Bioelectrochemical single-walled carbon nanotubes. Journal of the American Chemical Society, 124(43), 12664–12665. https://doi.org/10.1021/ja0272989. 4. Bauer, G., Pittner, F., & Schalkhammer, T., (1999). Metal nano-cluster biosensors. Microchimica Acta, 131(1, 2), 107–114. 5. Bhalla, N., Jolly, P., Formisano, N., & Estrela, P., (2016). Introduction to biosensors. Essays in Biochemistry, 60(1), 1–8. https://doi.org/10.1042/EBC20150001. 6. Bhushan, B., (2007). Nanotribology and nanomechanics of MEMS/NEMS and BioMEMS/ BioNEMS materials and devices. Microelectronic Engineering, 84(3), 387–412. https:// doi.org/10.1016/j.mee.2006.10.059. 7. Bolinder, J., Ungerstedt, U., & Arner, P., (1992). Microdialysis measurement of the absolute glucose concentration in subcutaneous adipose tissue allowing glucose monitoring in diabetic patients. Diabetologia, 35(12), 1177–1180. https://doi.org/10.1007/BF00401374. 8. Buzea, C., Pacheco, I. I., & Robbie, K., (2007). K. Nanomaterials and nanoparticles: Sources and toxicity. Biointerphases, 2(4), MR17–71. https://doi.org/10.1116/1.2815690. 9. Cai, H., Xu, C., He, P., & Fang, Y., (2001). Colloid Au-enhanced DNA immobilization for the electrochemical detection of sequence-specific DNA. Journal of Electroanalytical Chemistry, 510(1, 2), 78–85. https://doi.org/10.1016/S0022-0728(01)00548-4. 10. Chemla, Y. R., Grossman, H. L., Poon, Y., McDermott, R., Stevens, R., Alper, M. D., & Clarke, J., (2000). Ultrasensitive magnetic biosensor for homogeneous immunoassay. Proceedings of the National Academy of Sciences of the United States of America, 97(26), 14268–14272. https://doi.org/10.1073/pnas.97.26.14268. 11. Chen, Z., Zhang, Z., Zhai, X., Li, Y., Lin, L., Zhao, H., Bian, L., et al., (2020). Rapid and sensitive detection of anti-SARS-CoV-2 IgG, using lanthanide-doped nanoparticlesbased lateral flow immunoassay. Analytical Chemistry, 92(10), 7226–7231. https://doi. org/10.1021/acs.analchem.0c00784. 12. Crumbliss, A. L., Perine, S. C., Stonehuerner, J., Tubergen, K. R., Zhao, J., Henkens, R. W., & O’Daly, J. P., (1992). Colloidal gold as a biocompatible immobilization matrix suitable for the fabrication of enzyme electrodes by electrodeposition. Biotechnology and Bioengineering, 40(4), 483–490. https://doi.org/10.1002/bit.260400406. 13. Cui, Y., & Lieber, C. M., (2001). Functional nanoscale electronic devices assembled using silicon nanowire building blocks. Science, 291(5505), 851–853. https://doi.org/10.1126/ science.291.5505.851. 14. Cui, Y., Wei, Q., Park, H., & Lieber, C. M., (2001). Nanowire nanosensors for highly sensitive and selective detection of biological and chemical species. Science, 293(5533), 1289–1292. https://doi.org/10.1126/science.1062711. 15. Cullum, B. M., Griffin, G. D., Miller, G. H., & Vo-Dinh, T., (2000). Intracellular measurements in mammary carcinoma cells using fiber-optic nanosensors. Analytical Biochemistry, 277(1), 25–32. https://doi.org/10.1006/abio.1999.4341. 16. Curri, M. L., Agostiano, A., Leo, G., Mallardi, A., Cosma, P., & Della, M. M., (2002). Development of a novel enzyme/semiconductor nanoparticles system for biosensor application. Materials Science and Engineering, 22(2), 449–452. https://doi.org/10.1016/ S0928-4931(02)00191-1. 17. Davis, J. J., Coleman, K. S., Azamian, B. R., Bagshaw, C. B., & Green, M. L. H., (2003). Chemical and biochemical sensing with modified single walled carbon nanotubes. Chemistry, 9(16), 3732–3739. https://doi.org/10.1002/chem.200304872.

186

Sustainable Nanomaterials for Biosystems Engineering

18. De Corcuera, J. I. R., Cavalieri, R. P., & Powers, J. R., (2004). Encyclopedia of Agri, Food, and Biological Engineering (pp. 1–5). Marcel Dekker. 19. Drafts, B., (2001). Acoustic wave technology sensors. IEEE Transactions on Microwave Theory and Techniques, 49(4), 795–802. https://doi.org/10.1109/22.915466. 20. Draz, M. S., & Shafiee, H., (2018). Applications of gold nanoparticles in virus detection. Theranostics, 8(7), 1985–2017. https://doi.org/10.7150/thno.23856. 21. Drummond, T. G., Hill, M. G., & Barton, J. K., (2003). Electrochemical DNA sensors. Nature Biotechnology, 21(10), 1192–1199. https://doi.org/10.1038/nbt873. 22. Durmuş, N. G., Lin, R. L., Kozberg, M., Dermici, D., Khademhosseini, A., & Demirci, U., (2015). Acoustic-based biosensors. In: Li, D., (ed.), Encyclopedia of Microfluidics and Nanofluidics (pp. 28–40). Springer. 23. Dzyadevych, S. V., Arkhypova, V. N., Soldatkin, A. P., El’Skaya, A. V., Martelet, C., & Jaffrezic-Renault, N., (2008). Amperometric enzyme biosensors: Past, Present, and Future. IRBM, 29(2, 3), 171–180. 24. Fägerstam, L. G., Frostell, A., Karlsson, R., Kullman, M., Larsson, A., Malmqvist, M., & Butt, H., (1990). Detection of antigen-antibody interactions by surface plasmon resonance: Application to epitope mapping. Journal of Molecular Recognition, 3(5, 6), 208–214. https://doi.org/10.1002/jmr.300030507. 25. Gao, X., Cui, Y., Levenson, R. M., Chung, L. W., & Nie, S., (2004). In vivo cancer targeting and imaging with semiconductor quantum dots. Nature Biotechnology, 22(8), 969–976. https://doi.org/10.1038/nbt994. 26. González-Garcıa, M. B., Fernández-Sánchez, C., & Costa-Garcıa, A., (2000). Colloidal gold as an electrochemical label of streptavidin-biotin interaction. Biosensors and Bioelectronics, 15(5, 6), 315–321. https://doi.org/10.1016/s0956-5663(00)00074-9. 27. Gouvea, C., (2011). Chapter 3. Biosensors for health applications. In: Serra, P. A., (ed.), Biosensors for Health, Environment, and Biosecurity (Vol. 1, pp. 71–86). London-UK: Intech open. 28. Guiseppi-Elie, A., Lei, C., & Baughman, R. H., (2002). Direct electron transfer of glucose oxidase on Carbon nanotubes. Nanotechnology, 13(5), 559–564. https://doi. org/10.1088/0957-4484/13/5/303. 29. Haes, A. J., & Van, D. R. P., (2002). A nanoscale optical biosensor: Sensitivity and selectivity of an approach based on the localized surface plasmon resonance spectroscopy of triangular silver nanoparticles. Journal of the American Chemical Society, 124(35), 10596–10604. https://doi.org/10.1021/ja020393x. 30. Harisinghani, M. G., Barentsz, J., Hahn, P. F., Deserno, W. M., Tabatabaei, S., Van De, K. C. H., De La Rosette, J., & Weissleder, R., (2003). Noninvasive detection of clinically occult lymph-node metastases in prostate cancer. New England Journal of Medicine, 348(25), 2491–2499. https://doi.org/10.1056/NEJMoa022749. 31. Haun, J. B., Yoon, T. J., Lee, H., & Weissleder, R., (2010). Magnetic nanoparticle biosensors. Wiley Interdisciplinary Reviews. Nanomedicine and Nanobiotechnology, 2(3), 291–304. https://doi.org/10.1002/wnan.84. 32. Ho, C. K., Lindgren, E. R., Rawlinson, K. S., McGrath, L. K., & Wright, J. L., (2003). Development of a surface acoustic wave sensor for in-situ monitoring of volatile organic compounds. Sensors, 3(7), 236–247. https://doi.org/10.3390/s30700236. 33. Huang, B., Yu, F., & Zare, R. N., (2007). Surface plasmon resonance imaging using a high numerical aperture microscope objective. Analytical Chemistry, 79(7), 2979–2983. https://doi.org/10.1021/ac062284x.

Nanomaterials for Biosensing Applications 187 34. Jianrong, C., Yuqing, M., Nongyue, H., Xiaohua, W., & Sijiao, L., (2004). Nanotechnology and biosensors. Biotechnology Advances, 22(7), 505–518. https://doi.org/ 10.1016/j.biotechadv.2004.03.004. 35. Kelly, K. L., Coronado, E., Zhao, L. L., & Schatz, G. C., (2003). The optical properties of metal nanoparticles: The influence of size, shape, and dielectric environment. Journal of Physical Chemistry B, 107(3), 668–677. https://doi.org/10.1021/jp026731y. 36. Kim, E. J., Lee, Y., Lee, J. E., & Gu, M. B., (2002). Application of recombinant fluorescent mammalian cells as a toxicity biosensor. Water Science and Technology, 46(3), 51–56. https://doi.org/10.2166/wst.2002.0052. 37. Kissinger, P. T., (2005). Biosensors—A perspective. Biosensors and Bioelectronics, 20(12), 2512–2516. https://doi.org/10.1016/j.bios.2004.10.004. 38. Kulys, J., Higgins, I. J., & Bannister, J. V., (1992). Amperometric determination of phosphate ions by biosensor. Biosensors and Bioelectronics, 7(3), 187–191. https://doi. org/10.1016/0956-5663(92)87014-G. 39. Larsen, L. H., Kjær, T., & Revsbech, N. P., (1997). A microscale NO3– biosensor for environmental applications. Analytical Chemistry, 69(17), 3527–3531. https://doi.org/ 10.1021/ac9700890. 40. Liu, T., Tang, J. A., & Jiang, L., (2004). The enhancement effect of gold nanoparticles as a surface modifier on DNA sensor sensitivity. Biochemical and Biophysical Research Communications, 313(1), 3–7. https://doi.org/10.1016/j.bbrc.2003.11.098. 41. Malik, P., Katyal, V., Malik, V., Asatkar, A., Inwati, G., & Mukherjee, T. K., (2013). Nanobiosensors: Concepts and variations. ISRN Nanomaterials, 2013, 1–9. https://doi. org/10.1155/2013/327435. 42. Maxwell, D. J., Taylor, J. R., & Nie, S., (2002). Self-assembled nanoparticle probes for recognition and detection of biomolecules. Journal of the American Chemical Society, 124(32), 9606–9612. https://doi.org/10.1021/ja025814p. 43. Mehrotra, P., (2016). Biosensors and their applications—A review. Journal of Oral Biology and Craniofacial Research, 6(2), 153–159. https://doi.org/10.1016/j.jobcr.2015.12.002. 44. Jianrong, C., Yuqing, M., Nongyue, H., Xiaohua, W., & Sijiao, L., (2004). Nanotechnology and biosensors. Article in Biotechnology Advances, 22(7), 505–518. https://doi.org/ 10.1016/j.biotechadv.2004.03.004. 45. Nath, N., & Chilkoti, A., (2002). A colorimetric gold nanoparticle sensor to interrogate biomolecular interactions in real-time on a surface. Analytical Chemistry, 74(3), 504–509. https://doi.org/10.1021/ac015657x. 46. Nikolelis, D. P., & Nikoleli, G. P., (2018). Nanotechnology and Biosensors (1st edn., p. 470). Elsevier. 47. Pak, S. C., Penrose, W., & Hesketh, P. J., (2001). An ultrathin platinum film sensor to measure biomolecular binding. Biosensors and Bioelectronics, 16(6), 371–379. https:// doi.org/10.1016/s0956-5663(01)00152-x. 48. Pirzada, M., & Altintas, Z., (2019). Nanomaterials for healthcare biosensing applications. Sensors, 19(23), 5311. https://doi.org/10.3390/s19235311. 49. Purohit, H. J., (2003). Biosensors as molecular tools for use in bioremediation. Journal of Cleaner Production, 11(3), 293–301. https://doi.org/10.1016/S0959-6526(02)00072-0. 50. Qiu, G., Gai, Z., Tao, Y., Schmitt, J., Kullak-Ublick, G. A., & Wang, J., (2020). Dual-functional plasmonic photothermal biosensors for highly accurate severe acute respiratory syndrome coronavirus 2 detection. ACS Nano, 14(5), 5268–5277. https://doi. org/10.1021/acsnano.0c02439.

188

Sustainable Nanomaterials for Biosystems Engineering

51. Richardson, J., Hawkins, P., & Luxton, R., (2001). The use of coated paramagnetic particles as a physical label in a magneto-immunoassay. Biosensors and Bioelectronics, 16(9–12), 989–993. https://doi.org/10.1016/s0956-5663(01)00201-9. 52. Seo, G., Lee, G., Kim, M. J., Baek, S. H., Choi, M., Ku, K. B., Lee, C. S., et al., (2020). Rapid detection of COVID-19 causative virus (SARS-CoV-2) in human nasopharyngeal swab specimens using field-effect transistor-based biosensor. ACS Nano, 14(4), 5135–5142. https://doi.org/10.1021/acsnano.0c02823. 53. Sotiropoulou, S., Gavalas, V., Vamvakaki, V., & Chaniotakis, N. A., (2003). Novel Carbon materials in biosensor systems. Biosensors and Bioelectronics, 18(2, 3), 211–215. https:// doi.org/10.1016/s0956-5663(02)00183-5. 54. Srivastava, M., Srivastava, N., Mishra, P. K., & Malhotra, B. D., (2021). Prospects of nanomaterials-enabled biosensors for COVID-19 detection. Science of the Total Environment, 754, 142363. https://doi.org/10.1016/j.scitotenv.2020.142363. 55. Stern, E., Klemic, J. F., Routenberg, D. A., Wyrembak, P. N., Turner-Evans, D. B., Hamilton, A. D., LaVan, D. A., Fahmy, T. M., & Reed, M. A., (2007). Label-free immunodetection with CMOS-compatible semiconducting nanowires. Nature, 445(7127), 519–522. https://doi.org/10.1038/nature05498. 56. Su, X., Chew, F. T., & Li, S. F. Y., (2000). Design and application of piezoelectric quartz crystal-based immunoassay. Analytical Sciences, 16(2), 107–114. https://doi.org/10.2116/ analsci.16.107. 57. Umar, A., Rahman, M. M., Al-Hajry, A., & Hahn, Y. B., (2009). Highly-sensitive cholesterol biosensor based on well-crystallized flower-shaped ZnO nanostructures. Talanta, 78(1), 284–289. https://doi.org/10.1016/j.talanta.2008.11.018. 58. Van, G. P., Laureyn, W., Laureys, W., Huyberechts, G., Op De Beeck, M., Baert, K., Suls, J., et al., (1998). Nanoscaled interdigitated electrode arrays for biochemical sensors. Sensors and Actuators: Part B, 49(1, 2), 73–80. https://doi.org/10.1016/S0925-4005 (98)00128-2. 59. Wang, J., (2005). Carbon-nanotube based electrochemical biosensors: A review. Electroanalysis, 17(1), 7–14. https://doi.org/10.1002/elan.200403113. 60. Wang, J., (2002). Electrochemical nucleic acid biosensors. Analytica Chimica Acta, 469(1), 63–71. https://doi.org/10.1016/S0003-2670(01)01399-X. 61. Wollenberger, U., Schubert, F., & Scheller, F. W., (1992). Biosensor for sensitive phosphate detection. Sensors and Actuators: Part B, 7(1–3), 412–415. https://doi.org/ 10.1016/0925-4005(92)80335-U. 62. Woolston, B. M., Edgar, S., & Stephanopoulos, G., (2013). Metabolic engineering: Past and future. Annual Review of Chemical and Biomolecular Engineering, 4, 259–288. https://doi.org/10.1146/annurev-chembioeng-061312-103312. 63. World Health Organization, (2019). Global Status Report on Alcohol and Health 2018 (p. 472). https://www.who.int/publications-detail-redirect/9789241565639 (accessed on 9 July 2022).World Health Organization. 64. Xu, X., Liu, S., & Ju, H., (2003). A novel hydrogen peroxide sensor via the direct electrochemistry of horseradish peroxidase immobilized on colloidal gold modified screen-printed electrode. Sensors, 3(9), 350–360. https://doi.org/10.3390/s30900350. 65. Yang, S., (2003). Chapter 12; Sulfide nanowires. In: Wang, Z. L., (ed.), Nanowires and Nanobelts (Vol. 2, pp. 209–238). Springer. 66. Yun, Y. H., Eteshola, E., Bhattacharya, A., Dong, Z., Shim, J. S., Conforti, L., Kim, D., et al., (2009). Tiny medicine: nanomaterial-based biosensors. Sensors, 9(11), 9275–9299. https://doi.org/10.3390/s91109275.

Nanomaterials for Biosensing Applications 189 67. Zeng, S., Yong, K. T., Roy, I., Dinh, X. Q., Yu, X., & Luan, F., (2011). A review on functionalized gold nanoparticles for biosensing applications. Plasmonics, 6(3), 491–506. https://doi.org/10.1007/s11468-011-9228-1. 68. Zhao, J., O’daly, J. P., Henkens, R. W., Stonehuerner, J., & Crumbliss, A. L., (1996). A xanthine oxidase/colloidal gold enzyme electrode for amperometric biosensor applications. Biosensors and Bioelectronics, 11(5), 493–502. https://doi.org/10.1016/ 0956-5663(96)86786-8.

PART III BIONANOMATERIALS FOR RENEWABLE ENVIRONMENTAL TRENDS

CHAPTER 7

ADVANCED BIONANOMATERIALS FOR ENVIRONMENTAL REMEDIATION JAYA GANGWAR, JOSEPH KADANTHOTTU SEBASTIAN, and PREETHY CHANDRAN

ABSTRACT In the 21st century, water pollution caused by oil spillage, chemical discharges, and heavy metal releases from industries is a significant issue. Water scarcity affects economic growth and human health. Pollution reduces the availability of healthy foods and beverages, thus causing different epidemic diseases such as diarrhea, cholera, and dysentery, improving access to preserving and replenishing resources. Solid and liquid hazardous wastes generated by industries represent a significant risk to people and the environment. The waste includes contaminating packing, batteries, paints, clinical waste, hydrocarbons, industrial effluents, and chemical pollutants are generated every day. These wastes are transformed into renewable energy sources and various others. These transformations serve as circular economic solutions that diminish environmental impacts on the food chain, soil quality, etc. Nanoparticles (NPs) exhibit great potential in many fields, including environmental remediation, as they possess large surface area, solvent affinity, magnetic property, and photocatalytic property. NPs have now found different ways to purify groundwater. These cleaning methods are sorted by injecting NPs in affected areas, such as immobilization of metals, dechlorination of organic solvents, detoxifying pesticides, and transformation of fertilizers. For example, detoxifying pesticides using carbon nanotubes (CNTs) and nanosized zero-valent iron for environmental remediation can potentially degrade organic dyes, antibiotics, heavy metal ions, etc. Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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7.1 INTRODUCTION Clean water is an essential asset for all life forms on Earth. It serves as a critical raw material for industries, including the food and beverage, refinery, electronics, agricultural, and pharmaceuticals. By 2025, these sectors’ yearly water volume consumption is expected to rise over 50% compared with 1995 levels [75]. Contaminated water occurs when unwanted materials enter bodies of water or reservoirs, offering them unfit for drinking and other uses. Numerous chemical, physical, and mechanical aspects are associated with this emerging problem. Furthermore, researchers are trying to develop water purification methods cheaper by experimenting with various new technologies. Nanotechnology (NT) is a newly emerging field that can cleanse water relatively cheaper, with high effectiveness in removing contaminants, and with the potential to be reused [82]. NPs possess specific surface area and reactivity, and NPs have unique properties that allow their sensing and efficient removal of a wide range of targets, which includes chemicals released from industries, organic pollutants and gases, and biological substrates, from various media, such as natural waters, wastewaters, and air. NMs were efficiently used for environmental remediation, including cleaning processes such as oil-water separation, adsorption, organics degradation, and heavy metal ions from wastewater. By tailoring their uptake mechanism, NMs can be devised for increased selectivity against targeted pollutants. The researchers have used metal and metal oxides (MO) of silver, iron, gold (Au), titanium oxide, and zinc to synthesize NPs [22]. Currently, the toxicity of engineered NPs is assessed using a variety of methods. In vitro studies are the most advantageous because it requires less time and expenditure. However, in vitro studies conducted in numerous laboratories have yielded disparate results [6]. To improve water quality and reduce pollutants, it is crucial to warrant the wellbeing, adequacy, and operating capability of proper wastewater treatment technology to remove multiplex toxic compounds into innocuous or more straightforward complexes [46]. In this chapter, bionanomaterials for the environmental clean recovery process focus: on pollutants damaging the environment, NPs for cleanup, ecological, and operational parameters, toxicological studies, different mechanisms in water treatment, and bionanomaterials for cleanup, the toxicity of NPs, and advantages and disadvantages of advanced methods.

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7.1.1  CONVENTIONAL METHODS IN ENVIRONMENT CLEANUP The human body comprises 50–75% water which is vital for the survival of life. Water bodies are getting contaminated with solid and liquid wastes released from industries [72]. Massive production and discharge of raw industrial wastewater pollute environmental resources continuously, posing a significant challenge to preserving a safe and sustainable environment. Since ancient times, many different conventional treatment methods have been used, including adsorption, biosorption, coagulation, ion exchange, precipitation, electrodialysis, etc. The traditional approaches include physical, chemical, and biological processes (Figure 7.1).

FIGURE 7.1  Conventional methods for cleanup.

7.1.1.1  PHYSICAL METHODS The physical techniques include processes such as adsorption, electro-dialysis, sedimentation, and ion-exchange. The adsorption process involves the binding of NPs in contaminated sites, for example, iron oxide [49]. The electrodialysis method involves two charged membranes and is appropriate for tackling inorganic pollutants. The efficiency of these processes depends on numerous factors, including membrane quality, ion concentration. Sedimentation consists of the settlement of heavy metals due to gravitational forces and uses a clarifier for cleaning the pollutants [46]. Ion-exchange uses synthetic ion matrices, which is helpful in the treatment of heavy metal removal from polluted sites [53]. 7.1.1.2  CHEMICAL METHODS The process involves including chemical agents to pull out the metals into the aqueous phase for their removal from the system. In this method,

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different inorganic solvents, chelating agents, and detergents are used. The chemical method involves chemical leaching is a process in which chelators like Ethylenediaminetetraacetic acid (EDTA) and Nitrilotriacetic acid (NTA) are used to remove heavy metals. For example, studies suggest 0.1 M EDTA can efficiently remove 70% of petroleum and 60% copper and lead from the contaminated soils, respectively [70]. 7.1.1.3  BIOLOGICAL METHODS The selection of appropriate plant species is also essential in attaining high performance from biological methods. Combining metal mobilization and uptake with chelating agents and microorganisms has been suggested and used by many scientists. The biological process involves phytoremediation, which means using plants to treat polluted soil in simple terms. The growth of plants is damaged by getting exposed to heavy metals like cadmium, chromium, copper, lead, mercury, and selenium. The hyperaccumulator plants, for example, Thlaspi caerulescens and Sedum alfredi, have the potential to translocate metals from root to shoot within 48 to 72 hours of exposure [63]. 7.2  ADVANTAGES AND DISADVANTAGES OF CONVENTIONAL METHODS Nano-photocatalysts have played an essential role in mineralizing hazardous organic compounds at 25°C. Researchers have proved them to be an efficient and efficient method for water detoxification using Nano-photocatalysts. Furthermore, most nano-photocatalysts have advantages such as being less toxic, less costly, chemically stable, easily accessible and having excellent photoactive activity. One such practical approach, where magnetic nano-photocatalysts in wastewater treatment, could be used to overcome the disadvantage of catalyst recovery. When magnetic nano-photocatalysts are being used, the catalyst can be recovered using an external magnetic field, allowing for multiple recycling of Nanocatalysts and more efficient water decontamination processes [82]. 7.3  TYPES OF POLLUTANTS RELEASED IN THE ENVIRONMENT The different pollutants include physical, biological, chemical, biodegradable, non-biodegradable, and manufactured pollutants. Biological contaminants

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like harmful pollutants (x-ray, gamma radiation), chemical pollutants (heavy metals, pesticides), biological pollutants (infectious bacteria present in food and water, viral spores). The contaminants can be solid (dust, smoke), liquid (acids, fumes, and solvents), and gaseous (oxides of sulfur, oxides of nitrogen, carbon monoxide, and ozone). The artificial pollutants include synthetic dyes and chemicals [2, 17] (Table 7.1). Organic compounds, pathogens, pathogenic bacteria, radioactive contaminants, and nanopollutants are released in water bodies [4, 25]. TABLE 7.1  List of Pollutants Present in the Environment Pollutants

Source

References

Organic pollutants

Domestic and municipal sewage, wastewater

[25]

Pathogens

Wastewater

[25]

Agricultural runoff

Wastewater from the fertilizer industries and sewage

[25]

Inorganic pollutants

Industrial wastewater

[25]

Radioactive pollutants

Contaminated soil or leach into water bodies (rivers, lakes, or oceans)

[25]

Organic pollutants

Sewage and industries

[4]

Heavy metals

Sewage

[4]

Sulfur dioxide

Industries

[17]

Nitrogen dioxide

Combustion processes in the industry

[17]

Heavy metal contamination

Rivers

[10]

Azo dyes

Textile industry

[7]

Gaseous or particulate matter

Industrial emission

[80]

Pesticides

Soil and river water

[5]

Antibiotics waste

Rivers, wastewater

[5]

7.4  POLLUTANTS DAMAGING ENVIRONMENT The continuous release of pollutants in water bodies for the long term damages the environment and human health. Industry releases toxic substances such as carbon monoxide, nitrogen dioxide, and volatile compounds that damage lungs, endothelial dysfunction, DNA damage, and inflammation [8]. Monuments containing stony material that releases nitrogen dioxide, sulfur dioxide, etc., cause damage to the environment [64]. Pharmaceutical medicines are released in wastewater which is mutagenic and cytotoxic. Heavy metals released cause air pollution, which enters the food chain [5]. The reactive oxygen species

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(ROS) and superoxide damage DNA, lipid peroxidation that exerts toxicity [38]. Ground-level ozone and ROS are primary and secondary pollutants that cause coughing, irritation in the eyes and nose, headaches [80]. Incomplete combustion, released from indoor pollutants, generates carbon monoxide, sulfur dioxide, nitrogen oxide, and acute infections such as pneumonia, tuberculosis, and cancer [19]. The ultraviolet radiation causes cancer, and environmental pollutants such as benzo[a]pyrene cause cellular damage [13]. 7.4.1  NANOMATERIALS FOR CLEAN-UP Iron-based NPs are mostly used for remediation. With strong magnetic properties, iron-based NMs act as good adsorbents to remove targeted compounds from polluted sites and act as a magnetic element to captivate and hold on to NPs extracted from solutions. These NPs are used in environment cleaning due to their compact size ranging from 1–100 nm. These also include NPs like bimetallic, Ni/Fe; Cu/Fe, CNTs; and nanoscale zero-valent iron (Table 7.2). TABLE 7.2  Nanoparticles in Cleanup Nanoparticles Fe/Pd Fe/Cu Fe/Ag Pt–Ag Ni/Fe Carbon tubes Nanoscale zero-valent iron Iron nanoparticles Bimetallic nanoparticles

Degradation of Pollutants PCB Chromium, 1,2,4-trichlorobenzene Chromium, fast green dye Carbon monoxide 1,1,1-trichloroethane, sulfentrazone Combustion, heavy metal degradation Removal of orange II dye, pesticides, trichloroethene Degradation of toxic dyes Toxic pollutants

References [62] [62] [62] [16] [52, 67] [51, 54] [30, 36, 50] [69] [67]

7.4.1.1  BIMETALLIC PARTICLES The bimetallic NPs like Fe/Pd, Fe/Cu, and Fe/Ag target contaminants such as PCB and chromium [62]. Bimetallic NP Fe/Ag efficiently degraded fast green dye. Pt-Ag nanowires electrocatalyst and greater tolerance of carbon monoxide poisoning with broader applications [16]. Ni/Fe bimetallic NPs efficiently removed 1,1,1-trichloroethane [39].

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7.4.1.2  NI/FE; CU/FE The Fe/Cu bimetallic NPs removed chromium, dechlorinate 1,2,4-trichlorobenzene from wastewater. In conjunction with the colloidal stability of ChitosanFe/Cu, more surface reactive sites may be attributed to a positive effect of chitosan on Chromium reduction. In other words, chitosan, as a good adsorbent, could help to speed up Chromium transfer and adsorb more chromium [15, 32]. Iron-nickel and Pt-based bimetallic NPs efficiently remove Sulfentrazone by dechlorination and act as an electrocatalyst, respectively [52, 83]. 7.4.1.3  CARBON NANOTUBES CNTs, nanoforms, and related nanostructures are commonly found in the air, common, domestic, clean-burning gas sources, and they appear to be significant contributors to indoor and outdoor carbon nanoparticulate matter. CNTs have been used to degrade combustion gases which provide clean-burning of methane gases and helps in the degradation of wastes in landfills [51, 54]. 7.4.1.4  NANOSCALE ZERO VALENT IRON (NZVI) nZVI is used in dechlorinating excess trichloroethene and the degradation from contaminated soil, removal of organic pollutants such as pesticides, efficient removal of orange II dye, and removal of contaminants. Impurities separated from the aqueous solution by the NP-immobilized alginate bead by more than 99.8%. Furthermore, the metal let go from the support was 5% of the loaded Fe [27, 30, 36, 40, 50]. 7.4.2  ENVIRONMENTAL AND OPERATING PARAMETERS 7.4.2.1 TIME Time taken for the reaction is an important parameter that affects the efficiency of treatment. Efficient degradation relies on the size, structure, and specific surface area of the NMs. For example, the malachite green dye was removed efficiently using copper oxide NP-loaded activated carbon (CuO-NP-AC) particles [35].

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7.4.2.2  pH Heavy metal adsorption is more efficient due to their negative charge present on NMs and the restricted adsorption of heavy metals at lower pH. For example, acid blue 129 dye adsorption to CuO-NP-AC NPs at pH-2 degraded dyes with 100% degradation efficiency [35]. 7.4.2.3 TEMPERATURE Temperature can efficiently influence the degradation of organic contaminants. Temperature is one of the climatic components that have an impact on cultural heritage damage. Temperature cycles can occur over a broader range, depending on geographical location and time of year [80]. For example, as temperature increases from 20°C to 40°C helps Copper oxide NPs remove chromium from contaminated soil. Carbon, aerogel-supported copper oxide NPs, remove Rhodamine B dye when temperature increases from 30°C to 60°C [35]. 7.4.2.4 HUMIDITY Humidity also plays an essential role in the efficient degradation of organic contaminants. Humidity is inversely proportional to degradation efficiency. For example, when humidity (65%) hybrid NM (zeolite-Cu2O) degraded pollutants with 23% of degradation efficiency [35]. 7.4.3  TOXICOLOGICAL STUDIES The nanotoxicity leads to the toxicity of organisms or humans and genetic polymorphs in human beings, DNA damage, mutagen, and general toxicity. Two prerequisite stages may be required for adequate evaluation of the toxic effects of nanocomposites (NCs), though they may hinder the therapeutic use of drugs: elaboration of the related approach, which takes ample time to develop, and the corresponding experimental studies [21]. An increase in environmental pollution leads to lung infection, chronic inflammation, tumor formation, and mutation [12]. ZnO and titanium oxide NPs cause cancer and general toxicity [45]. The NPs cause cytotoxicity and inflammation of organs [60].

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7.4.3.1 IN-VITRO The exposure of silver nanoparticles (Ag-NPs) leads to ROS production (Reactive oxygen species), genotoxicity, DNA damage, inflammation, and increased nitric oxide [73]. Titanium oxide NPs exposure also leads to ROS production, cytotoxicity, and inflammation [31]. 7.4.3.2 IN-VIVO Polylobate 80-coated poly (butyl cyanoacrylate) NPs cause acute cytotoxicity and tumor formation [24]. They caused edema in tissues, inflammation, DNA damage, cytokine induction, and deformation in zebra fishes [73]. Titanium oxide NPs caused a carcinogenic effect on lungs in rats and cytotoxicity [31]. 7.4.4  WATER TREATMENTS BY USING NANOPARTICLES BY DIFFERENT MECHANISMS The mechanism for water treatment includes the adsorption approach and degradation approach. During the adsorption approach, the adsorption of NPs in the removal of organic contaminants. Zeolites, clay-based, and silica-based NPs, removes heavy metal contamination. Activated carbon is a commercial adsorbent that removes lead contamination, and CNTs eliminate heavy metals from contaminated areas [20]. Cellulose nanofibrils, NMs, and nanocrystals remove contaminants from wastewater treatment [47]. The carbon nanomaterial (CNM) adsorbs to the surface of inorganic and organic pollutants and eliminates them efficiently [23]. Graphene-based materials are efficient absorbent removes dye effluents efficiently [65]. CNMs efficiently removed contaminants from wastewater [71]. 7.4.5  BIONANOMATERIALS FOR ENVIRONMENT CLEAN-UP Green NT provides distinct socioeconomic-environmental advantages of pollutant removal and risk depletion, such as (i) abate use of toxic materials, (ii) apace depletion of pollutants, (iii) optimal operating expenditure, and (iv) a low life cycle footprint [81].

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7.4.5.1  USING PLANT AND THEIR EXTRACTS Iron and iron oxide NPs synthesized by green tea extract removed azo dyes and malachite green due to the presence of the high quantities of polyphenols [26, 59]. Silver oxide (Ag2O), copper oxide, and ZnO NPs, synthesized using crude extract of plant degraded methylene blue (MB) dye efficiently [66]. Magnetite NPs synthesized using coconut husk and Oryza sativa leaves were used to degrade heavy metals [68]. Ag-NPs are synthesized using Convolvulus arvensis plant extract, and Avicennia marina is used to degrade environmental pollutants [1, 61]. Zero Valent Iron NPs are synthesized from neem degrade water pollutants [57]. 7.4.5.2  USING MICROORGANISMS (BACTERIA, FUNGI, ALGAE, AND ACTINOMYCETES) Trichoderma is a potential bioremediation tool in the environment cleaning process [76]. Aspergillus Niger, and Cladosporium resinae, NPs were being used to remove heavy metals from polluted soil. Pichia jadinii synthesized gold nanoparticles (Au NPs) used to remove heavy metals. Au NPs are synthesized using Chlorella vulgaris to remove heavy metals and azo dyes [33]. Rhodotorula psychrophenolica NPs were capable of degrading phenols [42]. 7.4.5.3  USING ENZYMES AND BIOMOLECULES Cold active enzymes and biomolecules such as lipases and alpha-amylases help in the bioremediation process [42]. Organic and inorganic NMs help in cleaning persistent organic hydrocarbons (HCs) [9]. 7.4.5.4  USING INDUSTRIAL AND AGRICULTURAL WASTES Calcium carbonate and oxide particles are used to remediate organic and inorganic contaminants from calcium-rich agro-industries and industrial byproducts, especially by their processing by different approaches and properties. The recovery of these pollutants from the byproducts is cost-effective and environmentally friendly, and it helps reduce pollution. Biomasses from industrial wastes and Calcium-rich waste helps in the eradication of heavy

Advanced Bionanomaterials for Environmental Remediation 203

metal contamination, and organic and inorganic contaminants, respectively (Table 7.3) [48, 81]. 7.4.6  TOXICITY OF NANOPARTICLES NPs can enter the human beings and food chain due to environmental and human exposure. The NMs toxicity depends on shape, size, structure, and morphology and behaves differently in different biological systems. Some NPs accumulate in the human system and cause cytotoxicity. Inhalation of combustion smoke activates pro-inflammatory response and decreases lung capacity and damage of organs. In humans, Ag-NPs have also been shown to promote fibrin polymerization, cross-linking, and platelet aggregation. Cobalt, titanium, and iron NPs have been found to stimulate macrophage phenotypes that secrete elevated levels of tumor necrosis factor, a member of a group of cytokines involved in systemic inflammation [85]. ZnO, copper oxide, and titanium dioxide (TiO2) caused toxicity in Saccharomyces cerevisiae [34]. In-vitro and in-vivo studies have shown cytotoxicity, ROS production, decreased cell viability, dose-dependent genotoxicity, and damage to mitochondrial enzymes [6]. When NPs get accumulated in zebra fishes leads to deformation in zebra fishes and embryonic toxicity [18]. Accumulation of NPs in body parts of fishes leads to cytotoxicity [84]. NM toxicity was observed in BRL 3A rat liver cells exposed to silver, molybdenum, aluminum, iron oxide, and TiO2. Higher doses of NPs cause enzyme leakage and increased levels of ROS [29]. 7.4.7  ADVANTAGES AND DISADVANTAGES OF ADVANCED METHODS OF CLEAN-UP Bionanomaterials act as reducing and capping agents for synthesis and are less toxic than the conventional method. The plant-based remediation approach is cost-effective and takes advantage of its unique ability to bioaccumulate pollutants from the environment and metabolize them in the tissues. The primary targets for phytoremediation are toxic heavy metals and organic contaminants. The phytoremediation efficiency is dependent on understanding the processes that influence contaminant availability, rhizosphere processes, pollutant uptake, translocation, chelation, and volatilization are required [3, 14]. Phytoremediation, typically 2–10 times cheaper than traditional remediation approaches, can be influenced by the pollutant,

204

TABLE 7.3  Bionanomaterials in Clean-Up Reducing Agent

Metal Salt

Degradation of Pollutants

References

Green tea

Iron and iron oxide

Heavy metals, malachite green dye

[26, 59]

Convolvulus arvensis

Silver

Environment pollutants

[61]

Avicennia marina

Silver

Heavy metals

[1]

Magnetite

Heavy metals

[68]

–

Bioremediation

[42]

Calliandra haematocephala

Zinc oxide

Methylene blue dye

[79]

Biomasses from industrial and agricultural waste

–

Organic and inorganic pollutants

[81]

Triticum aestivum

Selenium

Acts as biofertilizer

[28]

Catha edulis

Silver

The potential heavy metal ion detector

[77]

Phyllanthus Emblica

Silver

Inhibitory action against the pathogen Acidovorax oryzae strain RS-2 of rice bacterial brown stripe

[44]

Myriostachya wightiana

Silver

Control agents against agricultural pests and pathogens

[78]

Solidago canadensis

Silver-gold

Cytotoxicity of nanoparticles

[11]

Acalypha indica

Silver

Effect on different plant diseases caused phytopathogenic fungi

[37]

Matricaria chamomilla

Zinc oxide

Antibacterial activity against Xanthomonas oryzae

[55]

Sustainable Nanomaterials for Biosystems Engineering

Coconut husk and Oryza sativa Lipases and alpha-amylase

Advanced Bionanomaterials for Environmental Remediation 205

substrate, and available alternative remediation methods. The plant’s ability to be used in varying proportions for numerous synergistic approaches results in environmental cleanup and ecosystem restoration. As more information becomes available, adjusting the phytoremediation process to the specifics of a contaminated environment will become more achievable [58]. The methods are described in detail, including the underlying principles, benefits, and limitations. The technique is more time-consuming and slower than traditional approaches, and it is less effective at sites with high contaminant concentrations [14, 41, 74]. One disadvantage of phytoremediation is the roots of plants must reach and act on the pollutant. Thus, the edaphic factors and toxicity level must be conducive to plant growth. At the same time, the pollutant must be physically accessible to the roots and bioavailable for the absorption of the pollutant. Phytoremediation also takes prolonged time than traditional approaches [58]. It is not easy to achieve concentration reductions of more than 95% and less than 0.1 ppm. The critical area is extensive; the generation of dust and vapor during land farming aeration may result in air quality issues [14, 35, 36]. Modern extraction techniques are used to apply cleanup steps, including long sample treatment cycles and large volumes of organic solvents being consumed. The targeted compounds concentration in the final extract is lower than the ones obtained through most conventional methods. The final extract concentration can be achieved by quantification and sensitivity of the extract [43]. 7.5 SUMMARY Nanotechnology is gaining attraction in various industries, and it is also gaining interest in the treatment of oily and contaminated wastewater. The distinctive properties of carbon-based NMs have the potential to transform conventional wastewater treatment. The distinctive properties of GO, CNTs, and carbon fibers have demonstrated their potential benefits to real-world applications. Modifying these carbon-based NPs to improve their properties and environmental friendliness indicates that these NMs have a promising future in oil-related industries. Linking the environmental and occupational health at the beginning of research and development (R&D) of different lithographic cleanup solvents can prevent the development of alternatives that would have brought in worker hazards and provided an opportunity to work around recent occupational health regulatory shortcomings. Incorporating several of these technological advancements for mitigating the harmful effects of oil spills on the environment will be most beneficial and

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parameters, like time, pH, temperature, and humidity, etc., have significant consequences on the overall performance of NP removal. ACKNOWLEDGMENT The authors extend thanks to the Center for Research, CHRIST (Deemed to be University), Bangalore, Karnataka, India, for rendering all technical support. KEYWORDS • • • • • •

bionanomaterials earth ethylenediaminetetraacetic acid nanoscale zero valent iron nanotechnology reactive oxygen species

REFERENCES 1. Abdi, V., Sourinejad, I., Yousefzadi, M., & Ghasemi, Z., (2018). Mangrove-mediated synthesis of silver nanoparticles using native Avicennia marina plant extract from southern Iran. Chemical Engineering Communications, 205(8), 1069–1076. 2. Aksu, Z., (2005). Application of biosorption for the removal of organic pollutants: A review. Process Biochemistry, 40(3, 4), 997–1026. 3. Al-Anzi, B. S., & Siang, O. C., (2017). Recent developments of carbon-based nanomaterials and membranes for oily wastewater treatment. RSC Advances, 7(34), 20981–20994. 4. Almasi, A., Dargahi, A., Ahagh, M., Janjani, H., Mohammadi, M., & Tabandeh, L., (2016). Efficiency of a constructed wetland in controlling organic pollutants, nitrogen, and heavy metals from sewage. Journal of Chemical and Pharmaceutical Sciences, 9(4), 2924–2928. 5. Aryal, N., Wood, J., Rijal, I., Deng, D., Jha, M. K., & Ofori-Boadu, A., (2020). Fate of environmental pollutants: A review. Water Environment Research, 92(10), 1587–1594. 6. Bahadar, H., Maqbool, F., Niaz, K., & Abdollahi, M., (2016). Toxicity of nanoparticles and an overview of current experimental models. Iranian Biomedical Journal, 20(1), 1–11. 7. Banerjee, P., Sau, S., Das, P., & Mukhopadhyay, A., (2014). Green synthesis of silvernanocomposite for treatment of textile dye. Nanoscience and Technology, 1(2), 1–6. 8. Barth, A., Brucker, N., Moro, A. M., Nascimento, S., Goethel, G., Souto, C., & Garcia, S. C., (2017). Association between inflammation processes, DNA damage, and exposure

Advanced Bionanomaterials for Environmental Remediation 207 to environmental pollutants. Environmental Science and Pollution Research, 24(1), 353–362. 9. Basak, G., Hazra, C., & Sen, R., (2020). Biofunctionalized nanomaterials for in situ clean-up of hydrocarbon contamination: A quantum jump in global bioremediation research. Journal of Environmental Management, 256, 1–20. 10. Bhuyan, M. S., Bakar, M. A., Akhtar, A., Hossain, M. B., Ali, M. M., & Islam, M. S., (2017). Heavy metal contamination in surface water and sediment of the Meghna River, Bangladesh. Environmental Nanotechnology, Monitoring & Management, 8, 273–279. 11. Botha, T. L., Elemike, E. E., Horn, S., Onwudiwe, D. C., Giesy, J. P., & Wepener, V., (2019). Cytotoxicity of Ag, Au, and Ag-Au bimetallic nanoparticles prepared using golden rod (Solidago canadensis) plant extract. Scientific Reports, 9(1), 1–8. 12. Brayner, R., Ferrari-Iliou, R., Brivois, N., Djediat, S., Benedetti, M. F., & Fiévet, F., (2006). Toxicological impact studies based on Escherichia coli bacteria in ultrafine ZnO nanoparticles colloidal medium. Nano-Letters, 6(4), 866–870. 13. Burke, K. E., & Wei, H., (2009). Synergistic damage by UVA radiation and pollutants. Toxicology and Industrial Health, 25(4, 5), 219–224. 14. Caliman, F. A., Robu, B. M., Smaranda, C., Pavel, V. L., & Gavrilescu, M., (2011). Soil and groundwater cleanup: Benefits and limits of emerging technologies. Clean Technologies and Environmental Policy, 13(2), 241–268. 15. Cao, J., Xu, R., Tang, H., Tang, S., & Cao, M., (2011). Synthesis of monodispersed CMC-stabilized Fe–Cu bimetal nanoparticles for in situ reductive dechlorination of 1,2,4-trichlorobenzene. Science of the Total Environment, 409(11), 2336–2341. 16. Cao, X., Wang, N., Han, Y., Gao, C., Xu, Y., Li, M., & Shao, Y., (2015). PtAg bimetallic nanowires: Facile synthesis and their use as excellent electrocatalysts toward low-cost fuel cells. Nano-Energy, 12, 105–114. 17. Cao, Y., Chen, M., Dong, D., Xie, S., & Liu, M., (2020). Environmental pollutants damage airway epithelial cell cilia: Implications for the prevention of obstructive lung diseases. Thoracic Cancer, 11(3), 505–510. 18. Celá, P., Veselá, B., Matalová, E., Večeřa, Z., & Buchtová, M., (2014). Embryonic toxicity of nanoparticles. Cells Tissues Organs, 199(1), 1–23. 19. Chakraborty, D., Mondal, N. K., & Datta, J. K., (2014). Indoor pollution from solid biomass fuel and rural health damage: A micro-environmental study in rural area of Burdwan, West Bengal. International Journal of Sustainable Built Environment, 3(2), 262–271. 20. Chenab, K. K., Sohrabi, B., Jafari, A., & Ramakrishna, S., (2020). Water treatment: Functional nanomaterials and applications from adsorption to photodegradation. Materials Today Chemistry, 16, 1–21. 21. Durnev, A. D., (2008). Toxicology of nanoparticles. Bulletin of Experimental Biology and Medicine, 145(1), 72–74. 22. Dutta, T., Kim, K. H., Deep, A., Szulejko, J. E., Vellingiri, K., Kumar, S., & Yun, S. T., (2018). Recovery of nanomaterials from battery and electronic wastes: A new paradigm of environmental waste management. Renewable and Sustainable Energy Reviews, 82, 3694–3704. 23. Farré, M., Sanchís, J., & Barceló, D., (2017). Adsorption 50 Fand desorption properties of carbon nanomaterials, the potential for water treatments and associated risks. In: Nanotechnologies for Environmental Remediation (pp. 137–182). Springer, Cham. 24. Gelperina, S. E., Khalansky, A. S., Skidan, I. N., Smirnova, Z. S., Bobruskin, A. I., Severin, S. E., & Kreuter, J., (2002). Toxicological studies of doxorubicin bound to

208

Sustainable Nanomaterials for Biosystems Engineering

polysorbate 80-coated poly (butyl cyanoacrylate) nanoparticles in healthy rats and rats with intracranial glioblastoma. Toxicology Letters, 126(2), 131–141. 25. Ghangrekar, M. M., & Chatterjee, P., (2018). Water pollutants classification and its effects on environment. In: Carbon Nanotubes for Clean Water (pp. 11–26). Springer, Cham. 26. Gottimukkala, K. S. V., Harika, R. P., & Zamare, D., (2017). Green synthesis of iron nanoparticles using green tea leaves extract. Journal of Nanomedicine and Biotherapeutic Discovery, 7(1), 1–4. 27. He, F., Li, Z., Shi, S., Xu, W., Sheng, H., Gu, Y., & Xi, B., (2018). Dechlorination of excess trichloroethene by bimetallic and sulfidated nanoscale zero-valent iron. Environmental Science & Technology, 52(15), 8627–8637. 28. Hu, T., Li, H., Li, J., Zhao, G., Wu, W., Liu, L., & Guo, Y., (2018). Absorption and bio-transformation of selenium nanoparticles by wheat seedlings (Triticum aestivum L.). Frontiers in Plant Science, 9, 1–10. 29. Hussain, S. M., Hess, K. L., Gearhart, J. M., Geiss, K. T., & Schlager, J. J., (2005). In vitro toxicity of nanoparticles in BRL 3A rat liver cells. Toxicology In Vitro, 19(7), 975–983. 30. Hwang, Y., Lee, Y. C., Mines, P. D., Huh, Y. S., & Andersen, H. R., (2014). Nanoscale zero-valent iron (nZVI) synthesis in a Mg-aminoclay solution exhibits increased stability and reactivity for reductive decontamination. Applied Catalysis B: Environmental, 147, 748–755. 31. Iavicoli, I., Leso, V., Fontana, L., Bergamaschi, A., Fontana, & Antonio, B., (2011). Toxicological effects of titanium dioxide nanoparticles: A review of in vitro mammalian studies. European Review for Medical and Pharmacological Sciences, 15(5), 481–508. 32. Jiang, D., Huang, D., Lai, C., Xu, P., Zeng, G., Wan, J., & Hu, T., (2018). Difunctional chitosan-stabilized Fe/Cu bimetallic nanoparticles for removal of hexavalent chromium wastewater. Science of the Total Environment, 644, 1181–1189. 33. Kapoor, R. T., Salvadori, M. R., Rafatullah, M., Siddiqui, M. R., Khan, M. A., & Alshareef, S. A., (2021). Exploration of microbial factories for synthesis of nanoparticles: A sustainable approach for bioremediation of environmental contaminants. Frontiers in Microbiology, 12, 1–16. 34. Kasemets, K., Ivask, A., Dubourguier, H. C., & Kahru, A., (2009). Toxicity of nanoparticles of ZnO, CuO, and TiO2 to yeast Saccharomyces cerevisiae. Toxicology in Vitro, 23(6), 1116–1122. 35. Khalaj, M., Kamali, M., Khodaparast, Z., & Jahanshahi, A., (2018). Copper-based nanomaterials for environmental decontamination: An overview on technical and toxicological aspects. Ecotoxicology and Environmental Safety, 148, 813–824. 36. Kim, H., Hong, H. J., Jung, J., Kim, S. H., & Yang, J. W., (2010). Degradation of trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) immobilized in alginate bead. Journal of Hazardous Materials, 176(1–3), 1038–1043. 37. Krishnaraj, C., Ramachandran, R., Mohan, K., & Kalaichelvan, P. T., (2012). Optimization for rapid synthesis of silver nanoparticles and its effect on phytopathogenic fungi. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 93, 95–99. 38. Lackner, R., (1998). “Oxidative stress” in fish by environmental pollutants. In: Fish Ecotoxicology (pp. 203–224). Birkhäuser, Basel. 39. Li, H., Qiu, Y. F., Wang, X. L., Yang, J., Yu, Y. J., & Chen, Y. Q., (2017). Biochar supported Ni/Fe bimetallic nanoparticles to remove 1,1,1-trichloroethane under various reaction conditions. Chemosphere, 169, 534–541.

Advanced Bionanomaterials for Environmental Remediation 209 40. Luo, S., Qin, P., Shao, J., Peng, L., Zeng, Q., & Gu, J. D., (2013). Synthesis of reactive nanoscale zero-valent iron using rectorite supports and its application for orange II removal. Chemical Engineering Journal, 223, 1–7. 41. Mahfuz, M., Gazi, M. A., Hossain, M., Islam, M. R., Fahim, S. M., & Ahmed, T., (2018). General and advanced methods for the detection and measurement of aflatoxins and aflatoxin metabolites: A review. Toxin Reviews, 39(2), 123–137. 42. Margesin, R., & Feller, G., (2010). Biotechnological applications of psychrophiles. Environmental Technology, 31(8, 9), 835–844. 43. Martins, J. G., Chávez, A. A., Waliszewski, S. M., Cruz, A. C., & Fabila, M. M. G., (2013). Extraction and clean-up methods for organochlorine pesticides determination in milk. Chemosphere, 92(3), 233–246. 44. Masum, M., Islam, M., Siddiqa, M., Ali, K. A., Zhang, Y., Abdallah, Y., & Li, B., (2019). Biogenic synthesis of silver nanoparticles using Phyllanthus Emblica fruit extract and its inhibitory action against the pathogen Acidovorax oryzae strain RS-2 of rice bacterial brown stripe. Frontiers in Microbiology, 10, 1–18. 45. Meißner, T., Oelschlägel, K., & Potthoff, A., (2014). Implications of the stability behavior of zinc oxide nanoparticles for toxicological studies. International NanoLetters, 4(3), 1–13. 46. Mishra, S., Chowdhary, P., & Bharagava, R. N., (2019). Conventional methods for the removal of industrial pollutants, their merits and demerits. In: Emerging and Eco-Friendly Approaches for Waste Management (pp. 1–31). Singapore: Springer. 47. Mohammed, N., Grishkewich, N., & Tam, K. C., (2018). Cellulose nanomaterials: Promising sustainable nanomaterials for application in water/wastewater treatment processes. Environmental Science: Nano, 5(3), 623–658. 48. Mosa, K. A., Saadoun, I., Kumar, K., Helmy, M., & Dhankher, O. P., (2016). Potential biotechnological strategies for the cleanup of heavy metals and metalloids. Frontiers in Plant Science, 7, 1–14. 49. Mueller, N. C., & Nowack, B., (2010). Nanoparticles for remediation: Solving big problems with little particles. Elements, 6(6), 395–400. 50. Mueller, N. C., Braun, J., Bruns, J., Černík, M., Rissing, P., Rickerby, D., & Nowack, B., (2012). Application of nanoscale zero-valent iron (NZVI) for groundwater remediation in Europe. Environmental Science and Pollution Research, 19(2), 550–558. 51. Murr, L. E., Bang, J. J., Esquivel, E. V., Guerrero, P. A., & Lopez, D. A., (2004). Carbon nanotubes, nanocrystal forms, and complex nanoparticle aggregates in common fuel-gas combustion sources and the ambient air. Journal of Nanoparticle Research, 6(2), 241–251. 52. Nascimento, M. A., Lopes, R. P., Cruz, J. C., Silva, A. A., & Lima, C. F., (2016). Sulfentrazone dechlorination by iron-nickel bimetallic nanoparticles. Environmental Pollution, 211, 406–413. 53. Ndimele, P. E., (2017). The Political Ecology of Oil and Gas Activities in the Nigerian Aquatic Ecosystem (1st edn., p. 486). Academic Press. 54. Nowack, B., David, R. M., Fissan, H., Morris, H., Shatkin, J. A., Stintz, M., & Brouwer, D., (2013). Potential release scenarios for carbon nanotubes used in composites. Environment International, 59, 1–11. 55. Ogunyemi, S. O., Abdallah, Y., Zhang, M., Fouad, H., Hong, X., Ibrahim, E., & Li, B., (2019). Green synthesis of zinc oxide nanoparticles using different plant extracts and their antibacterial activity against Xanthomonas oryzae pv. oryzae. Artificial cells, Nanomedicine, and Biotechnology, 47(1), 341–352.

210

Sustainable Nanomaterials for Biosystems Engineering

56. Onwurah, I. N. E., Ogugua, V. N., Onyike, N. B., Ochonogor, A. E., & Otitoju, O. F., (2007). Crude oil spills in the environment, effects, and some innovative clean-up biotechnologies. International Journal of Environmental Research, 1(4), 307–320. 57. Pattanayak, M., & Nayak, P. L., (2013). Green synthesis and characterization of zerovalent iron nanoparticles from the leaf extract of Azadirachta indica (neem). World Journal of Nano-Science and Technology, 2(1), 6–9. 58. Pilon-Smits, E. A., & Freeman, J. L., (2006). Environmental cleanup using plants: Biotechnological advances and ecological considerations. Frontiers in Ecology and the Environment, 4(4), 203–210. 59. Plachtová, P., Medrikova, Z., Zboril, R., Tucek, J., Varma, R. S., & Maršálek, B., (2018). Iron and iron oxide nanoparticles synthesized with green tea extract: Differences in ecotoxicological profile and ability to degrade malachite green. ACS Sustainable Chemistry & Engineering, 6(7), 8679–8687. 60. Powers, K. W., Palazuelos, M., Moudgil, B. M., & Roberts, S. M., (2007). Characterization of the size, shape, and state of dispersion of nanoparticles for toxicological studies. Nanotoxicology, 1(1), 42–51. 61. Rasheed, T., Bilal, M., Li, C., Nabeel, F., Khalid, M., & Iqbal, H. M., (2018). Catalytic potential of bio-synthesized silver nanoparticles using Convolvulus arvensis extract for the degradation of environmental pollutants. Journal of Photochemistry and Photobiology B: Biology, 181, 44–52. 62. Reddy, A. V. B., Yusop, Z., Jaafar, J., Reddy, Y. V. M., Aris, A. B., Majid, Z. A., & Madhavi, G., (2016). Recent progress on Fe-based nanoparticles: Synthesis, properties, characterization, and environmental applications. Journal of Environmental Chemical Engineering, 4(3), 3537–3553. 63. RoyChowdhury, A., Datta, R., & Sarkar, D., (2018). Heavy metal pollution and remediation. In: Green Chemistry (pp. 359–373). Elsevier. 64. Sanjurjo-Sánchez, J., & Alves, C., (2012). Decay effects of pollutants on stony materials in the built environment. Environmental Chemistry Letters, 10(2), 131–143. 65. Santhosh, C., Velmurugan, V., Jacob, G., Jeong, S. K., Grace, A. N., & Bhatnagar, A., (2016). Role of nanomaterials in water treatment applications: A review. Chemical Engineering Journal, 306, 1116–1137. 66. Sapawe, N., Ariff Rustam, M., Hafizan, H. M. M., Kamal, E. M. L. M., Raidin, A., & Farhan, H. M., (2019). A novel approach of in-situ electrosynthesis of metal oxide nanoparticles using crude plant extract as the main medium for supporting electrolyte. Materials Today: Proceedings, 19, 1441–1445. 67. Scaria, J., Nidheesh, P. V., & Kumar, M. S., (2020). Synthesis and applications of various bimetallic nanomaterials in water and wastewater treatment. Journal of Environmental Management, 259, 1–17. 68. Sebastian, A., Nangia, A., & Prasad, M. N. V., (2018). A green synthetic route to phenolics fabricated magnetite nanoparticles from coconut husk extract: Implications to treat metal-contaminated water and heavy metal stress in Oryza sativa L. Journal of Cleaner Production, 174, 355–366. 69. Sharma, G., Kumar, A., Naushad, M., Kumar, A., Ala’a, H., Dhiman, P., & Khan, M. R., (2018). Phytoremediation of toxic dye from aqueous environment using monometallic and bimetallic quantum dots-based nanocomposites. Journal of Cleaner Production, 172, 2919–2930.

Advanced Bionanomaterials for Environmental Remediation 211 70. Sharma, S., Tiwari, S., Hasan, A., Saxena, V., & Pandey, L. M., (2018). Recent advances in conventional and contemporary methods for remediation of heavy metal-contaminated soils. 3 Biotech, 8(4), 1–18. 71. Smith, S. C., & Rodrigues, D. F., (2015). Carbon-based nanomaterials for removal of chemical and biological contaminants from water: A review of mechanisms and applications. Carbon, 91, 122–143. 72. Sousa, J. C., Ribeiro, A. R., Barbosa, M. O., Pereira, M. F. R., & Silva, A. M., (2018). A review on environmental monitoring of water organic pollutants identified by EU guidelines. Journal of Hazardous Materials, 344, 146–162. 73. Stensberg, M. C., Wei, Q., McLamore, E. S., Porterfield, D. M., Wei, A., & Sepúlveda, M. S., (2011). Toxicological studies on silver nanoparticles: Challenges and opportunities in assessment, monitoring, and imaging. Nanomedicine, 6(5), 879–898. 74. Sutton, P., Wolf, K., & Quint, J., (2009). Implementing safer alternatives to lithographic cleanup solvents to protect the health of workers and the environment. Journal of Occupational and Environmental Hygiene, 6(3), 174–187. 75. Teow, Y. H., & Mohammad, A. W., (2019). New generation nanomaterials for water desalination: A review. Desalination, 451, 2–17. 76. Tripathi, P., Singh, P. C., Mishra, A., Chauhan, P. S., Dwivedi, S., Bais, R. T., & Tripathi, R. D., (2013). Trichoderma: A potential bioremediation for environmental cleanup. Clean Technologies and Environmental Policy, 15(4), 541–550. 77. Tsegay, M. G., Gebretinsae, H. G., Sackey, J., Maaza, M., & Nuru, Z. Y., (2021). Green synthesis of khat mediated silver nanoparticles for efficient detection of mercury ions. Materials Today: Proceedings, 36, 368–373. 78. Vadlapudi, V., & Amanchy, R., (2017). Phytofabrication of silver nanoparticles using Myriostachya wightiana as a novel bioresource, and evaluation of their biological activities. Brazilian Archives of Biology and Technology, 60, 1–13. 79. Vinayagam, M., Ramachandran, S., Ramya, V., & Sivasamy, A., (2018). Photocatalytic degradation of orange G dye using ZnO/biomass activated carbon nanocomposite. Journal of Environmental Chemical Engineering, 6(3), 3726–3734. 80. Watt, J., Tidblad, J., Kucera, V., & Hamilton, R., (2009). The Effects of Air Pollution on Cultural Heritage (1st edn., p. 306). Boston-MA: Springer. 81. Yadav, V. K., Yadav, K. K., Cabral-Pinto, M., Choudhary, N., Gnanamoorthy, G., Tirth, V., & Khan, N. A., (2021). The processing of calcium rich agricultural and industrial waste for recovery of calcium carbonate and calcium oxide and their application for environmental cleanup: A review. Applied Sciences, 11(9), 1–25. 82. Yaqoob, A. A., Parveen, T., Umar, K., & Mohamad, I. M. N., (2020). Role of nanomaterials in the treatment of wastewater: A review. Water, 12(2), 1–30. 83. Zhang, B. W., Yang, H. L., Wang, Y. X., Dou, S. X., & Liu, H. K., (2018). A comprehensive review on controlling surface composition of Pt-based bimetallic electrocatalysts. Advanced Energy Materials, 8(20), 1–41. 84. Zhu, Z. J., Carboni, R., Quercio, Jr. M. J., Yan, B., Miranda, O. R., Anderton, D. L., & Vachet, R. W., (2010). Surface properties dictate uptake, distribution, excretion, and toxicity of nanoparticles in fish. Small, 6(20), 2261–2265. 85. Zoroddu, M. A., Medici, S., Ledda, A., Nurchi, V. M., Lachowicz, J. I., & Peana, M., (2014). Toxicity of nanoparticles. Current Medicinal Chemistry, 21(33), 3837–3853.

CHAPTER 8

ADVANCED BIONANOMATERIALS FOR ENVIRONMENTAL CLEAN RECOVERY PROCESSES NOSHIN AFSHAN and ALINA BARI

ABSTRACT With the increase in the global population, the adequate supply of resources has become limited. It is imperative to develop pollution-free environmental restoration technologies and clean energy supply to promote the sustainable development of human society. For this purpose, bionanomaterials mimicking the properties of nanomaterials (NMs) for a clean environment are the best choice, and bionanotechnology has a favorable impact on the development of “clean and environment-friendly” technologies rendering significant benefits for human health and the ecosystem. It finds applications in exploring the potential to provide solutions for managing, mitigating, and cleaning up the air, water, and land pollution and improving the performance of traditional technologies. Hence, this chapter deals with the impact of bionanotechnology on sustainable development bringing forth solutions to the environmental problems with low energy consumption, affordable cost, renewability, high selectivity, and no secondary pollution. Moreover, the principles of green chemistry would also be explained, affecting their recovery and reusability, applications, and limitations. Although remediation techniques using bionanomaterials retain remarkable performance and high efficiency, monitoring their adverse effects on human health and the environment is necessary. Since the inherently complex nature of pollutants leading the conventional and unconventional treatment techniques to the end limit Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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has paved the way to the applicability of the intelligent bionanomaterials with enhanced response efficiency, fast response time, and lack of byproducts as pollutants. Hence, it has been expected to apply the architecture and function of the intelligent bionanomaterials to the industrial scale in the near future. 8.1 INTRODUCTION The history of humanity has recorded the achievements of various science and technology guided by the natural world around us. A subgroup of nanotechnology (NT), inspired by the biological world, has been helping us enter the nanoscale world, named bionanotechnology. It is one of the best subsets of NT, offering potential applications in various fields. In this field, NT turns to the world of biology to advance research endeavors. It was shown as the use of natural biological components such as proteins, lipids, nucleic acids, and carbohydrates in conjunction with the specificity and biological activity to develop nanoscale technology [37]. In this chapter, the term “bio-nanotechnology” describes biomolecular tools such as recognition and assembly for NT-based applications, especially clean and green environments. The bionanotechnology market relies on programmable engineered NMs, including clean environmental recovery, electronics, energy, defense, cosmetics, medical, food, and agricultural sectors. In any case, it includes the synthesis and applications of physical, chemical, and biological systems, starting from a single atom or molecule in nanometer (nm) scale to the resulting nanostructures up to microscale. It exhibits unique characteristic as programmability and fine-tuning at the nano- and micro-scale differing from those on larger scales. For example, a DNA double-helix structure is about 2 nm in diameter, and a water molecule is about 0.3 nm [37]. 8.1.1  ENVIRONMENTAL SAFETY The prime challenge facing the world in this era is to provide humans with better living standards, reducing human activities’ impact on the ecosystem. In the aurora of the long-awaited bionanotechnology era, along with various bionanotechnology related discoveries and breakthroughs in the chemical, medical, electronics, computer, automotive, and food industries, there are certainly several examples of environmental applications of bionanotechnology and bionanomaterials to leverage bionanotechnology as a tool to

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improve the environment. The development of bionanotechnology and its applications goes beyond the original concept of pollution prevention, and green techniques present a more straightforward approach. They are now considered an essential component of achieving sustainability. Bionanotechnology offers potential economic, social, and environmental benefits [28]. Bionanotechnology paves the way towards new technological avenues that would substitute the currently employed technologies in the developing countries or enable them to take advantage of bionanotechnology to meet some of their key demands. The development of bionanoscience and bionanotechnology is aimed to play a crucial part in the rehabilitation of a clean environment. The main objective of bionanoscience and bionanotechnology to offer clean environmental recovery processes is to advance an economically simple route to design new bionanomaterials that may effectively remove a series of pollutants in the environment easily recycled multiple times. Various bionanomaterials have been used for the treatment of pollution in the environment. Hence, bionanotechnology exhibits potential applications in pollution reduction, generating renewable energy, and biomedical fields [28]. 8.1.2 BIONANOMATERIALS Bionanomaterials refer to biodegradable materials of nanometer size along any of its dimensions. They retain various shapes such as round, tubular, square, lozenge, hexagonal or irregular. They differ in their chemical composition, including organic or inorganic and amorphous or crystalline. The nanoscale size and peculiar structure predict their physicochemical characteristics dictating their role in the industry, including clean environmental recovery processes. Their widespread applications induce temptation and curiosity in their future perspectives. Moreover, owing to public awareness, reduction in fossil resources and increasing wastes have attracted researchers’ attention towards the field of material chemistry; for example, waste from agriculture like lignocellulose has been turned into bionanomaterials to strengthen bionanocomposite (NC) polymer, which retain multifunctional behavior and capability to give rise to naturally biodegradable materials [26, 35]. 8.1.3  SELF-ASSEMBLY OF BIONANOMATERIALS Self-assembly is a simple and effective technique leading to discrete bionanomaterials with a specified geometry tending to perform novel functions

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[48]. It consists of two approaches that are bottom-up approach and the top-down approach. The bottom-up self-assembly gives rise to macroscopic bionanomaterials self-assembled from tiny building blocks, leading to smaller discrete structures up to molecular scale. Usually, the interactions are intermolecular or intramolecular following hydrogen bonding, electrostatic interactions, or weak Vander-Waals forces. Such approaches are common in biological systems and nanoscience. For example, Willner et al. have reported the self-assembled nanostructures’ applicability as biosensors [47]. Various bionanomaterials mimicking the naturally self-assembled bionanomaterials have been artificially self-assembled. The building blocks impregnated with a series of modifications have been adsorbed onto nanotubes, nanowires, beads, planar structures, liposomes, and suspensions reasonably quickly and economically. Such self-assembled bionanomaterials may have the biological function of gene introduction in preventing the breakdown of the available molecules with the cell membrane. The peptides, DNA, protein, lipid bilayers, and ATP synthase are significant materials for selfassembly. Owing to their programmability, unique molecular characteristics, assigning discrete geometry, and adaptable functions, the self-assembled bionanomaterials find their potential applications in the fields of tissue engineering, biomedical engineering, materials science, nanodevices, and biosensors. Moreover, there are certain factors to control the geometry of the biomacromolecules, such as nature of the interactions, DNA base pair sequence, number of DNA helices, angle of curvature, or external stimuli such as temperature, pH, or enzymes [47]. 8.1.4  CATEGORIES OF BIONANOMATERIALS Biomolecular engineering, for example, enzymatic/chemical conjugation, genetic engineering, and protein engineering, solve the problem of programmable self-assembly of such biological molecules as peptides, nucleic acids, carbohydrates, and proteins. It has been serving as the foundation of biological systems, offering a series of advantages in manipulating the engineered bionanomaterials’ structure, function, and properties. Furthermore, the engineered bionanomaterials have been employed in various fields, including gene therapy, biosensing, theranostics, bioanalysis, bioimaging, and biocatalysis. Table 8.1 enlists some crucial categories of biomolecular engineering along with their functions and applications [38].

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TABLE 8.1  Categories of Biomolecular Engineering Followed by Their Functions and Applications [38] Biomolecular Engineering

Functions of Biomolecules Applications

Nucleic acid engineering

Self-assembly

Biosensing

Gene engineering

Molecular binding

Theranostics

Enzymatic conjugation

Molecular transport

Bioimaging

Chemical conjugation

Molecular identification

Biocatalysis

Protein engineering

Electron shifting

Bioanalysis

Linker engineering

Catalysis

Tissue engineering

Carbohydrate engineering

Energy transfer

Bioelectronic devices

Peptide engineering

Photoluminescence

Cell/organ/DNA/protein chip

8.1.4.1  NUCLEIC ACID SELF-ASSEMBLY Nucleic acids (DNA and RNA) perform a variety of critical biochemical roles to regulate gene expression, store, and transfer genetic makeup, molecular recognition, theranostics, and catalysis [38]. Nucleic acid self-assembly employing base-pair recognition is key to DNA/RNA NT, as it involves DNA/RNA motifs as building blocks to self-assemble into nanostructures such as nanotubes, nanowires, nanorods, wireframes, framework nucleic acid (FNA), DNAzymes, nanoflowers, origami, skeleton, RNA enzymes, and DNA/RNA ribosomes. To create stable motifs of DNA tiles, cross patterns are designed through mutual DNA exchange and branched patterns through sticky ends and cross-connect patterns, including Sierpinski triangles and tensegrity triangles. Such DNA tiles might also be self-assembled into nanotubes, helical groups, and complex DNA motifs and nanostructures [38]. DNA self-assembly occurs through the specific pairing of complementary bases under the appropriate temperature and optimal concentration of Na+/Mg2+ ions. Unique geometries can be developed when complementary single-stranded DNA (ssDNA) molecules are annealed together to design double-stranded DNA molecules. For example, molecular self-assembly gives rise to complex but straightforward structures. Molecular selfassembly employs solid and liquid non-covalent interactions to yield specific geometrical shapes. Synthesis of nanoscale structures using various techniques, including gas condensation, vapor deposition, chemical precipitation, biological templates, and the biologically imitated system [9]. To create nanostructures, the two main approaches include the top-down approach and

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the bottom-up approach. The top-down approach results in the nanostructures employing manufacturing methods such as lithography. The bottom-up approach in the manufacture of NMs directly at the molecular scale using molecular recognition to construct various structures. The best example of the bottom-up approach is DNA self-assembly. The self-assembly approach finds its applicability in biological systems where the nanometer scale often coheres by nonbonded interactions such as microtubules, filaments, and construction of the double helices [9]. 8.1.4.2  DNA/RNA ORIGAMI Despite its proven validity, the traditional “multi-strand” approach has certain drawbacks. The construction of larger structures demands precise stoichiometry, sequence optimization, and often oligonucleotides purification, which is susceptible to errors and lengthy synthetic procedures. To solve those problems, Rothemund reported a new approach to creating large DNA nanostructures in 2006, called “DNA origami” [9]. Unlike the conventional “multistranded” approach, DNA origami is the process in which a long ssDNA scaffold undergoes folding into various arbitrary complex patterns, structures, and 3D objects with the help of multiple complementary staples. It is relatively easy to handle and biocompatible, resulting in a large amount of the required product regardless of purity and stoichiometry of the oligonucleotides [41]. The high-performance efficiency of this technique is the outcome of the benefits of entropy employing a single long scaffold. Owing to the generation of complex nanostructures with predefined geometry following dramatically reduced experimental errors and annealing time, this technique has become highly significant in the field of DNA NT. It may extend the DNA origami system from 2D to 3D; for example, dsDNA may be combined to control the relative position of adjacent dsDNA with a crossover or may use interconnecting strands to collapse a 2D origami domain into 3D geometry. The 3D DNA sequences with such topologies as cubes, polyhedra, prisms, and buckyballs have successfully been created, benefiting from edge stiffness and junction flexibility [21]. Secondary interactions within the RNAs lead to differences in the folding characteristics of RNAs and DNAs. For this instance, tertiary interactions centered on RNA tectonics; for example, hairpin-hairpin or hairpin-receptor interactions have been introduced in the RNA self-organization. The basic principle of DNA origami remains the same for RNA origami, such as building a new and diverse RNA architecture using three- and four-way intersections

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is the same as DNA branching. Moreover, both of the approaches may give rise to a jigsaw puzzle [21]. Among the significant features of origami, the most important one is that each building block retains programmability and dictates the ability of origami to place the functional parts linked to the staples in the desired position. For example, proteins, nanoparticles (NPs), or dyes have been positioned on 2D origami selectively in a controlled manner. Origami scaffold can find its applicability in DNA nanorobots, biomolecular functions with improved selectivity, and single-molecule imaging. Moreover, its prospective applications include its utility as scaffolding for X-ray crystallography, biosensors, photonics, nanomechanical devices, biomimetic systems for energy transfer, and clinical theranostics [21, 29, 40]. 8.1.4.3 APTAMERS Aptamers or artificial antibodies are small-sized single-stranded nucleic acids (ssRNA or ssDNA) isolated from chemically synthesized combined oligonucleotides through in-vitro selectivity showing the profound ability of binding to the target site with enhanced selectivities such as drugs, proteins, DNA nanostructures, peptides, and complex issues. Various protocols, including next-generation sequencing, systematic evolution of ligands by exponential enrichment (SELEX), and advanced bioinformatics for in-vitro aptamers selection, have been designed. Unlike the conventional processes, which rely upon the complex sample pretreatment, expensive detection equipment, and experimental environment to exhibit environmental clean recovery process, aptamers are exceptionally advantageous, rendering simple preparation, easy to label, highly stable, target-specific, highly selective, and sensitive in their mode of action. Besides their wide-spread usage in the theranostic, detection of proteins, viruses, cells, antibodies, pesticides, heavy metals, and sugars, they have been showing potential applications in the fields of targeted drug delivery, gene therapy, bionanosensors as optical aptasensors, and electrochemical aptasensors and diagnostic reagents [38, 45]. 8.1.4.4 RIBOZYMES Ribozymes, a subclass of bionanomaterials, are RNA molecules that catalyze phosphodiester bonds and specifically inhibit gene expression through

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RNA substrate cleavage, as in cancer, genetic diseases, and viral therapy. The clamping sequence surrounding the RNA catalytic motif directs the ribozyme to its target site, stabilizing the complex. They follow WatsonCrick base pairing to bind with the RNA substrate leading to the cleavage of the substrate sequence. In such cases, the divalent ions such as magnesium facilitate the fission reaction, which may occur after any NUH triplet (N being nucleotide and H being A, U or C) in the target RNA. The kinetics of such reactions varies widely along with the varying combinations of tripletflanking sequences [38]. The ribozymes catalyze a series of chemical reactions such as formation, fission, and rearrangement, for example, RNA substrate breakdown, Diels-Alder reaction, N-glycoside bond formation, amide bond formation, acylation, and alkylation without producing the secondary pollutants. Instead, they serve as highly efficient, eco-friendly, and clean recovery tools for the environment. It may elevate their catalytic performance, nuclease resistance, and group diversity by introducing chemical modifications linked to the nucleotides. They may also be expressed from vectors offering the advantage of continuous intracellular production. They often require a carrier for efficient delivery into target cells. A range of NMs such as polymer micelles, liposomes, and nucleic acids inhibit nuclease-based degradation and also improve intracellular transduction [38, 43]. 8.1.4.5  GENE ENGINEERING It has been serving as a dominant tool of technology. To design artificial genes has made their translation possible into enzymes and proteins with the required set of unique and diverse properties, including self-assembly, molecular binding/identification/transport, catalysis, electron shifting, energy transfer, and photoresponse, leads to the discovery of new bionanomaterials. This technique has facilitated the development of in-vitro genes through repetitive recombination procedures. In addition to assisting protein engineering, it comes up with DNA randomization, DNA sequence amplification, gene mutagenesis, and gene fusion leading to the fusion libraries and genetic diversity. For example, in-vitro gene manipulation has enabled various types of gene alterations via insertion, deletion, or replacement of codon(s) under gene mutagenesis, switching domains among gene sequences as DNA fusing and shuffling domains in the form of fusion genes leading to the diverse collection of mutant genes [38].

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8.1.4.6  PROTEIN ENGINEERING Engineering topology of protein as bionanomaterials has played a vital role in bionanotechnology, biomedical research, and biological sciences, manifesting the environmental safety concerns under strict consideration. It has been serving as an indispensable hazard-free technology tool for bionanotechnology for designing valuable motifs as building blocks to create various nano-size protein systems, proteins having immobilized peptides on NP, and those for application to bioimaging, gene therapy, biosensing, bioelectronic devices, and biocatalysis [10, 24]. 8.2  ADVANCED BIONANOMATERIALS EXHIBITING ENHANCED SITE REMEDIATION Advances in bionanotechnology and material science have been coming out with materials to enhance in-situ recovery from the persistent and most abundant contaminants, improve the visualizing strength for the source areas, and measure the recovery progress. The multifunctional character of the bionanomaterials enables them to target specifically and selectively multiple contaminants simultaneously, leading to the enhanced in-situ recovery of the contaminants [52]. 8.2.1  BIONANOMATERIALS WITH MULTI-FUNCTIONAL CHARACTERISTICS At recovery sites, there is a high concentration of such pollutants as heavy metals, e.g., Pb, Hg, Cd, metal oxides (MO) such as those of antimony, Arsenic (As), Chromium, and Selenium, and chlorinated systems organic pollutants, for example, polycyclic-aromatic-hydrocarbons (HCs). Various pollutants found in the water resources require different reagents and, in turn, different treatment techniques. For example, pollutants of organic nature undergo either redox reactions or adsorption, and MO and heavy metals are immobilized with the help of adsorption or precipitation techniques. The ineffectiveness and requirement of a longer timespan with higher energy demand exclude the available recovery methods for commercial applications. Hence, bionanomaterials serve as a competent and advantageous platform with multifunctional characteristics such as high pollutants removal

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efficiency, eco-friendly, affordable cost, easy to operate, and renewability. For example, surfactants based bionanomaterials, on the one hand, absorb the organic pollutants based on hydrophobic interactions, and on the other hand, absorb heavy metals via electrostatic interactions leading to robust remediation at pH value ranging from 4 to 9 [52]. 8.2.2  SPECIFICITY AND SELECTIVITY OF BIONANOMATERIALS Bionanomaterials have various advantages, including their specificity and selectivity against pollutants, enhanced reactivity, and improved absorption capacity. These characteristics increase their limit of depletion while reacting with background metal ions and organic compounds. Hence, selective removal of pollutants contradicts adverse effects; for example, in the case of agriculture, bionanomaterials cause retention of soil function and lack of toxic by-products [33, 52]. 8.2.3 BIONANOTRACERS Since pollution is a substantial global concern adversely affecting human life and socio-economic aspects, various technologies have been practiced to clean the environment. One of the promising technologies mainly practiced in agriculture, life sciences, and physical sciences is to use nano-traces which track the pollutants and their migration routes in soil, air, and water employing labeled materials. Traditionally, stable isotopes, natural silica, artificial chlorides, bromides, and fluorescent dyes were used as nano-traces leading to various shortcomings such as the high cost of the nano-tracer, for example, fluoro benzoic acid, the appearance of background signals, or false determination of the pollutants. Hence, there is a need to discover highly efficient nano-traces, such as DNA-based nanotraces [34, 36]. DNA nano-traces have been particular and selective in their mode of action performing safe and clean function with improved accuracy, enhanced efficiency, better performance with multipoint detection, high sensitivity, and stable migration. Every DNA nano-tracer retains a unique DNA sequence that imparts good features; for example, they have been serving as an effective strategy in hydrological research. Since the DNA is an essential component of life, has been ubiquitous in air, food, and water, it is naturally non-toxic because the sequence of DNA nano-tracer is synthetic, which lack the hereditary genome sequences and leads to their safe usage [33].

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8.2.4  STIMULI-RESPONSIVE BIONANOMATERIALS Various shortcomings have accompanied Chemical-based therapeutics. These include low solubility, poor cell uptaking, weak bioavailability because of fast renal clearance, the incompetence to target or accumulation at the target site. Since NT is an interdisciplinary field, significant efforts have been devoted to discovering bionanomaterials in response to stimuli [7]. Different approaches have been developed, paving the way to demonstrate the ability to respond autonomously when triggered by external stimuli such as heat, chemicals, light, etc. NMs such as liposomes [23], polymers [11, 20], solid NPs [2], micelles, Au nanorods [46], MNPs [5], and some DNA origami have shown stimuli triggering response with a profound demonstration of their potential in biosensing, drug delivery, and theranostics. Such responses generally include morphological exchange, expansion or contraction of conformation, assembly or aggregation, disassembly or reduction, and movement induction [12]. Stimulus-responsive DNA NMs make up a significant class of functional bionanomaterials exhibiting vital applications. Some of the latest examples of such bionanomaterials with particular reference to their design and triggered mechanism have been described as under. 8.2.4.1  pH-RESPONSIVE BIONANOMATERIALS The pH gradient has long been triggering stimuli-responsive bionanomaterials exhibiting various applications in the biomedical field. Such bionanomaterials consist of specific groups wherein a slight change in pH value induces remarkable structural changes. For example, i-motif exists in stabilized form only in slightly acidic conditions and of FNA has been successfully self-assembled only in a slightly acidic medium, otherwise neutral or slightly primary conditions would let them orient into random coils or double helices [12]. 8.2.4.2  METAL IONS RESPONSIVE BIONANOMATERIALS A series of DNA motifs interacted specifically with metal ions, including Pb2+, Mg2+, Hg2+, K+, Au+, and Ag+. The metal ions-mediated DNA nanostructures find potential applications in the detection of the heavy metal ions,

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construction of logical gates as DNA based nanoelectronic devices, environmental monitoring, target-specific drug delivery, and food safety [12]. 8.2.4.3  OLIGONUCLEOTIDE RESPONSIVE BIONANOMATERIALS The discrete rigid 3D DNA nanostructures have been self-assembled by packaging multiple helices, for example, a DNA box created by Gothelf and Kjems. This kind of DNA origami consists of nanoarrays of antiparallel helices, which are densely packed, rendering interconnection at the 3D pattern of crossovers. Such a set of crossovers predicts how the interconnections of the adjacent helices determine the origami’s geometry [3]. One of the strategies to control changes in the layout of DNA origami is DNA strand transfer. The foot-mediated strand transfer enables reconfiguration of the DNA origami or a part of it upon the addition of DNA staples, such as control over the opening and closing of the assembled DNA box. Before the addition of the fuel strands, the box is tightly closed with a lid. While the fuel strands added into it would be hybridized with the cover DNA strand on the lid, striving it free. Hence, the box is then opened, and the molecular charge in the box is released. Such reversible changes have been evidenced by high-resolution atomic force microscope (AFM) [12]. Zadegan et al. [51] reported fuzzy and Boolean logic gates that follow the strand transfer strategy. Moreover, such a versatile strategy has also been employed to regulate transcription pathways, to differentiate single nucleotide variants, to sense in-vitro microRNAs, and to detect cancer biomarkers in the living cells [6, 49]. 8.2.4.4  ENZYME RESPONSIVE BIONANOMATERIALS Since enzymes are a vital component of biochemical procedures, enzymes catalyzing DNA boost the host’s immunity, protecting them from the impact of DNA on foreign infectious entities. Enzyme responsive bionanomaterials employ enzymes as input signals exhibiting excellent biocompatibility, high selectivity, and increased sensitivity and are widely used for biomedical applications. For example, they enable the construction of logic gates using endonucleases as input, and two different endonucleases do construct twoinput and three-input logic gates imparting enhanced efficiency [12].

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8.3  BIONANOTECHNOLOGY COMPLEMENTING EXISTING REMEDIATION TECHNOLOGIES 8.3.1  ENHANCED BIODEGRADATION The NMs exhibiting bioremediation promote the recovery process of the groundwater. Physicochemical procedures, including surfactant rinsing, thermal treatment, and chemical oxidation, have well-performed bioremediation transforming pollutants into biodegradable, less toxic, and exceedingly soluble by-products, thereby increasing the microbial content [19]. The biodegradation process also shows the same capability with enhanced potential [17]. Combining bionanomaterials with bioremediation technologies broadens the range of degradable pollutants because some microorganisms may carry out alternatives. For example, microorganisms with the redox capability efficiently carry out soil bioremediation removing the petroleum HCs [52]. 8.3.2  THERMAL TECHNIQUE The thermal technique has been serving as a practical approach for the in-situ removal of organic pollutants. It includes electrically resistive heating, steam injection, and natural gas combustion, causing very high treatment potential and more incredible energy, which may limit the applications of this technique [52]. 8.4  IMPACT OF GREEN CHEMISTRY ON BIONANOSCIENCE Owing to the European strategy 2020, intensely competitive, green, and sustainable economies have been expected to meet the demand of the hour. This approach has been based on resource-saving economy, climate adaptation, low-carbon content, decreased level of pollution, and restoration of the clean and healthy ecosystem [37]. 8.4.1  GREEN SYNTHESIS OF BIONANOMATERIALS Clean and economical biosynthetic methods result in the absorption of some toxic chemicals on the material’s surface. Green synthesis, an eco-friendly

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approach for NP synthesis on a broad scale, manipulating microorganisms may overcome the toxicity issues. Metal-based green bionanomaterials have been synthesized following various biosources that are more efficient, low cost, lack toxic substrates, have no secondary wastes, and have better yield [1]. Interestingly, many plant extracts, algae, and microorganisms, including bacteria, yeast, and fungi, have become an efficient synthetic tool for bionanomaterials. For example, microalgae assisting the scalable and permanent photobioreactors promote the synthesis of sustainable bionanomaterial fabrics. The bionanomaterials exhibit various applications in the biomedical field, for example, gene transmission, target-specific drug delivery, drug carriers, food packaging, cell labeling, wound dressings, and bionanosensors. However, several applications such as magnetic responsive drug delivery and photographic thermal therapy are still at their nascent stage [4, 39]. Some of the synthetic procedures of green bionanomaterials are Tollens procedure, polysaccharide procedure, biological procedure, polyoxometalates (POMs) procedure, and irradiation. 8.4.1.1  TOLLENS PROCEDURE Tollens procedure consisting of the single-step synthetic route gives rise to silver nanoparticles (Ag-NPs) with controlled geometry. In its modified procedure, silver ions undergo reduction through saccharides under ammonia as a medium producing silver nanoparticle-based films with particle sizes ranging from 50 nm to 200 nm and silver hydrosols with a particle size of 20–50 nm. Moreover, it also gives rise to Ag-NPs in different shapes [44]. 8.4.1.2  POLYSACCHARIDE PROCEDURE Mainly in the Polysaccharide technique, Ag NPs are assembled utilizing water and polysaccharides as closure agents, or in certain instances, polysaccharides act as diminishing and restricting agents. In a softly heated environment, to illustrate, starch NPs were synthesized using starch as a capping product and D-glucose as the reduction agent. Furthermore, the binding relationship between the essential and the Ag NPs is weak and may be undone at extremely high temperatures, allowing dissociation of the NMs. In general, starch-protected NMs may be easily incorporated into pharmacological and biological systems [44].

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8.4.1.3  BIOLOGICAL PROCEDURE In the production of Ag NPs, organism extracts can function as decreasing and restricting agents. The elimination of Ag+ ions by a mixture of macromolecules contained in this extract, including such enzymes, polysaccharides, vitamins, and amino acids, creates a safe yet chemically complicated microenvironment [44]. 8.4.1.4  POLYOXOMETALATES PROCEDURE Polyoxometalates, or POMs, can be used to manufacture Ag NPs so they are water-soluble and may undergo a slow multi-electron oxidation process without altering their framework [44]. 8.4.1.5 IRRADIATION Numerous irradiation methods were used to produce Ag NPs successfully. Laser irradiation of an aqueous solution of silver salt and surfactant, for example, can produce Ag NPs with a very healthy form and particle size. There is no need for a reduction agent in this approach [44]. 8.4.2  WASTEWATER RECOVERY PROCESS BY BIONANOMATERIALS Industrialization and the ever-growing population adversely affect clean drinking water resources [18]. Moreover, hazardous chemicals such as dyes, heavy metals, and fluorides severely contaminate water reservoirs, making it global. It has been reported that the groundwater resources of almost 25 countries have already been contaminated with increased concentrations of fluorides [31]. To control this global issue, various treatment techniques employing different materials such as bionanomaterials have continuously been practiced. The bionanomaterials showing such peculiar characteristics as remarkable efficiency, enhanced reactivity, non-toxicity, and renewability, exhibit a range of potential applications such as photocatalysis, nanofiltration (NF), an alternative source of renewable energy. Hence, such treatment techniques are appropriate and sustainable to provide eco-friendly solutions

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making safe drinking water available from contaminated water resources. For example, a bionanomaterial based scaffold consisting of Ag-NPs has been reported to act as a superabsorbent showing high capability to remove contaminants like fluorides and dyes from water [31]. 8.4.3 PHOTOCATALYSIS The incompetencies of conventional techniques regarding sustainable development have urged to design of advanced and the most effective treatment technique, Advanced Oxidation Processes (AOP), involving NT-based wastewater treatment strategies. The main objective of the AOP is to rapidly degrade and mineralize pollutants of organic nature, pesticides, toxicants, pathogens, and disinfectants through in-situ production of free radicals or charged particles exhibiting environmental remediation [27]. Photocatalysis deals with the catalytic degradation of pollutants, for example, pharmaceuticals, dyes, phenols, endocrine disruptors (EDs), and insecticides, leading to the successful removal of the pollutants from wastewater. Currently, bionanomaterial-based photocatalysis such as photocatalytic oxidation has come out as a powerful recovery technique employing sunlight or artificial light as a source of energy. The bionanocatalysts have significantly been used to render significant characteristics such as enhanced efficiency, nontoxicity, reusability, cost-efficacy, high reactivity, lack of hazardous by-products, and their effectiveness against a wide range of pollutants [27]. The photocatalytic oxidation process primarily relies on the generation of hydroxyl radicals which are highly reactive and capable of converting toxicants into non-toxic end products like CO2 and H2O. The development of efficient semiconductor-based photocatalysts which may function either in sunlight or UV is a drastic challenge. They convert solar energy into electricity, fuel, or active radicals for the environmental remediation generating electron-hole pairs. One of the widely used metal oxide photocatalysts is TiO2 which shows non-corrosive behavior and the set mentioned above of characteristics. It effectively degrades pollutants photo catalytically, lowering their concentration up to 10% compared to their initial concentration in just two hours. Since weak crystallinity of TiO2 limits its photocatalytic activity (PCA), it paves the way towards the discovery of more efficient photocatalysts and even treatment techniques with great remediation potential [27].

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8.4.4  WATER FILTRATION USING BIONANOFILTERS Water is an essential material for the economic growth of most countries as it is one of the essential components for agriculture and the livelihood of communities worldwide. Since water pollution has been increasing, the availability of fresh water for daily life continues to decline, and wastewater treatment has been one of the significant issues. Bionanotechnology can be used as a crucial solution for providing purified water for daily use, manipulating bionanomaterials such as bionanofilters, nanotubes, and nanocapillary arrays [42]. Bionanofilteration using bionanofilters can be used for the removal of the materials such as sediment, trace elements, chemical effluents, organic pollutants, oils, pesticides, and pathogens from water to purify it. Moreover, it may soften the hard water eliminating multivalent and divalent ions. Bionanofilters are advantageous compared to conventional ones because they are more efficient, require less pressure to filter water, and retain a large surface area [25]. Membrane filtration, considered the technology of choice, has been a broadly accepted and preferable treatment technique employing a physical barrier, that is, a thin semipermeable layer, to remove the unwanted entities effectively. Owing to their peculiar chemical and physical characteristics, it has found widespread applicability worldwide over three decades, successfully separating various pollutants to purify water. Moreover, it has been equipped with simplicity, high efficiency, without demanding additives and chemicals, easy up-gradation, fast separation process, and flexibility to cope up with other advanced treatment techniques [27]. 8.4.5  GENERATING RENEWABLE ENERGY Owing to the increase in world population, natural fossil fuels have been consumed rapidly, which leads to their reduction and releases many harmful pollutants into the environment. Because of such consequences, the whole world is looking for an alternative clean energy source, namely renewable energy. Bionanotechnology may provide a pollution-free, more efficient, and cost-effective energy-generating platform. Photoactive materials have efficiently been used to convert light energy into a form of consumable electrical energy [42].

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8.4.6  LIMITS OF GREEN BIONANOTECHNOLOGY Green bionanotechnology is a developing field encountering its limitations and challenges that must be addressed. The main challenges include policies to regulate synthetic procedures, economic, and Technical limits, analysis of their active life-cycle, scaling-up techniques, and toxicity monitoring. These factors act as the backbone for sustainable green development. Although green bionanotechnology is an eco-friendly approach that results in pollutants removal, the cost and risks of bionanomaterials limit their applications. Since it has been undergoing significant development, sustainability has preferably been focused on its applications. However, in the viewpoint of their commercial applications, research is still underway [27]. 8.5  INTELLIGENT BIONANOMATERIALS Depending on their ambient circumstances, bionanomaterials that serve as “nanomachines” self-adapt to maximize the probability of attaining the intended aim. These bionanomaterials are considered as the “intelligent” bionanomaterials. Despite its rising popularity, the research and use of intelligent bionanomaterials in production is somewhat sluggish and still at an early stage. There were several fascinating exploratory research is done on the subject of extraordinary things bionanomaterials throughout the decades, many of which provide solutions that appear new and revolutionary [8]. 8.5.1  SELF-HEALING BIONANOMATERIALS FOR ENVIRONMENTAL APPLICATIONS In actuality, surface molecules can be progressively destroyed or eliminated by mechanical stress, or they can lose their intended purpose when subjected to sun irradiation and highly reactive substances in water and air. Therefore, it is undeniable that self-healing bionanomaterials will have several uses, particularly in applications that require long-term dependability in inaccessible locations. The extraordinary self-healing powers of living creatures to restore health and developing capacity, including rebuilding tissue structures and damaged bones, are demonstrated. This has been a significant source of motivation for researchers and bionanotechnology developers to develop artificial bionanomaterials that promote tissue repair. The notion of gradual but steady self-healing has gained popularity in the last decade,

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with robust environmental remediation. Several experimental studies have been conducted to equip traditional environmental considerations with selfhealing bionanomaterials. Still, they are not restricted to purifying water [16, 30], water, and oil segregation, pollutant absorption, [13], and surface antifouling [32]. Self-healing compounds are classified into two kinds based on the source of the self-healing agent: extrinsic and intrinsic self-healing substances. Extrinsic self-healing substances have healing ingredients incorporated in the host matrix as micro- or nano-capsules or vascular systems. When there is injury, the capsule or vascular tissue ruptures, allowing the healing agent to be released and the recovery process to start. In comparison, intrinsic self-healing minerals do not need the matrix’s extra mending agents and can operate as healing agents independently. As a result, intrinsic self-healing substances are more flexible and widely employed in engineering remediation than external self-healing material [8]. Mechanical cracking and loss of surface function are examples of material damage. The latter might be caused by the loss of surface-based functional components or by surface pollution. As a result, it has been divided into three sections: (i) self-healing from physical cracks; (ii) self-restoration of manufactured functional components; and (iii) self-cleaning of polluted surfaces [22]. 8.5.1.1  SELF-HEALING OF PHYSICAL CRACKS The use of self-healing from physiological injuries to ecological change is a novel field. The porous membranes produced by micelles triblock copolymer have shown their applicability in water filtering. The self-healing and residual chlorine hydrogels have also been synthesized utilizing products obtained as a primary building block and Fe3+ ions as the physical crosslinks [22]. The selfhealing screenings membrane has been fabricated, introducing an extrinsic microcapsule with a polyurethane (PU) shell and an isophorone diisocyanate code into the polyethersulfone (PES) membrane [30]. When a microcapsule ruptures, the isocyanate healing process is released and distributed to the fracture site. It reacts with the surrounding water to create a PU plug to cover the injured spot. Correspondingly, water flow and membrane particle rejection returned to 103% and 90% of their previous levels after cure. Nonetheless, extrinsic self-healing agents with microcapsules create a lot of healing cycles in particular regions. Kim et al. [30] created a PES membrane for water purification with holes filled with the hydrogel. The

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swelling action of the hydrogel filling the pores at the site of injury and the strong H-bonding and molecules interfusion of the hydrogel polymeric chains contribute to the membrane’s self-healing capacity. Consequently, particle rejections by the membranes are up to 99% after self-healing, contrasted to as low as 30% after injury. Given the rapid mobility of the polyelectrolytes, as well as their electrostatic interaction and inverse h-bonding, damage to the architecture and antifouling function of the film may be healed fast [8]. 8.5.1.2  SELF-RESTORATION OF FABRICATED FUNCTIONAL COMPONENTS Surface function, particularly surface wet, is often accomplished by depositing an ultrahigh, single molecular-based functional layer on the substrate material, which allows the surface function to degrade readily even in the absence of major structural breaking. Self-healing from surface wetness, in particular, is primarily dependent on energy-free surface migration between hydrophilic or hydrophobic polymerization. In practice, hydrophobic surface compounds can be dissolved or destroyed by mechanical force, complete electric or oxidative agents. With the release of hydrophobic molecules from the surface, surface area rises in the air, attracting low surface light energy from below or near the injured location to the outermost layer to restore their original hydrophilic nature [14]. This method can also be caused by the fact that air is a water-insoluble type of media. Low surface different concentration levels prefer to make contact with air as per the solubility principle. Conversely, hydrophilic molecules in water tend to migrate to the contact to replenish molecules lost there and restore the wettability of the water’s surface. Sun et al. described a self-healing hydrophobic surface consisting of fluoroalkyl silane vacuum distillation on an acquired polyelectrolyte layer in 2010 as proof of this self-healing notion of surface wetness. When gone, the thermoplastic barrier can be recovered at ambient temperature by selfmigration from the fluoroalkyl chain to the outermost layer of the bottom polyelectrolyte layer to reduce the interface’s cheap electricity [8]. Wang et al. [47] extended this superhydrophobic self-healing process to photothermal membranes in 2019 and is the first study about the use of plastics as photodynamic nanomaterials for solar power-driven transpiration and water treatment. According to this study, solar radiation intensity can expedite the migration of fluoroalkyl molecules to the layer’s outer surface, and self-healing can be cycled several times [8].

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8.5.1.3  SELF-CLEANING OF CONTAMINATED SURFACES During usage, the surface of understanding the effect is unavoidably clogged and absorbed by pollutants such as dirt, germs, oils, and proteins, resulting in a rough structure and firm performance. As a result, materials with selfcleaning surfaces are highly desirable in a wide range of environmental operations. They are necessary before one can create an optimal antifouling surface if one exists. There are three types of self-cleaning surfaces: (1) super hydrophilic, (2) superhydrophobicity, and (3) photocatalysis. The water permeability on a highly hydrophilic surface can be as low as 0°, allowing water to spread in the thin layer film of water between dirt particles and its lower part, causing fragments to separate from the surface. Superhydrophobic surfaces have a very high water contact angle and a slight water slide slope in the air, relying on particle rotation to help remove impurities [8]. Self-cleaning ionic liquids are well researched. Several self-cleaning materials with superhydrophobic surfaces and low adhesion qualities have been documented thus far. Some of these materials are employed in rightwing, anti-icing, resistance to corrosion, concentrated solar evaporation, light energy expenditure by solar cells, and robust reducing energy harvesting. Pollutants are wiped away from photocatalytic self-cleaning surfaces by the synergistic effects of photocatalysis and the photo-induced phenomenon of super hydrophilicity [8]. Generally, self-healing materials reduce the need for considering other factors such as monitoring, care, and repair, potentially prolonging their lifetime. The farm is still in its infancy, and the use of self-healing materials has only enabled the use of water purification, oil-water separation, and coating surfaces [8]. 8.5.2  EMERGING NANOFIBROUS-TYPE AIR FILTERS FOR PM2.5 REMOVAL The earth’s atmosphere has a varied and complex chemical composition because of its different sources, such as suspended dust, high temp zinc anode, atmospheric reactions, and numerous combustion process activities, including vehicle emissions, coal burning, and industrial combustion products. PM2.5 and PM10 particles generally have aerodynamic dimensions of less than 2.5 m and 10 m, respectively. Because of its capacity to penetrate deep into lung tissues and organs, PM2.5 offers even more severe health

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risks to humans than PM10, making it a well-known air pollutant across the world [8, 15]. The central air conditioning system is most efficient at filtering PM and creating fresh air on cloudy days. However, this technique is only accessible in new commercial buildings, takes a lot of energy for bulk water pumps, and could be utilized for self-protection in outdoor situations. As a result, a mechanically ventilated air filter is an ideal green method of obtaining fresh air because it requires no further energy input and is suited for interior and exterior application settings. Furthermore, rising public health awareness has prompted the implementation of practical and cost-effective protective gear to remove PM2.5 at the household and national levels worldwide [8, 53]. Perforated membranes created by creating holes on dense surfaces and fibrous micro-membranes comprised of layered fibers with a size in the micrometer range are traditional air filters for eliminating PM particles. Nevertheless, these methods are ineffective for PM2.5 removal and result in an unpleasant decrease in air pressure around the membrane. In comparison to the conventional spongy unpaid leave for air, nanofiber moisture air filters with fiber diameters ranging from 10 to 1,000 nm offer a variety of intriguing properties such as high effective surface area, greater porosity, interrelated layered surface, low resistance to the airway, extra active site web, accessible here from, and high mechanical properties [15]. Because of different ions and water vapors in the atmosphere, PM particulates tend to be highly polar. With this insight, high polarity nanofiber membranes have been developed to achieve strong adhesion contacts among PM particles and NPs. As PM particles are caught, the directly arriving particles adhere and mix with the preexisting PM along with the fiber, resulting in a stable spherical aggregation surrounding the nanofiber. This effect is advantageous for PM removal because it permits PM particles to increase their surface area with nanostructures closely bound to it [8]. Thermal management to nanofibers exhaust system gloves was reported for the first time for individual current warming reasons. Because of its openness to intermediary thermal light and electron-altered NCs on the polyethylene (PE) substrate, nanopolyethylene was chosen as the supporting substrate in this design [50]. Self-cleaning and antistatic capabilities would extend the filter’s lifetime, as that would better heat control for greater comfort while in use. The mixture of harvesting energy and power production, including piezoelectric or triboelectric substances, enables specific novel applications, such as air filters, powered sensing devices, or led lights. The mechanism of interaction among PM particles and NPs has gotten little study, leaving it primarily unknown. As a result, introductory, and comprehensive study in

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this subject is necessary. It would be logically developed more efficient air filters in the future with a better knowledge of the interaction processes [8]. 8.6  CHALLENGES AND FUTURE PERSPECTIVES Bionanotechnology has become more and more well-liked over time. It's possible that bionanotechnology has a highly promising future. Future uses of bionanotechnology are anticipated to be numerous. Excellently biocompatible, bionanomaterials have a wide range of uses in the construction, electronics, coatings, agriculture, medical, water treatment, textiles, renewable energy, and environmental safety industries. In order to better serve mankind, research on self-healing bionanomaterials has also been expanded to include the repair of mechanical damage and clean environmental cleanup [8]. The usage of biological materials with conjugations of NMs is very important for the development of bionanotechnology applications. It may employ biological systems in a number of ways to advance bionanotechnology. Bionanotechnology is now used in a number of industries, including energy generation, electronics, biomaterials, and medicine. These industries are gaining from the new tools and technologies that bionanotechnology is producing. Frequent use of bionanotechnology also poses a severe threat to the environment and human health [8]. The threats include: • The human body has mainly been affected by various NMs, which pose a severe threat to the human body, devastating their health; • The world economy has been affected by the potential use of NT; • Matrix released with NMs is very dangerous; • Workplaces and environments with higher NMs concentrations are hazardous; • Their waste material is as much dangerous as it can cause diseases such as cancer. However, the field of bionanotechnology has been facing the following challenges: • The main challenge of bionanotechnology is to synthesize NPs that cannot harm humans, natural flora, and the ecosystem; • Another challenge is that competent authorities must access the developed bioNM safety issues, such as bionanomaterial-coated face masks and hand sanitizers.

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8.7 SUMMARY Bionanotechnology deals with using biological systems in conjunction with NT leading to the discrete, programmable nanoscale materials with novel characteristics and functionality. Owing to its special applications, the interdisciplinary field has attracted the keen interest of researchers. Assurance of reliable access to clean drinking water and pollution-free air has been the most significant global issue. It would practice innovative treatment technologies and resource management efficiently and vital legislation that makes them incredibly challenging to overcome such issues. Bionanotechnology has been offering promising solutions for a clean and green ecosystem, including wastewater reuse, water treatment, and availability of clean air. Industrial bionanotechnology leverages a biology-based approach to yield NMs employing biological resources to lessen the production of lethal wastes, which is a crucial advantage of NM biosynthesis. Various techniques have been designed to open a new era of the bionanomaterials with defined dimensions and complexity employing biomolecular self-assembly features regulated by molecular-based interactions between peptides, nucleotides, lipids, small ligands, and proteins. Hence, it has been concluded that: • Bionanotechnology may provide a way out of energy crises; • It may provide NMs that might clean polluted soil, water, and the ecosystem; • It may revolutionize the electronics sector in terms of engineering, designing, and creating user-friendly nanodevices. This innovation is just the beginning to serve humanity, and it still needs to go a long way. Many diseases that have no cure yet may be treated by bionanotechnology shortly. Apart from its benefits, it has some drawbacks as well. This has been a challenge for researchers and scientists. Since promising applications have accompanied it, the advances in this field of research would continue along with authentic testing to assure public safety. If all goes well in the following years, bionanomaterials will become an inevitable part of our daily life. ACKNOWLEDGMENT We pay special thanks to Mr. Kashif Javed, Department of Information Technology, Masood Textile Mills Faisalabad, Punjab, Pakistan, for his contribution and for providing all the technical assistance.

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KEYWORDS • • • • • • •

advanced oxidation processes framework nucleic acid nanometer polyethersulfone polyethylene single-stranded DNA single-stranded nucleic acids

REFERENCES 1. Abdel-Aziz, S. M., Prasad, R., Hamed, A. A., & Abdelraof, M., (2018). Fungal Nanobionics: Principles and Applications (pp. 61–87). Singapore: Springer Nature Pte Ltd. 2. An, X., Zhu, A., Luo, H., Ke, H., Chen, H., & Zhao, Y., (2016). Rational design of multi-stimuli-responsive nanoparticles for precise cancer therapy. ACS Nano, 10(6), 5947–5958. 3. Andersen, E. S., Dong, M., Nielsen, M. M., Jahn, K., Subramani, R., Mamdouh, W., Golas, M. M., et al., (2009). Self-assembly of a nanoscale DNA box with a controllable lid. Nature, 459, 73–76. 4. Barabadi, H., Honary, S., Mohammadi, M. A., Ahmadpour, E., Rahimi, M. T., & Alizadeh, A., (2017). Green chemical synthesis of gold nanoparticles by using Penicillium aculeatum and their scolicidal activity against hydatid cyst protoscolices of echinococcus granulosus. Environmental Science and Pollution Research, 24(6), 5800–5810. 5. Bhattacharya, D., Behera, B., Sahu, S. K., Ananthakrishnan, R., Maiti, T. K., & Pramanik, P., (2016). Design of dual stimuli-responsive polymer-modified magnetic nanoparticles for targeted anti-cancer drug delivery and enhanced MR imaging. New Journal of Chemistry, 40(1), 545–557. 6. Bi, S., Yue, S., Wu, Q., & Ye, J., (2016). Triggered and catalyzed self-assembly of hyperbranched DNA structures for logic operations and homogeneous CRET biosensing of microRNA. Chemical Communications, 52(31), 5455–5458. 7. Blum, A. P., Kammeyer, J. K., Rush, A. M., Callmann, C. E., Hahn, M. E., & Gianneschi, N. C., (2015). Stimuli-responsive nanomaterials for biomedical applications. Journal of the American Chemical Society, 137(6), 2140–2154. 8. Chang, J., Zhang, L., & Wang, P., (2018). Intelligent environmental nanomaterials. Environmental Science: Nano, 5(4), 811–836. 9. Chen, Y., Sun, W., Yang, C., & Zhu, Z., (2020). Scaling up DNA self-assembly. ACS Applied Bio Materials, 3(5), 2805–2815. 10. Chueng, S. T. D., Yang, L., Zhang, Y., & Lee, K. B., (2016). Multidimensional nanomaterials for the control of stem cell fate. Nano-Convergence, 3(1), 1–15.

238

Sustainable Nanomaterials for Biosystems Engineering

11. Crucho, C. I., (2015). Stimuli-responsive polymeric nanoparticles for nanomedicine. ChemMedChem, 10(1), 24–38. 12. Dai, Z., Leung, H. M., & Lo, P. K., (2017). Stimuli-responsive self-assembled DNA nanomaterials for biomedical applications. Small, 13(7), 1–16. 13. Fang, W., Liu, L., Li, T., Dang, Z., Qiao, C., Xu, J., & Wang, Y., (2016). Electrospun N-substituted polyurethane membranes with self-healing ability for self-cleaning and oil/water separation. Chemistry of European Journal, 22(3), 878–883. 14. Fujiwara, M., & Imura, T., (2015). Photo induced membrane separation for water purification and desalination using azobenzene modified anodized alumina membranes. ACS Nano, 9(6), 5705–5712. 15. Garcia-Mayagoitia, S., Perez-Hernandez, H., Medina-Perez, G., Campos-Montiel, R. G., & Fernandez-Luqueño, F., (2020). Bio-nanomaterials in the air pollution treatment. In: Nanomaterials for Air Remediation, Micro, and Nano-Technologies (pp. 227–248). Elsevier Inc. 16. Getachew, B. A., Kim, S. R., & Kim, J. H., (2017). Self-healing hydrogel pore-filled water filtration membranes. Environmental Science & Technology, 51(2), 905–913. 17. Gong, X., Huang, D., Liu, Y., Peng, Z., Zeng, G., Xu, P., & Wan, J., (2018). Remediation of contaminated soils by biotechnology with nanomaterials: Bio-behavior, applications, and perspectives. Critical Reviews in Biotechnology, 38(3), 455–468. 18. Gonzalez, M. A., Trócoli, R., Pavlovic, I., Barriga, C., & La Mantia, F., (2016). Capturing Cd (II) and Pb (II) from contaminated water sources by electro-deposition on hydrotalcite-like compounds. Physical Chemistry Chemical Physics, 18(3), 1838–1845. 19. Gou, Y., Yang, S., Cheng, Y., Song, Y., Qiao, P., Li, P., & Ma, J., (2019). Enhanced anoxic biodegradation of polycyclic aromatic hydrocarbons (PAHs) in aged soil pretreated by hydrogen peroxide. Chemical Engineering Journal, 356, 524–533. 20. Gulzar, A., Gai, S., Yang, P., Li, C., Ansari, M. B., & Lin, J., (2015). Stimuli-responsive drug delivery application of polymer and silica in biomedicine. Journal of Materials Chemistry B, 3(44), 8599–8622. 21. Guo, P., (2010). The emerging field of RNA nanotechnology. Nature Nanotechnology, 5(12), 833–842. 22. Huang, S., Yang, L., Liu, M., Phua, S. L., Yee, W. A., & Liu, W., (2013). Complexes of polydopamine-modified clay and ferric ions as the framework for pollutant-absorbing supramolecular hydrogels. Langmuir, 29(4), 1238–1244. 23. Jiang, T., Mo, R., Bellotti, A., Zhou, J., & Gu, Z., (2014). Gel-liposome-mediated co-delivery of anticancer membrane-associated proteins and small-molecule drugs for enhanced therapeutic efficacy. Advanced Functional Materials, 24(16), 2295–2304. 24. Kafi, M. A., Cho, H. Y., & Choi, J. W., (2016). Engineered peptide-based nanobiomaterials for electrochemical cell chip. Nano-Convergence, 3(1), 1–12. 25. Karimi, H., Rahimpour, A., & Shirzad, K. M. R., (2016). Pesticides removal from water-using modified piperazine-based nanofiltration (NF) Membranes. Desalination and Water Treatment, 57(52), 24844–24854. 26. Kaur, M., Mehta, A., Bhardwaj, K. K., & Gupta, R., (2020). Bionanomaterials from agricultural wastes. In: Ahmed, S., & Ali, W., (eds.), Green Nanomaterials: Advanced Structured Materials (Vol. 126, pp. 243–260). Singapore: Springer Nature Pte Ltd. 27. Khan, S. H., (2020). Green nanotechnology for the environment and sustainable development. In: Naushad, M., & Lichtfouse, E., (eds.), Green Materials for Wastewater Treatment, Environmental Chemistry for a Sustainable World (Vol. 38, pp. 13–46). Springer, Cham.

Advanced Bionanomaterials for Environmental Clean 239 28. Kharat, M. G., Murthy, S., & Kamble, S. J., (2017). Environmental applications of nanotechnology: A review. ADBU Journal of Engineering Technology, 6(3), 1–11. 29. Kim, H., Park, Y., Kim, J., Jeong, J., Han, S., Lee, J. S., & Lee, J. B., (2016). Nucleic acid engineering: RNA following the trail of DNA. ACS Combinatorial Science, 18(2), 87–99. 30. Kim, S. R., Getachew, B. A., Park, S. J., Kwon, O. S., Ryu, W. H., & Taylor, A. D., (2016). Toward microcapsule-embedded self-healing membranes. Environmental Science & Technology Letters, 3(5), 216–221. 31. Kumar, A., Paul, P., & Nataraj, S. K., (2017). Bionanomaterial scaffolds for effective removal of fluoride, chromium, and dye. ACS Sustainable Chemistry & Engineering, 5(1), 895–903. 32. Li, L., Yan, B., Yang, J., Huang, W., Chen, L., & Zeng, H., (2017). Injectable selfhealing hydrogel with antimicrobial and antifouling properties. ACS Applied Materials & Interfaces, 9(11), 9221–9225. 33. Liao, R., Yang, P., Wu, W., Luo, D., & Yang, D., (2018). A DNA tracer system for hydrological environment investigations. Environmental Science & Technology, 52(4), 1695–1703. 34. Ma, G., Wang, Y., Bao, X., Hu, Y., & Liu, Y., (2015). Nitrogen pollution characteristics and source analysis using the stable isotope tracing method in Ashi River, northeast China. Environmental Earth Sciences, 73(8), 4831–4839. 35. Moon, R. J., Martini, A., Nairn, J., Simonsen, J., & Youngblood, J., (2011). Cellulose nanomaterials review: Structure, properties, and nanocomposites. Chemical Society Reviews, 40(7), 3941–3994. 36. Mora, C. A., Schärer, H. J., Oberhänsli, T., Ludwig, M., Stettler, R., & Stoessel, P. R., (2016). Ultrasensitive quantification of pesticide contamination and drift using silica particles with encapsulated DNA. Environmental Science & Technology Letters, 3(1), 19–23. 37. Morganti, P., (2015). Bionanotechnology & bioeconomy for a greener development. Journal of Applied Cosmetology, 33(1, 2), 51–65. 38. Nagamune, T., (2017). Biomolecular engineering for nanobio/bionanotechnology. NanoConvergence, 4(1), 1–56. 39. Ovais, M., Raza, A., Naz, S., Islam, N. U., Khalil, A. T., & Ali, S., (2017). Current state and prospects of the phytosynthesized colloidal gold nanoparticles and their applications in cancer theranostics. Applied Microbiology and Biotechnology, 101(9), 3551–3565. 40. Pinheiro, A. V., Han, D., Shih, W. M., & Yan, H., (2011). Challenges and opportunities for structural DNA nanotechnology. Nature Nanotechnology, 6(12), 763–772. 41. Pinto, A., Chen, S. X., & Zhang, D. Y., (2018). Simultaneous and stoichiometric purification of hundreds of oligonucleotides. Nature Communications, 9(1), 1–9. 42. Rohela, G. K., Srinivasulu, Y., & Rathore, M. S., (2019). A review paper on recent trends in bio-nanotechnology: Implications and potentials. Nanoscience & NanotechnologyAsia, 9(1), 12–20. 43. Rouge, J. L., Sita, T. L., Hao, L., Kouri, F. M., Briley, W. E., Stegh, A. H., & Mirkin, C. A., (2015). Ribozyme – spherical nucleic acids. Journal of the American Chemical Society, 137(33), 10528–10531. 44. Sahayaraj, K., & Rajesh, S., (2011). Bionanoparticles: Synthesis and antimicrobial applications. Science against Microbial Pathogens: Communicating Current Research and Technological Advances, 23, 228–244.

240

Sustainable Nanomaterials for Biosystems Engineering

45. Sun, H., & Zu, Y., (2015). A highlight of recent advances in aptamer technology and its application. Molecules, 20(7), 11959–11980. 46. Tang, H., Kobayashi, H., Niidome, Y., Mori, T., Katayama, Y., & Niidome, T., (2013). CW/pulsed NIR irradiation of gold nanorods: Effect on transdermal protein delivery mediated by photothermal ablation. Journal of Controlled Release, 171(2), 178–183. 47. Wang, L., Gong, C., Yuan, X., & Wei, G., (2019). Controlling the self-assembly of biomolecules into functional nanomaterials through internal interactions and external stimulations: A review. Nanomaterials, 9(2), 285–312. 48. Wang, L., Sun, Y., Li, Z., Wu, A., & Wei, G., (2016). Bottom-up synthesis and sensor applications of biomimetic nanostructures. Materials, 9(1), 53–81. 49. Xie, N., Huang, J., Yang, X., Yang, Y., Quan, K., & Wang, H., (2016). A DNA tetrahedronbased molecular beacon for tumor-related mRNA detection in living cells. Chemical Communications, 52(11), 2346–2349. 50. Yang, A., Cai, L., Zhang, R., Wang, J., Hsu, P. C., & Wang, H., (2017). Thermal management in nanofiber-based face mask. Nano-Letters, 17(6), 3506–3510. 51. Zadegan, R. M., Jepsen, M. D., Hildebrandt, L. L., Birkedal, V., & Kjems, J., (2015). Construction of a fuzzy and Boolean logic gates based on DNA. Small, 11(15), 1811–1817. 52. Zhang, T., Lowry, G. V., Capiro, N. L., Chen, J., & Chen, W., (2019). In-situ remediation of subsurface contamination: Opportunities and challenges for nanotechnology and advanced materials. Environmental Science: Nano, 6(5), 1283–1302. 53. Zhao, X., Li, Y., Hua, T., Jiang, P., Yin, X., Yu, J., & Ding, B., (2017). Low-resistance dual-purpose air filter releasing negative ions and effectively capturing PM2.5. ACS Applied Materials and Interfaces, 9(13), 12054–12063.

CHAPTER 9

ADVANCED BIONANOMATERIALS FOR HEAVY METALS AND RADIOACTIVE METALS RECOVERY PROCESSES GAYATHRI VIJAYAKUMAR, SURYA ARCOT VENKATESAN, SUPARNA PERUMAL, and SHIVANI KUMAR

ABSTRACT Nanotechnology is a versatile science that has its applications in nearly all fields of today’s science. Developing feasible and environmentally friendly Nanomaterials (NMs) is of great importance because NMs produced from inorganic sources have potentially adverse impacts on the ecosystem, for example, inhalation-related complications in animals and humans, potential contamination of surface and groundwater, so it is essential to develop biocompatible and biodegradable NMs which will coexist with the ecosystem. This chapter advanced bionanomaterials for solids, heavy metal, and radioactive metal recovery process mainly focuses on bionanomaterials, types of bionanomaterials, i.e., bionanomaterials based on proteins (Gelatin, collagen), polysaccharides (alginate, chitosan, cellulose, lignin), lipids (liposomes), nucleic acids, carbon (carbon nanotubes (CNTs), carbon NPs), methods of preparation of bionanomaterials which includes two-step procedure based on emulsification, one-step procedure, preparation by the drying process, electrospraying, spray drying, supercritical drying. Secondly, it draws about the nano-adsorbents for heavy metal recovery, nanocomposites (NCs) for heavy metal recovery, biosorption, solid recovery, and radioactive metal recovery. Finally, it ends by discussing the prospects of this topic. Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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9.1 INTRODUCTION Nanotechnology is the production and application of particles whose size is less than 1,000 nm. Reduction in particle size from large surface area to volume ratio to a nanoscale offers much enhancement to its physical, mechanical, optical, and electrical properties. Advancement NM production increases its applications too [80]. Developments of NPs are sometimes done from natural or biological sources like proteins, polysaccharides, nucleic acids, and lipids rather than using chemically or inorganically (metals and their oxides, QDs) synthesized NPs. Currently, interest is shown in these biological NPs because of their advantage in abundant availability, ecofriendly, and non-immunogenic nature [68]. One of the main applications of bionanomaterials is recovering heavy metals as water treatment [55]. Water bodies like rivers, lakes, and oceans act as dump yards for many factory effluents, waste materials, and many more. Therefore, this water consists of both organic and inorganic substances. Inorganic substance comprises of metal ions like arsenic (As (III)), cadmium (Cd (II)), copper (Cu (II)), lead (Pb (II)), zinc (Zn (II)), mercury (Hg), chromium (Cr (III)) and so on. Strategies like ion exchange, osmosis, oxidation, membrane filtration are costlier, have corrosion problems, and are not economically feasible. On the other hand, usage of bio NPs for adsorption of these metal ions is easier, cost-effective, and has high efficiency. This chapter gives information on bionanomaterials, their types (protein, polysaccharides, lipids, nucleic acids, and carbon-based), preparation, and application in the recovery of heavy metals and radioactive metals, and with their future aspects. 9.2 BIONANOMATERIALS Bionanomaterials are made of biological molecules either wholly or partially. These biological molecules can be polysaccharides, proteins, lipids, nucleic acids, antibodies, viruses, and cells. The materials produced from the biomolecules mentioned above results in molecular structures having a nanoscale dimension. These materials are known for their potential applications as biosensors, nanofibers, fixatives, and potent role players in bioremediation [34]. A material having at least one of its dimensions in nanoscale is said to be a NM. According to international standardization, a nanometer represents 1 billionth of a meter, i.e., 0.000000001 m or 10–9 meters. NMs are in a size range of 1–1,000 nm and commonly have a 1–100 nm [9]. Subsequently,

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bio-nanomaterials are finding their applications in various fields, including agriculture, health care, removal of pollutants, etc. Bio-nanomaterials are of increasing interest in many fields. Its consumer products will soon find themselves a place in the environment. So, in the future, the investigation about the environmental risk associated with bio-nanostructures is also of great importance. 9.3  TYPES OF BIONANOMATERIALS Bionanomaterials can be produced from numerous biological sources and molecules (Figure 9.1). In this chapter, we are mainly concentrating on the bionanomaterials produced from proteins, polysaccharides, lipids, nucleic acids, and carbon from biosources.

FIGURE 9.1  Types of bionanomaterials: (A) protein-based nanoparticle; (B) liposome; (C) chitosan nanoparticle; (D) carbon nanotubes.

9.3.1 PROTEIN Extremely valuable for producing novel bionanomaterials are peptides and proteins. Peptides and proteins have phenomenal specificity towards a target. These organic compounds will uphold a more significant primary adjustment, including electric/magnetic fields, temperature, ionic strength, and pH. 9.3.1.1 COLLAGEN Recently, the use of collagen (a green polymer) based on biodegradable films in the food industry is gaining importance [54]. Apart from their potential

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applications in the food industry, collagen is also used in heavy metal recovery, tannins immobilized in collagen is used for the potential recovery of heavy metals from industrial wastewater, the bio adsorbent showed great potential in the removal of heavy metals like copper chromium and lead [43]. The properties of the incorporated adsorbent were described by Fourier transform infrared spectroscopy, X-ray diffraction (XRD), and temperature investigation methods. Hydrogels of collagen are substances that can ingest and hold immense measures of water in their design without being broken up [50]. 9.3.1.2 GELATIN Recently, the use of collagen (a green polymer) based on biodegradable films in the food industry is gaining importance [54]. Fish gelatin (FG), a macromolecule sustainable, biodegradable, and processable, offers energizing prospects in bio packaging. Be that as it may, but there are specific issues with utilizing FG, which are low mechanical strength, and easily prone to damages caused by water. The FG film application measure requires much investigation, mainly on the actual perspectives to suit the bio package application [35]. Based on recent scientific, literary works, gelatin can be used to make Nanoporous nanogels adsorbents to remove heavy metals like Cu2+ and Ni2+ [56]. 9.3.2 POLYSACCHARIDES The allure over bio-polysaccharides has seen a potential surge in recent times due to its abundance and insurmountable properties like biodegradability, biocompatibility, and the capability to undergo feasible and facile modifications. Two primary sources of polysaccharides are marine organisms (macroalgae and crustaceans) and terrestrial plants. The polysaccharide which is widely used for the production of NMs includes chitin, chitosan, alginate, starch, cellulose, dextran, Lignin, and carrageenan [49]. 9.3.2.1  FROM MARINE SOURCES 9.3.2.1.1 Alginate Alginate is obtained from the cell wall of Phaeophyceae as an integral component of diverse polysaccharides present in these organisms, including

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laminarin, cellulose, and sulfated hexouronoxylo fucans, alginate, and fucoidan. Despite the presence of different polysaccharides in the cell wall, the abundance of alginate is about 45% of the dry weight of these macroalgae. The presence of alginate in high amounts in these cell walls is responsible for its extensive flexibility, mechanical, and structural capabilities [26]. The chemical structure of alginate found in the Phaeophyceae cell wall is analogous to pectin found in terrestrial plants. Structurally it is emphasized as an anionic polymer made up of two subunits, (1→4) linked β-D-mannuronic acid (M) and α-L-guluronic acid (G). The relative abundance of each monomer might vary in different varieties of alginates [4]. NMs in environmental remediation and pollutant adsorption are of great value due to their vast surface area and more excellent absorptivity than available materials for the applications mentioned above. Application of alginate in environmental prevention and remediation processes is based on the fact that it houses a viable set of functional groups which could capture cationic or metallic ions by performing ion exchange between cross-linking and pollutants such as dyes or heavy metals [73]. The alginate can form cross-linked gel matrices without much difficulty in the presence of divalent positively charged ions, and that’s why calcium cross-linked matrices are preferred in the gel phase to have better efficiency of heavy metal adsorption [12]. Due to the presence of influential carboxylic functional groups in alginate structures, it has excellent potential to be used as an effective absorbent, the metal ions in the polluted medium can form complexes with the carboxylic groups found in the structure of alginate [13]. 9.3.2.1.2 Chitosan Chitin is the source of chitosan by processing chitin (deacetylation), chitosan can be obtained, the second most abundant bio-polysaccharide next to cellulose. The structure of chitosan comprises β- (1→4) -linked d-glucosamine residues and n-acetyl-d-glucosamine distributed randomly [63]. The percentage of abundance and the sequence of these units will determine chitosan’s biological and physical-chemical properties. Being the most abundantly used biopolymer obtained from marine sources, the application of chitosan varies in diverse forms, i.e., NPs, membranes, film, beads, etc. Chitosan is one of the potential biopolymers used to remove low concentrations of heavy metals, dyes, proteins, and a few other pollutants from contaminated water [19]. This fact is attributed to some essential primary amino, acetamido, and hydroxyl functional groups in their spatial

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arrangement. This is also because of the properties like high hydrophilicity due to the presence of many hydroxyl groups in its glucose units, chemical reactivity of these functional groups, and chain flexibility [18]. Chitosan will bind with group 3 transition metal ions with the help of highly reactive amino groups present in its structure. In addition to this, in the case of media with lower pH, chitosan adapts to show a cationic behavior, leading to the protonation of the amino group, thereby aiding the adsorption of heavy metal ions by the ion exchange process. Collectively the properties mentioned above show that chitosan has a potential role in heavy metal removal from water and liquid drink [48] and dyes [78]. 9.3.2.2  FROM PLANT SOURCES Plants for industrial use offer lots of cheap, renewable, biocompatible, nontoxic materials widely available worldwide. Lignin (20–30%), cellulose (40–50%), and hemicellulose (20–40%) are products of farming activity or plant residue components [1] (Table 9.1). One of the rapidly expanding fields worldwide in nanotechnology (NT). Synthesis of non-toxic NPs with high bioactivity, biocompatibility, and bioactivity can be done by using plant-based extracts [64]. TABLE 9.1  Components of Plant Residues Plant Residues

Compound Present

Flower

Lignocellulosic (high percentage of cellulose in flower cell wall)

Leaves

Lignin, cellulose, hemicellulose

Stalks, seeds, fruits

Lignin, cellulose

Wood

Mainly cellulose, also lignin and hemicellulose

9.3.2.2.1 Lignin Lignin contains aromatic rings with many hydroxyl groups and a natural polymer. The existence of lignin is seen in most plants as it forms the skeleton of plants along with cellulose and hemicelluloses. Hence the above compounds are present in more than 90% of the wood components. Lignin is obtained as the primary pollutant of the paper-making industry at a cheaper price for huge quantities [20]. Methods of extraction and separation, their location, and species of plant may affect its physical properties. Due to the

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various properties and purposes in different field’s lignin has been gaining scientific attention to form NPs and other nanostructures. In the rapid removal of lead ions from water and soil, the puffiness behavior is seen due to porous lignin NCs, thereby aiding the remediation of the environment [74]. NC hydrogels derived from porous lignin composite nano-sphere on polymerization with Ziegler-Natta vanadium could also be used in water purification [73]. 9.3.2.2.2 Cellulose A renewable, non-toxic, and biodegradable natural biopolymer, Cellulose is found abundant. Lignocellulosic materials are the primary form from which Cellulose is obtained. Structure of Cellulose contains repeating units of cellobiose of molecular formula (C6H10O5) n with beta (1–4) linked D-glucose units, a linear backbone (Figure 9.2) [2]. One is due to the wide availability, sustainability, renewability, and surface modification [2]. Plentiful, Cellulose-based materials are available and are inexpensive as they have low economic value. Different parts of plants like fibers, roots, shells, leaves, stems, bark, seed, and husk are used in making various forms of cellulosic adsorbents. An effective medium to remove Cd2+ ions from water by using carboxy cellulose nanofibers processed from untreated Australian spinifex grass by a nitro-oxidation method [71]. According to recent studies, numerous nanocompounds such as mesoporous cellulose nanocrystals (CNC), thin transparent and slim with elasticity, hydro-gels, and aero-gels produced from plant celluloses are environmentally friendly. The hydroxyl groups present in the exterior of Cellulose helps in the incorporation of chemical moieties, in a way improving adsorption of pollutants [75]. 9.3.3 LIPIDS In the Nanobiotechnology field, lipid-based NPs appear to be budding nanodrug delivery systems (DDS) and a potential encapsulant. Liposomes, SLN (solid lipid NPs), and nanoemulsions are parts of lipid-based NPs. Lipid NPs also exhibit long shelf life, scaling up to industrial from lab-scale is easy, storage constancy, entrap compound with diverse solubility and entrap compound [72].

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FIGURE 9.2  Cellobiose.

9.3.3.1 LIPOSOMES The liposome is made of phospholipids and cholesterol in a biliary spherical carrier structure. The phospholipids present provide biocompatibility, and the cholesterol is for stability, and it also acts as an anti-agglomerative and much other specific function like gene delivery [66]. Many advantages like high biocompatibility, biodegradable, large-scale production, ease of synthesis, similar to the biological membrane, non-stimulating agent for the immune system, and application on various drugs of different nature are attained by using liposomes [59]. From soy lecithin (extracted from soya beans) process of strong sonication, dehydration-rehydration-heating, thinfilm ultrasonic dispersion to form a concentric bilayer of phospholipids that encloses an aqueous solution inside is one of the preparation methods for liposomes production. This method manufactures high lipid concentration that is an eco-friendly and straightforward process [31]. Liposome’s NPs are mainly used in drug delivery function, as they carry both hydrophobic and hydrophilic molecules, increase the drug action time using prolonged half-life, has no or very low toxicity, and controlled release of drug [58]. 9.3.4  NUCLEIC ACID Owing to their structural simplicity, nucleic acids like DNA and RNA can be used as precursors for forming bio-nanoparticles like nanoscaffolds.

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Furthermore, nucleic acids have a fascinating capacity to self-collect into tiny and stable formations with exact nanomolecular size, formulation, and dimensions [61]. 9.3.5  CARBON FROM AGRICULTURAL WASTES The preference for carbon obtained from agricultural waste over coal obtained from non-replenishable coal deposits is attributable to the facts such as efficacy, cheap availability, and abundance [51]. Agricultural waste materials could be a better raw material for the production of carbon. Agricultural waste is a cluster of natural and non-natural by-products such as cotton or corn, coconut oil, grapes, oats, wheat, banana, etc. These can be potentially used in carbon nanomaterials (CNMs) [80]. The interest in agricultural waste products for NM production arises from the inevitable fact that certain other Industrial waste materials are hazardous and need sophisticated technology and proper technical handling, tedious procedure to be furnished into a NP. 9.3.5.1  CARBON NANOTUBES The allure over CNTs for potential applications like effluent treatment is gaining importance day by day. CNTs are tube-like structures made from graphite sheets (by rolling them up in a tabular form) [60]. It comprises two types of multi-walled CNTs and single-walled carbon nanotubes (made using multiple layers of sheets obtained from graphene. The primary role of CNTs in effluent treatment is based on its property of adsorption, which is based on specific functional groups, the surface area of exposure, type of CNT, i.e., closed or open-ended, and also purity [3]. Compared to the strength of sp3 bonds found in alkanes, the sp2 chemical bonds in CNTs provide these structures a potential and unique strength. The heavy metal sequestering property of CNTs can be enhanced by the incorporation of certain oxygen-containing groups by employing specific processes such as plasma, Ozone, and acid treatment [57], the modified CNTs containing these groups are capable of absorbing heavy metals like mercury, As, nickel, cadmium, and also radionuclides. The capability of raw CNTs was compared with that of modified CNTs, targeting chromium (III) recovery from marine water. During the examination process, maximum absorption was found to be achieved by increasing the pH from 4 to 7. It was evident that no removal

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of heavy metals occurred in the case of raw CNTs, but comparatively modified CNTs showed better potential and quicker adsorption capabilities. When the potential of CNTs doped with fluorine was tested for the absorption of chromium (III), it showed an interesting result of 50 to 65% removal of heavy metal within a stipulated time of 20 minutes of contact (at a temperature of 28°C). CNTs were modified with the addition of ethylenediaminetetraacetic acid (EDTA) and sulfuric acid and examined over the recovery of chromium (IV). The results showed that at a pH of 3 and for a dosage of 60 mg adsorbent, maximum absorption was observed in a time of 150 minutes [36]. The critical factor pH controls the entire adsorption process; according to the literature currently available, it is understood that maximum absorption of Cr (IV) and Cr (III) occurs at a pH range of 1 to 4 and 5 to 8, respectively. The best experimental data could be obtained by using the pseudo-second-order model and Langmuir isotherm model [6]. 9.3.5.2  CARBON PARTICLE Carbon NPs can be produced by diverse methods, out of which a method that includes a reactor and controlled heating mechanism is found to be efficient because the NMs produced as a result of this mechanism are found to be in a scattered form due to high pressure and temperature inside the chamber, the optimum temperature usually exceeds 700 CO along with the presence of a suitable catalyst [22]. Polymers like polylactic acid (PLA) are gaining interest as a potential precursor of carbon NPs due to their biodegradability property. Additionally, thermoplastic polymers (like polypropylene, polyethylene (PE), polyvinyl chloride (PVC), polystyrene, etc.), are the fundamental parts of civil solid waste [33]. Many massive loads of plastic waste are unloaded each year, the more significant part of which is burned or buried. The use of these Polymers as a raw material for the production of porous NMs, CNTs, and renewable fuel sources is booming based on the concept of wealth out of waste [8]. 9.4  METHODS OF PREPARATION To extend the application of bionanomaterials in various fields, it is very significant that more importance should be given to the research and development (R&D) in the design and synthesis of biological NPs to impact nature and human beings positively. While selecting the process for bionanomaterials,

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more criteria and constraints from a biotechnological point of view include properties like proper composition, uniformity in size, and gratuitously high purity [62]. In this chapter, we have discussed so time methods that can use for the synthesis of biological NMs, which includes two-step procedures based on emulsification, one-step procedures, preparation by drying process supercritical drying, electrospraying, spray drying, and green synthesis. 9.4.1  TWO-STEP PROCEDURE BASED ON EMULSIFICATION Based on the advancement of new technology and devices for the process of emulsification past few decades, the two-step procedure based on emulsification is identified as an effective method in the synthesis of biological NMs [44]. Based on the nature of the dispersed medium and dispersion phase, the emulsion can be of three types’ oil in oil, water in oil, and oil in water emulsion. It can use several solvent extraction mechanisms such as solvent diffusion and solvent evaporation to produce NMs from the emulsion generated. Gelation and polymerization are the available alternative techniques for fabricating NPs from the emulsion. High batchto-batch reproducibility and high encapsulation efficiency are put forward in the method of emulsification. Additionally, narrow size distribution NPs are obtained from this method. During the preparatory step, avoiding heat treatment makes emulsification a helpful approach in encapsulating highly thermolabile compounds. On the other hand, the final dispersion is undesirable as the presence of residual solvent causes regulatory concerns. To eliminate these residual solvents, intensive washing procedures are carried out [15]. 9.4.2  ONE STEP PROCEDURE NPs synthesis from lipophilic solution’s semi-polar solution displacement followed by the polymer interfacial deposition is known as nano-precipitation [28]. Solvent displacement or interfacial deposition methods are other names given. Quick diffusion in the aqueous or non-solvent phase by polymer solution such as acetone to form NPs [28]. Enhancement of surface area and quick precipitation, NPs are obtained due to interfacial tension reduction among phases. In the presence or absence of mechanical stirring, a process can take place. The production of biological NPs is rapid and straightforward even at low concentrations by using biological polymers and peptides with

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high reproducibility in this method. Yet, the entrapment competency being low for polar molecules (like drugs) and low concentration of polymer requirement leads to low NP recovery yield, which is a hindrance to the nano-precipitation method [44]. Desolvation (Coacervation) is a process in which a solution of biomolecules dissolving agents, for instance, salts, solvents, alcohol (e.g., acetone) addition leads to thermodynamic, proteins self-assembly, which are due to separation and coacervation of molecules in aqueous phase [10]. Support for the self-assembly of protein for the process is attained due to the electrostatic interactions. The above method supports the fabrication of numerous protein types, albumins (human serum albumin and bovine serum albumin (BSA)), DNA, and oligonucleotides, gliadin, and gelatine [5]. 9.4.3  PREPARATION BY DRYING PROCESS Regular assessments have driven specialists to quit utilizing solvents and search for paltry cycles to tie NPs [5]. This unprejudiced drying step is viewed as a good choice for assessing the standard procedure referenced above, which is wary of regular NP arrangement, rehearses. In any case, dry testing of NPs regularly prompts corruption arranged advancement, so because of the flexibility and usability of hand-made particles, they are effectively adjusted to a broad scope of uses. Outrageous planning of fluid can be accomplished as far as length and definition [77]. Likewise, the nanocirculation ought to be dried in a conventional, more fitting, and arranged approach to get quantifiable potential outcomes dependent upon the situation. Accordingly, the dry covering measure gives an effective technique to keep up with the inborn suspension qualities of the dry powder, where the dry NPs can be straightforwardly added to a solitary filtration with no extra drying step. Three standard designs for general NP conveyance by supercritical drying, splash drying, and electric spout techniques might be unique [62]. 9.4.4  ELECTRO SPRAYING Electric shock is the electric discharge of a liquid at a consistently rated point in the action of electrical energy. In the 16th century, William Gilbert (William Gilbert) first published miracles about liquids equipped with electric fields. He charted how bright water droplets could negatively affect an object’s design [23]. Insulin is used as a protein test to confirm the robust quality of

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the electric shower and provides a single diffuse protein molecule to ensure average growth. Control room testing directed by electrochemical insulin and insulin receptors was equivocal, suggesting that improved insulin is often aspirated after electro bath. The powerful scope of molecular and biomolecular research using these contact techniques and electric showerheads is quickly becoming apparent, especially in drug delivery applications [47]. 9.4.5  SPRAY DRYING Spray drying is an effective alternative procedure for producing minute particles or powder; utilization of this method is specific for the production of biological NMs has its Origins from the early 1990s, the time during which the world witnessed the significance of drug delivery or therapeutic proteins through parliamentary route [14]. Initially, during the spray drying, a solution that consists of biomolecules is atomized to form an aggregate of minute droplets, which is for the bride in a what app to generate solid particles. Through a cyclone, the air-dried particles are subsequently collected. The spray drying process has become more efficient in the past decades, and numerous bio NPs or nanopowders are produced from biological samples through this technology. In these methods, piezoelectric actuators play an essential role in producing minute droplets, much smaller than the droplets produced by conventional spray dryers. Based on the conditions in which the system is operating and the presence or absence of certain surfactants, the size of the particles could be altered [77]. Despite the growing significance of the spray drying process, a billion-dollar question is whether it can produce a biologically active material in all cases? This question is based on the fact that the biomolecules might be thermolabile in some cases and, when subjected to drying with the help of hot air, could lose their biological potentials [46]. This effect on thermolabile molecules such as enzymes, peptides, and proteins can be minimized by the use of surfactants or disaccharides in the process. 9.4.6  SUPERCRITICAL DRYING The supercritical drying method works based on using a supercritical fluid as a medium of drying (anti-solvent), which has some specific features such as solvating power and density similar to liquid and gas-like transport properties (viscosity and diffusivity). Carbon dioxide is a widely used compound in precritical fluid processing [53]. Currently, numerous methods are at

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hand for the synthesis of NPs using supercritical drying. In this technique of supercritical drying, carbon dioxide is used to solubilize biological constituents, and then it is decompressed bypassing via a small opening into the laboratory environment. This process aids homogenous nucleation and precipitation of the biological components into well-dispersed particles. Even though the technique can be carried out in a solvent-free environment, the solubility of many pharmaceutical components in carbon dioxide is very modest. These led to the development of new supercritical technology based on solution enhanced depression by supercritical solution. In this methodology, the solubility of pharmaceutical compounds carbon dioxide is enhanced by the use of co-solvents. This method finds application in the precipitation of specific protein NPs, for example, insulin, Dornase alfa, and lysozyme. Here ethanol is involved as a co-solvent to perform precipitation from its aqueous solution, thereby targeting a yield of NPs in size range of 100–500 nm [5]. 9.4.7  GREEN SYNTHESIS The ‘Top Down’ or ‘Bottom Up’ approach is usually used to create NPs. Through various physical and chemical ways to reduce the size of NPs, the production of NPs is done in the top-down approach. While the NPs synthesis is done using small particles like atoms and molecules, it is a bottom-up approach through primary oxidation or reduction reactions. The NPs obtained through these greener ways have minimum flaws and have homogenous chemical composition. Plant extracts plus microbial extracts are extensively used in the biological synthesis of NPs (Table 9.2) [30]. For choosing the finest microorganism or its extracts, the precise characteristics of those microbes, for instance, their biochemical pathway, phytochemical content, enzyme activity, cell growth, and optimal reaction conditions, are considered. UV-Visible spectra are used to examine the shape and size of NPs in aqueous suspension [30]. The size of 2–100 nm NPs is characterized at a wavelength range of 300 to 800 nm. Removal of virus from drinking water is done by using biogenic silver produced with Lactobacillus fermentum [76]. Commercially available water purifiers such as aqua pure and QSInano for residence use have Ag-NPs as a disinfectant. For gene delivery and delivery of beta-galactosidase plasmid in both in vivo and in vitro conditions, Magnetotactic bacteria (MTB) NPs are used. Functions as remediation of heavy metals from soil and disinfection of water, iron (Fe) NPs have much significance [79].

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TABLE 9.2  Biological Compound and Metal Ions Used for Green Synthesis Along with Their Application Metal Titanium dioxide (TiO2)

Biological Compound Eclipta prostrata (leaf extract)

Copper oxide (CuO) Malva sylvestris and Phyllanthus amarus (leaf) Zinc oxide (ZnO) Cassia auriculata (flower extract) Cadmium sulfide Coriolus Versicolor (CdS) (immobilized fungus)

Application Fields of coating, cosmetics, food additive. Effective photo-catalyst towards the remediation of pollution. Antimicrobial activity against bacteria. Biocidal activity higher against various pathogens. Remediation of toxic metals from soils.

9.5  NANO-ADSORBENTS FOR HEAVY METAL RECOVERY 9.5.1  NANO-MAGNETITE CHITOSAN FILMS A primary metal, low voltage is surprisingly unapproved and can consistently create trouble and trouble with the design of life. However, these strategies are highly cost-effective and can, in essence, create utility when releasing certain hazardous scrap metals. Adsorption is an anchor point, and current efforts have directly convinced this innovation and the scheme of various metal particles in water. A standard, the giant nail-joint NP can stand out to everyone because it has a starting position. The attractive work area adsorption process is commonly used in water treatment and household cleaning. Iron oxide nano-magnetite is guaranteed for mechanical wastewater treatment because of the base rate, substantial adsorption limitation, simple division, and increasing stability [38]. This study uses chitosan and its dependence on past use of biomass. Chitosan is probably the most abundant biofilmforming agent in nature, and it has been named the cheapest adsorbent with a high adsorption limit. It is an acceptable state formed by the cross-linking of some metal particles and drugs. The use of purified chitosan with adsorbents for low soil surfaces is applicable. To date, some analysts have promoted the use of bound chitosan to remove metal particles. Chitosan has a stable metal chelation limit because all five channels of chitosan contain amines and hydrographs, so it has several advantages [41]. You can also participate in the attractive remote adsorption region without a proper stretch situation in an adsorption setting. By implication, as plotted using the usual size of 25 nanometers, the Circular nanocrystalline Film embraces this thought, as if various studies had been made from the size of 25 nanometers [45].

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9.5.2  MAGNETIC CHITOSAN NANOPARTICLES It miles amazing those profound metal particles have addressed a genuine chance to a common framework and extensive success in light of their frightful and nonbiodegradable homes. Nearby these follow, the expulsion of massive steel particles in wastewater is a central issue [81]. Select strategies, including substance precipitation, atom trade, layer division, and adsorption, had been applied to the expulsion of solid steel particles from wastewater. Among these frameworks, adsorption headway, depending intensely on the outrageous degree adsorbent materials, is indeed possible the very least tangled methodologies considering its healthy development, absurd ability, and most minimal expense. In this point of view, NMs these days have shown an essential utility in wastewater treatment credited to their great homes like superfluous surface areas, bountiful extraordinary locales, and phenomenal sorption limits. As a stunning nano-adsorbent, magnetic chitosan NPs or NCs had been explored at the discharge of steel garbage as of past due [69] on account of their extraordinary sorbent retouching through primary usage of engaging outside area, first-class selectivity, and strong metal chelating limit as a result of the presence of adequate amino and hydroxyl packages in chitosan chain. On this foundation, investigated several mind-boggling procedures for buying arranged chitosan NMs. One of the standard technique two or three levels, which consolidate the blend of drawing in the trash, the joining, covering, or disseminating of the connecting particles with a chitosan blueprint and the cross-linking exchange among chitosan through the improvement of various chelating ligands firmly mixed carboxymethyl chitosan modified magnetic cored dendrimers in a three-level procedure. The other method for setting in chitosan NMs is an in situ planned course that is refined using compound coprecipitation of chitosan, Fe2+ and Fe3+ under fundamental condition coordinated Fe2O3 or chitosan NPs inside the reasonable in-situ way and the most genuine sorption cut-off of the as organized adsorbent for Cu(II) changed into 35.5 mg. Extraordinarily, those blend strategies for the magnetic chitosan NMs are risky and can’t be ready through mass or relentless creation. Like this, there was a strong interest in improving splendid adjusting to ranges that offer decision pathways over traditional techniques for continuous masterminding of engaging chitosan NMs. The advancement of cycle uplifting, which gives the improvement of novel gear and frameworks, has been extensively applied in a constant status of NPs with over-the-top creation skill ability [11].

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9.5.3  MAGNETITE-ALGINATE NANOPARTICLES Metal Ion pollution in water bodies is a significant problem, even though it can create comparatively more minor levels of damage. Metal ions, for example, iron, lead, cobalt, and nickel, are poisonous and comparatively non-biodegradable to that of other solid wastes, thereby creating difficulty for the sustenance of life forms in the water ecosystem. The following are the techniques that are currently applied for the remuneration of wastewater [27]. Among these methods, the technique of adsorption is of great significance because of its advantages, including comparatively less tedious and lower energy requirement in the process of metal ion recovery. According to the research articles, it is seen that nanosorbants have a more significant absorption potential when targeted towards the removal of metal ions from water bodies. Magnetite NPs are primarily used in the bioremediation of wastewater and also for effluent treatment; this application is attributable to their super magnetic properties and comparatively more diminutive size, and also these magnetite bio NPs can be regained from the field of usage by using a magnet, and it has less potential to create adverse effects [17]. 9.5.4  QUERCETIN LOADED NANOPARTICLES BASED ON ALGINATE The heavy metal lead has some exceptional qualities, making it an important role player in various industrial applications [25]. The properties possessed by lead include resistance towards corrosion, a comparatively lower melting point than other heavy metals, and very high malleability. Lead can find its path inside the human body through various means, significantly through inhalation and ingestion of soil, water, air, and food contaminated with lead. Lead poisoning can harm the Kidneys, blood pressure, and central nervous system. Based on the above facts and proof from scientific literature, it is clear that it is a hazardous material of environmental concern with high toxicity stability and frequency of appearance [24]. Quercetin decorated alginate NPs are prepared based on alginate in water emulsion with external gelation. While preparing the NPs of concern, the effects on production are caused by factors like the initial pH concentration of lead and other heavy metal ions. The first loaded NPs based on alginate showed comparatively better efficiency in adsorbing lead from the medium of concern. These decorated alginate NPs have a comparatively smaller diameter (58.23 nm) than conventional alginate NPs (95.06 nm). The optimum pH for the efficient

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removal of lead from the medium is 7, essential because the entire process is highly pH-dependent. The adsorption capability of loaded NPs was about 140.37 ± 5.04 mg g–1, and subsequently, the desorption rate was about 90.07 ± 3.39% [32]. 9.5.5  CELLULOSE-BASED ADSORBENTS Adsorption is defined as the process of pollutant transfer from the bulk solution to the exterior of the adsorbent. The reaction rate depends on intra-particle diffusion or film formation and sometimes both. Owing to its abundant, cost-effective nature, different cellulose compounds such as leaves, roots, shells, bark, stems, and much more are made into adsorbents [65]. To remove cadmium (Cd) and lead (Pb) metal ions using sunflower stalks are done with batch adsorption to increase the efficiency. Coconut husk waste is used to make basic mercury adsorbents (Table 9.3) [75]. Different adsorption capacity is resulted due to changes in the morphology and functional groups of surfaces after mercerization and bleaching treatments. TABLE 9.3  The Adsorption Capacity of Coconut Fiber or Pith on Mercury Ions [75] Cellulose Adsorbent (Coconut) Coconut pith–NaOH Pristine coconut pith Coconut fiber–NaOCl Coconut fiber–H2O2 Coconut fiber–NaOH Coconut pith–NaOCl Coconut fiber

Adsorption Value 956.282 mg/g 730.250 mg/g 639.948 mg/g 634.347 mg/g 611.678 mg/g 501.126 mg/g 431.773 mg/g

According to most adsorption studies, high-quality adsorption potential is seen in only a few untreated cellulosic compounds. Its quality of adsorbents is altered due to chemical and physical treatment. A successful means for Cd2+ ions removal from water is using carboxy cellulose nano-fibers found in Australian spinifex grass through the nitro oxidation method. Within more than 5 mins, an insufficient number of nano-fibers can remove the vast concentration of Cd2+ ions from water. At a 250 ppm Cd2+ ions concentration, the maximum removal efficiency is 84%, and the highest removal capacity is about 2,550 mg/g. Some other cellulose derivatives and their application in heavy metal removal (Table 9.4) [39].

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TABLE 9.4  Cellulose Derivatives and Their Application Name

Procedure

Heavy Metals Points

Cellulosic adsorbents

Halogenation of microcrystalline cellulose followed by functionalization with pyridine diacid.

Removal of Pb (II) and Co (II) from aqueous solution.

Amount of carboxyl group present (1.32 mmol/g) responsible for higher metal ion adsorption.

TEMPOModified with polyoxidized fibrous ethyleneimine via crosscellulose linking glutaraldehyde.

Adsorption of Cu (II)

Exhibit higher adsorption of copper ions at pH of 5.

Functionalization Selective oxidation of nanocellulose C2 and C4 hydroxyl groups, by oxidizing the aldehyde group to form 2,3-dicarboxyl groups.

Adsorption of copper (2+) ions

Maximum adsorption capacity for Cu (II) at pH – 4

Nanocellulose paper

Synthesized by phosphory- Copper lated nanocellulose paper adsorption that act as ion exchangers from aqueous solution.

Water containing Cu2+ ions are passed through nano-paper

9.5.6 TITANITE/TIO2 ADDED LIGNIN From plant stalks, through processing, alkaline lignin is extracted. By acid precipitation, the obtained lignin is purified. For the need of additives, titanate nanotubes are arranged. The characteristics of these materials to act as heavy metal adsorbents are studied by adsorption tests such as X-Ray Diffraction (XDR), Brunauer–Emmett–Teller (BET), Fourier Transform Infra-Red (FT-IR), Transmission Electron Microscope (TEM), and Scanning Electron Microscope (SEM) [29]. Rapid adsorption of organic and inorganic NPs is done quickly by using titrate nanotubes with solid ion exchange capacity and large specific surface area, thus forming one-dimensional NPs. The porous and hollow structure of NPs and the ion exchange capacity is due to the above property. Thus, titrate nanotubes are capable of adsorbents in heavy metal removal [71]. The lignin powder preparation process detail is depicted in Figure 9.3 [74]. Above powder of 7 g, each is taken in four beakers of 50 ml of 16% NaOH and at room temperature. To get a uniform suspension, they are magnetically stirred for an hour and transferred, Teflon lined stainless-steel high-pressure reaction vessel of 100 ml capacity to be kept in an autoclave for 2 hours at 130°C. The residue is obtained and filtered by centrifugation, all allowed to cool at room temperature. Lignin residue is obtained by heating the filtrate in

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a water bath at 50°C for 45 minutes, with continuous stirring and drop wise addition of 10% HCl acid of pH around 3. The precipitate is further separated by centrifugation after aging for 60 minutes. The content was obtained for overnight drying at 102°C after repeated washing with pH 6 distilled water. A homogenous mixture is prepared at room temperature by mixing 50 mL of 10 mol 1 NaOH solution in one liter. About 10 g of lignin powder and 1 g anatase TiO2 (titrate nanotubes) for 45 minutes, magnetically. A reaction vessel of 100 ml lined with tetrafluoroethylene is used to store the suspension for 24 hours at 150°C. It is allowed to cool to room temperature on removal of the reactor.

FIGURE 9.3  The lignin powder preparation process detail.

At last, it is suction filtered and rinsed till pH 7 approx. Using distilled water, dried overnight at 80°C. The lead ions are adsorbed with pH 6 and temperature, being 25°C, in a time of 5 minutes. Just 0.2 g/L adsorbent is required. Overall, WL-TNTs are economical and high-quality adsorbents with numerous applications [74]. 9.6  NANOCOMPOSITES FOR HEAVY METAL RECOVERY 9.6.1  CARBON NANOTUBES (CNTS)/CA-ALGINATE BEADS CNTs are extensively used for different applications based on their specific structural and chemical properties [29]. With a different composition of multi-walled carbon nanotubes and pH values was tested for the adsorption of some stains like methylene blue (ME) and methyl orange; based on results obtained, it was interpreted that multi-walled carbon nanotubes

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can show an increased rate of absorption over MB and methyl orange dyes compared to that of calcium alginate composites. Despite the enhanced absorption capabilities of CNTs, the limiting factors preventing the wide usage of these structures are attributable to a tedious centrifugation process associated with it [75]. 9.6.2  RECOMBINANT FUSION PROTEIN PBRD CROSS-LINKED TO CALCIUM ALGINATE NANOPARTICLES Heavy metal pollution because of lead is of the tremendous surge in recent years due to excessive urbanization and industrialization; the wastewater contaminated with lead makes it unfit for human consumption [16]. The South African rivers are losing their quality because of excessive lead contamination. Based on these novel potential problems, new strategies are being developed to remove or reduce lead contamination in wastewater. The Cheapest way of Sustainable remediation of lead from water can be achieved by using bacterial cells as an alternative to chemical methods [37]. This problem can be mitigated by attaching some Lead targeting peptides with the bacterial cells. Still, the problem is that the efficient growth of modified bacterial cells in an external environment is of great uncertainty. So, to provide an efficient methodology of using bacterial cells to remove the heavy metal lead from water. A type of non-absorbent is used to exploit the lead binding properties of bacterial protein. PbrD Protein will bind the lead ion intracellular, ensuring the reduced cellular toxic effect of lead at huge concentrations. Calcium alginate NPs were used to increase the stability of PbrD protein. The stability is achieved by immobilizing protein onto calcium alginate NPs. The calcium alginate NP can ensure stability against fluctuation in pH and temperature change, thereby enhancing the remediation of lead [52], and also it is biodegradable. Calcium alginate NPs were coupled with the metallochaperone PbrD protein to generate mono-dispersed spherical particles with a diameter of 80 nm approximately. Lead Ions are positively charged, and the negatively charged bio adsorbent can enhance the ability to bind with it thereby increasing absorptivity [67]. 9.7 BIOSORPTION Biosorption is presumably portrayed as the ejection/prohibiting of needed substances from watery relationships via natural texture. Such substances

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can be expected and inorganic and are both dissolvable and insoluble designs [21]. In the composition, sportive homes of a broad extent of ordinary biomasses usually endeavor for wastewater cure, extraordinarily wherein the assembly of pollution is fewer than 100 mg L–1. The utilization of other cure methodologies is deficient and took over the top [42]. Biosorption: Definition Sorption is a term applied for every osmosis and adsorption; these expressions are as often as possible frustrated. Ingestion turns an individual from a substance in a solitary country into another explicit country (i.e., liquids being eaten up through a hearty or gases being eaten up with the guide of water). Adsorption is the genuine adherence or holding of particles and ions onto the outside of the solid texture. For this model, the fabric amassed on the interface is the adsorbate, and the durable surface is the adsorbent [21]. Biosorption is a subcategory of adsorption, where the sorbent is a characteristic matrix. Biosorption is an association of speedy and reversible confining of particles from liquid arrangements onto valuable social affairs, which can be accessible at the open air of biomass. This exchange is self-supporting on cell absorption. Biosorption has included the composition as a capable and exact connection. Biosorption might be acted in a broad extent of pH regards three–nine and temperature regards 4–90°C. As the ideal bio sorbent particle length is someplace in the scope of 1 and 2 mm, the congruity circumstance of every adsorption and desorption is done quickly [40]. 9.8  RADIOACTIVE METAL RECOVERY Removal of UO22+ from aqueous solution, using synthesized multiwall carbon nanotubes (MWCNT) grafted with carboxymethyl cellulose (CMC), by batch technique process. Treatment of raw MWCNT with N2 plasma in a reactor, built for grafting with continuous stirring for 40 minutes. At 70 W, 650 V, 60 mA, and 10 Pa are the conditions for N2 plasma treatment. MWCNT-treat would be the name for plasma-treated MWCNT. Following the plasma treatment process, MWCNT-treat is placed in a grafting reactor at 80°C, where CMC solution (100 mL 1.50 g/L) is injected and stirred continuously for a week. In anticipation of no detection of CMC in the high-performance liquid chromatography-mass spectroscopy (HPLC-MS) method, the obtained sample (supernatant) is washed with Milli-Q water. The obtained sample is now known as MWCNT-g-CMC with is separated from the suspension each time by centrifugation (Beckman Coulter 64R) for 60 minutes at 18,000 pm. Finally, the MWCNT-g-CMC compound is obtained by oven-dried at 95°C

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for 24 hours. Comparing the sorption capacity of MWCNT-g-CMC and raw MWCNT on UO22+ removal, it is found that MWCNT-g-CMC has approx. 8 times more capacity than the other [70]. 9.9  FUTURE PROSPECTS Green NMs are in a significantly insightful stage for the treatment and assurance of harmful development, yet a conclusive steadiness is open to question clinical primers. Other extra freedoms have come into account as per the usage of green NMs, inferable from their biocompatibility and sufficiency. Moreover, various illnesses that don’t have fixes today may be eased by these green NMs later on. Likewise, escalated appreciation of key physiological blocks in vivo is the best approach to pass on NPs into the tumor effectively. Besides, the data concerning the prosperity of NMs isn’t sufficient, and expansive serious and steady destructiveness in clinical examinations should be believed to perceive the risks related to the use of NPs. It is entirely expected that green NMs could emerge as future danger therapeutics and diagnostics experts as soon as possible [7]. 9.10 SUMMARY Bionanomaterials have been of great interest in recent days because of their potential to recover hazardous chemical compounds like heavy metals and radioactive substances from wastewater. In this chapter, we have discussed the sources of biopolymers by which the bionanomaterials are made, their chemical composition, and the current usage of these biopolymers in the production of bionanomaterials. A detailed description of the methods by which these bionanomaterials can be produced with greater feasibility and efficiency is also included in this chapter. The different methods and bionanomaterials used for heavy metal recovery are summarized in the second half of the chapter, including bio NCs, bio adsorbents, and other bionanomaterials. We have also discussed the use of bionanomaterials and their derivatives potentially to recover radioactive compounds from the medium of interest. In the future, the barriers in the large-scale production and feasibility of these bionanomaterials should be dilated, and also should study the adverse effects of these bionanomaterials in the environment in detail.

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KEYWORDS • • • • • • •

Brunauer–Emmett–Teller fish gelatin Fourier transform infra-red magnetotactic bacteria scanning electron microscope transmission electron microscope X-ray diffraction

REFERENCES 1. Azamal, H., & Khwaja, S. S., (2014). Phytosynthesis of nanoparticles: Concept, controversy, and application. Nanoscale Research Letters, 9(1), 1–24. 2. Abdolali, A., Guo, W. S., Ngo, H. H., Chen, S. S., Nguyen, N. C., & Tung, K. L., (2014). Typical lignocellulosic wastes and by-products for biosorption process in water and wastewater treatment: A critical review. Bioresource Technology, 160, 57–66. 3. Agnihotri, S., Mota, J. P. B., Rostam-Abadi, M., & Rood, M. J., (2006). Theoretical and experimental investigation of morphology and temperature effects on adsorption of organic vapors in single-walled carbon nanotubes. Journal of Physical Chemistry B, 110(15), 7640–7647. 4. Agulhon, P., Markova, V., Robitzer, M., Quignard, F., & Mineva, T., (2012). Structure of alginate gels: Interaction of diuronate units with divalent cations from density functional calculations. Biomacromolecules, 13(6), 1899–1907. 5. Allouche, J., Boissière, M., Hélary, C., Livage, J., & Coradin, T., (2013). Biomimetic coreshell gelatine/silica nanoparticles: A new example of biopolymer-based nanocomposites, Journal of Materials Chemistry, 16(30), 3120–3125. 6. Anastopoulos, I., Anagnostopoulos, V. A., Bhatnagar, A., Mitropoulos, A. C., & Kyzas, G. Z., (2017). A review for chromium removal by carbon nanotubes. Chemistry and Ecology, 33(6), 572–588. 7. Barabadi, H., Ovais, M., Shinwari, Z. K., & Saravanan, M., (2017). Anti-cancer green bionanomaterials: Present status and future prospects. Green Chemistry Letters and Reviews, 10(4), 285–314. 8. Bazargan, A., Hui, C. W., & McKay, G., (2013). Porous carbons from plastic waste. Advances in Polymer Science, 266, 1–26. 9. Boverhof, D. R., Bramante, C. M., Butala, J. H., Clancy, S. F., Lafranconi, W. M., West, J., & Gordon, S. C., (2015). Comparative assessment of nanomaterial definitions and safety evaluation considerations. Regulatory Toxicology and Pharmacology, 73(1), 137–150. 10. Boyd, B. J., (2008). Past and future evolution in colloidal drug delivery systems. Expert Opinion on Drug Delivery, 5(1), 69–85.

Advanced Bionanomaterials for Heavy Metals 265 11. Cao, C., Xiao, L., Chen, C., Shi, X., Cao, Q., & Gao, L., (2014). In situ preparation of magnetic Fe3O4/chitosan nanoparticles via a novel reduction–precipitation method and their application in adsorption of reactive azo dye. Powder Technology, 260, 90–97. 12. Cataldo, S., Gianguzza, A., Milea, D., Muratore, N., & Pettignano, A., (2016). Pb(II) adsorption by a novel activated carbon-alginate composite material: A kinetic and equilibrium study. International Journal of Biological Macromolecules, 92, 769–778. 13. Cataldo, S., Muratore, N., Orecchio, S., & Pettignano, A., (2015). Enhancement of adsorption ability of calcium alginate gel beads towards Pd(II) ion. A kinetic and equilibrium study on hybrid Laponite and Montmorillonite–alginate gel beads. Applied Clay Science, 118, 162–170. 14. Chan, H. K., & Kwok, P. C. L., (2011). Production methods for nanodrug particles using the bottom-up approach. Advanced Drug Delivery Reviews, 63(6), 406–416. 15. Chaturvedi, S. P., & Kumar, V., (2012). Production techniques of lipid nanoparticles: A review. Biological and Chemical Science, 3, 525–541. 16. Çimen, A., Torun, M., & Bilgiç, A., (2015). Immobilization of 4-amino-2-hydroxy acetophenone onto silica gel surface and sorption studies of Cu(II), Ni(II), and Co(II) ions. Desalination and Water Treatment, 53(8), 2106–2116. 17. Crini, G., (2005). Recent developments in polysaccharide-based materials used as adsorbents in wastewater treatment. Progress in Polymer Science, 30(1), 38–70. 18. Crini, G., (2006). Non-conventional low-cost adsorbents for dye removal: A review. Bioresource Technology, 97(9), 1061–1085. 19. Cui, W., Li, J., Dong, F., Sun, Y., Jiang, G., Cen, W., Lee, S. C., & Wu, Z., (2017). Highly efficient performance and conversion pathway of photocatalytic NO oxidation on SrO-clusters@amorphous carbon nitride. Environmental Science and Technology, 51(18), 10682–10690. 20. Daemi, H., & Barikani, M., (2012). Synthesis and characterization of calcium alginate nanoparticles, sodium homopolymannuronate salt and its calcium nanoparticles. Scientia Iranica, 19(6), 2023–2028. 21. Davood, K., Payam, P., Majid, S., Behzad, P., & Mohammad, H. B., (2015). Synthesis of carbon nanoparticles from polystyrene wastes. International Journal of Sciences, 1(8), 53–57. 22. Elkordy, A. A., Ahmad, R. H., Faheem, A. M., & Haggag, Y. A., (2015). Evaluation of nanospray drying as a method for drying and formulation of therapeutic peptides and proteins. Frontiers in Pharmacology, 6, 1–140. 23. El-Shamy, O. A. A., El-Azabawy, R. E., & El-Azabawy, O. E., (2019). Synthesis and characterization of magnetite-alginate nanoparticles for enhancement of nickel and cobalt ion adsorption from wastewater. Journal of Nanomaterials, 2019, 1–8. 24. El-Sharaky, E. A., Mishrif, M. R., & El-Shamy, O. A. A., (2018). Synthesis and evaluation of a new trianionic surfactant for the removal of Pb(II) by flotation method. Tenside Surfactants Detergents, 55(2), 148–152. 25. Enoi, M., Miranda, S., Marcolla, C., Ovis, C., Rodrígues, A., Wilhelm, H. M., Sierakowski, M. R., Belí, E. B. T. M., & Alves De, F. R., (2006). Chitosan and N-carboxymethyl chitosan: I. The role of N-carboxymethylation of chitosan in the thermal stability and dynamic mechanical properties of its films. Polymer International, 55, 961–969. 26. Fan, H. L., Zhou, S. F., Jiao, W. Z., Qi, G. S., & Liu, Y. Z., (2017). Removal of heavy metal ions by magnetic chitosan nanoparticles prepared continuously via high-gravity reactive precipitation method. Carbohydrate Polymers, 174, 1192–1200.

266

Sustainable Nanomaterials for Biosystems Engineering

27. Fessi, H., Puisieux, F., Devissaguet, J. P., Ammoury, N., & Benita, S., (1989). Nanocapsule formation by interfacial polymer deposition following solvent displacement. International Journal of Pharmaceutics, 55(1), 1–4. 28. Fu, Y., Liu, X., & Chen, G., (2019). Adsorption of heavy metal sewage on nano-materials such as titanate/TiO2 added lignin. Results in Physics, 12, 405–411. 29. Gopinath, K., Karthika, V., Gowri, S., Senthilkumar, V., Kumaresan, S., & Arumugam, A., (2014). Antibacterial activity of ruthenium nanoparticles synthesized using Gloriosa superba L. leaf extract. Journal of Nanostructure in Chemistry, 4(1), 1–6. 30. Guner, S., & Oztop, M. H., (2017). Food grade liposome systems: Effect of solvent, homogenization types and storage conditions on oxidative and physical stability. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 513, 468–478. 31. Hefa, C., & Yuanan, H., (2010). Lead (Pb) isotopic fingerprinting and its applications in lead pollution studies in China: A review. Environmental Pollution, 158(5), 1134–1146. 32. Hamilton, J. D., Reinert, K. H., Hagan, J. V., & Lord, W. V., (2012). Polymers as solid waste in municipal landfills. Journal of the Air & Waste Management Association, 45(4), 247–251. 33. Honek, J. F., (2013). Bionanotechnology and bionanomaterials: John Honek explains the good things that can come in very small packages. BMC Biochemistry, 14(1), 1–2. 34. Hosseini, S. F., & Gómez-Guillén, M. C., (2018). A state-of-the-art review on the elaboration of fish gelatin as bioactive packaging: Special emphasis on nanotechnologybased approaches. Trends in Food Science & Technology, 79, 125–135. 35. Hossini, H., Rezaee, A., Rastegar, S. O., Hashemi, S., & Safari, M., (2014). Equilibrium and kinetic studies of chromium adsorption from wastewater by functionalized multi-wall carbon nanotubes. Reaction Kinetics, Mechanisms, and Catalysis, 112(2), 371–382. 36. Jarosławiecka, A., & Piotrowska-Seget, Z., (2014). Lead resistance in micro-organisms. Microbiology, 160(1), 12–25. 37. Jha, M. K., Upadhyay, R. R., Lee, J. C., & Kumar, V., (2008). Treatment of rayon waste effluent for the removal of Zn and Ca using Indian BSR resin. Desalination, 228(1–3), 97–107. 38. Johari, K., Saman, N., Song, S. T., Chin, C. S., Kong, H., & Mat, H., (2016). Adsorption enhancement of elemental mercury by various surface modified coconut husk as eco-friendly low-cost adsorbents. International Biodeterioration & Biodegradation, 109, 45–52. 39. Kazem, N., Ramin, N., Reza, S., Amir, H. M., Forough, V., Kamyar, Y., Azar, G., & Shahrokh, N., (2007). Biosorption of lead (II) and cadmium (II) by protonated sargassum glaucescens biomass in a continuous packed bed column. Journal of Hazardous Materials, 147(3), 785–791. 40. Kawamura, Y., Yoshida, H., Asai, S., & Tanibe, H., (1997). Breakthrough curve for adsorption of mercury (II) on polyaminated highly porous chitosan beads. Water Science and Technology, 35(7), 97–105. 41. Keshav, V., Franklyn, P., & Kondiah, K., (2019). Recombinant fusion protein PbrD cross-linked to calcium alginate nanoparticles for Pb remediation. ACS Omega, 4(16), 16816–16825. 42. Kim, H. U., Kim, K. H., Chang, Y. Y., Lee, S. M., & Yang, J. K., (2012). Heavy Metal Removal from Aqueous Solution by Tannins Immobilized on Collagen (Vol. 48, No. 1–3, pp. 1–8). New Pub: Balaban.

Advanced Bionanomaterials for Heavy Metals 267 43. Kumar, R., & Lal, S., (2016). Synthesis of organic nanoparticles and their applications in drug delivery and food nanotechnology: A review. Journal of Nanomaterials & Molecular Nanotechnology, 3, 1–4. 44. Lasheen, M. R., El-Sherif, I. Y., Sabry, D. Y., El-Wakeel, S. T., & El-Shahat, M. F., (2014). Removal and Recovery of Cr (VI) by Magnetite Nanoparticles (Vol. 52, No. 34–36, pp. 6464–6473). New Pub: Balaban. 45. Lee, S. H., Heng, D., Ng, W. K., Chan, H. K., & Tan, R. B. H., (2011). Nanospray drying: A novel method for preparing protein nanoparticles for protein therapy. International Journal of Pharmaceutics, 403(1, 2), 192–200. 46. Lee, Y. H., Wu, B., Zhuang, W. Q., Chen, D. R., & Tang, Y. J., (2011). Nanoparticles facilitate gene delivery to microorganisms via an electrospray process. Journal of Microbiological Methods, 84(2), 228–233. 47. Liu, B., Wang, D., Gao, X., Zhang, L., Xu, Y., & Li, Y., (2011). Removal of arsenic from laminaria japonica aresch juice using As(III)-imprinted chitosan resin. European Food Research and Technology, 232(5), 911–917. 48. López-López, E. A., Hernández-Gallegos, M. A., Cornejo-Mazón, M., & HernándezSánchez, H., (2015). Polysaccharide-based nanoparticles. Food Engineering Series, 4, 59–68. 49. Ma, G., Yang, D., Li, Q., Wang, K., Chen, B., Kennedy, J. F., & Nie, J., (2010). Injectable hydrogels based on chitosan derivative/polyethylene glycol dimethacrylate/N,Ndimethyl acrylamide as bone tissue engineering matrix. Carbohydrate Polymers, 79(3), 620–627. 50. Malik, R., Ramteke, D. S., & Wate, S. R., (2007). Adsorption of malachite green on groundnut shell waste based powdered activated carbon. Waste Management, 27(9), 1129–1138. 51. Maruthamuthu, M. K., Ganesh, I., Ravikumar, S., & Hong, S. H., (2014). Evaluation of zraP gene expression characteristics and construction of a lead (Pb) sensing and removal system in a recombinant Escherichia coli. Biotechnology Letters, 37(3), 659–664. 52. Mehta, P., Haj-Ahmad, R., Rasekh, M., Arshad, M. S., Smith, A., Van, D. M. S. M., Li, X., et al., (2017). Pharmaceutical and biomaterial engineering via electrohydrodynamic atomization technologies. Drug Discovery Today, 22(1), 157–165. 53. Mihalca, V., Kerezsi, A. D., Weber, A., Gruber-Traub, C., Schmucker, J., Vodnar, D. C., Dulf, F. V., et al., (2021). Protein-based films and coatings for food industry applications. Polymers, 13(5), 769. doi: 10.3390/POLYM13050769. 54. Muga, H. E., & Mihelcic, J. R., (2008). Sustainability of wastewater treatment technologies. Journal of Environmental Management, 88(3), 437–447. 55. Nematidil, N., Nezami, S., Mirzaie, F., Ebrahimi, E., Sadeghi, M., Farmani, N., & Sadeghi, H., (2021). Fabrication and characterization of a novel nanoporous nanoaerogel based on gelatin as a biosorbent for removing heavy metal ions. Journal of Sol-Gel Science and Technology, 97(3), 721–733. 56. Nishikiori, H., Tanigaki, T., Endo, M., & Fujii, T., (2014). Quantitative characterization of acidic groups on acid-treated multi-walled carbon nanotubes using 1-aminopyrine as a fluorescent probe. Carbon, 66, 560–566. 57. Ozpolat, B., Sood, A. K., & Lopez-Berestein, G., (2014). Liposomal siRNA nanocarriers for cancer therapy. Advanced Drug Delivery Reviews, 66, 110–116. 58. Palareti, G., Legnani, C., Cosmi, B., Antonucci, E., Erba, N., Poli, D., Testa, S., & Tosetto, A., (2016). Comparison between different D-Dimer cutoff values to assess the

268

Sustainable Nanomaterials for Biosystems Engineering

individual risk of recurrent venous thromboembolism: Analysis of results obtained in the DULCIS study. International Journal of Laboratory Hematology, 38(1), 42–49. 59. Pan, B., & Xing, B., (2008). Adsorption mechanisms of organic chemicals on carbon nanotubes. Environmental Science and Technology, 42(24), 9005–9013. 60. Panigaj, M., & Reiser, J., (2016). Aptamer guided delivery of nucleic acid-based nanoparticles. DNA and RNA Nanotechnology, 2(1), 42–52. 61. Peltonen, L., Valo, H., Kolakovic, R., Laaksonen, T., & Hirvonen, J., (2010). Electrospraying, spray drying and related techniques for production and formulation of drug nanoparticles. Expert Opinion on Drug Delivery, 7(6), 705–719. 62. Pillai, C. K. S., Paul, W., & Sharma, C. P., (2009). Chitin and chitosan polymers: Chemistry, solubility, and fiber formation. Progress in Polymer Science, 34(7), 641–678. 63. Qi, B., Wang, C., Ding, J., & Tao, W., (2019). Editorial: Applications of Nanobiotechnology in Pharmacology. Frontiers in Pharmacology, 10, 1451. doi: 10.3389/FPHAR. 2019.01451. 64. Qi, Y., Jiang, M., Cui, Y. L., Zhao, L., & Zhou, X., (2015). Synthesis of quercetin loaded nanoparticles based on alginate for Pb(II) adsorption in aqueous solution. Nanoscale Research Letters, 10(1), 1–9. 65. Ramezani, R., Sadeghizadeh, M., Behmanesh, M., & Hosseinkhani, S., (2013). Characterization of zwitterionic phosphatidylcholine-based bilayer vesicles as efficient self-assembled virus-like gene carriers. Molecular Biotechnology, 55(2), 120–130. 66. Ren, H., Gao, Z., Wu, D., Jiang, J., Sun, Y., & Luo, C., (2016). Efficient Pb(II) removal using sodium alginate–carboxymethyl cellulose gel beads: Preparation, characterization, and adsorption mechanism. Carbohydrate Polymers, 137, 402–409. 67. Saallah, S., & Lenggoro, I. W., (2018). Nanoparticles carrying biological molecules: Recent advances and applications. KONA Powder and Particle Journal, 35, 89–111. 68. Santhosh, C., Velmurugan, V., Jacob, G., Jeong, S. K., Grace, A. N., & Bhatnagar, A., (2016). Role of nanomaterials in water treatment applications: A review. Chemical Engineering Journal, 306, 1116–1137. 69. Shao, D., Jiang, Z., Wang, X., Li, J., & Meng, Y., (2009). Plasma induced grafting carboxymethyl cellulose on multiwalled carbon nanotubes for the removal of UO22+ from aqueous solution. Journal of Physical Chemistry B, 113(4), 860–864. 70. Sharma, P. R., Chattopadhyay, A., Sharma, S. K., Geng, L., Amiralian, N., Martin, D., & Hsiao, B. S., (2018). Nanocellulose from spinifex as an effective adsorbent to remove cadmium (II) from water. ACS Sustainable Chemistry & Engineering, 6(3), 3279–3290. 71. Tamjidi, F., Shahedi, M., Varshosaz, J., & Nasirpour, A., (2013). Nanostructured lipid carriers (NLC): A potential delivery system for bioactive food molecules. Innovative Food Science & Emerging Technologies, 19, 29–43. 72. Thakur, S., Govender, P. P., Mamo, M. A., Tamulevicius, S., Mishra, Y. K., & Thakur, V. K., (2017). Progress in lignin hydrogels and nanocomposites for water purification: Future perspectives. Vacuum, 146, 342–355. 73. Tian, D., Hu, J., Bao, J., Chandra, R. P., Saddler, J. N., & Lu, C., (2017). Lignin valorization: Lignin nanoparticles as high-value bio-additive for multifunctional nanocomposites. Biotechnology for Biofuels, 10(1), 1–11. 74. Varghese, A. G., Paul, S. A., & Latha, M. S., (2018). Remediation of heavy metals and dyes from wastewater using cellulose-based adsorbents. Environmental Chemistry Letters, 17(2), 867–877.

Advanced Bionanomaterials for Heavy Metals 269 75. Warluji, R. R., Lakkakula, J. R., Kolekar, N. S., Mendhulkar, V. D., & Kashid, S. B., (2009). Phytosynthesis of silver nanoparticle using Gliricidia sepium (Jacq.). Current Nanoscience, 5(1), 117–122. 76. Wang, B., Gao, B., Zimmerman, A. R., & Lee, X., (2018). Impregnation of multiwall carbon nanotubes in alginate beads dramatically enhances their adsorptive ability to aqueous methylene blue. Chemical Engineering Research and Design, 133, 235–242. 77. Wang, L., & Wang, A., (2007). Adsorption characteristics of Congo red onto the chitosan/ montmorillonite nanocomposite. Journal of Hazardous Materials, 147, 979–985. 78. Wang, T., Jin, X., Chen, Z., Megharaj, M., & Naidu, R., (2014). Green synthesis of Fe nanoparticles using eucalyptus leaf extracts for treatment of eutrophic wastewater. Science of the Total Environment, 466, 467, 210–213. 79. Yurteri, C. U., Hartman, R. P. A., & Marijnissen, J. C. M., (2010). Producing pharmaceutical particles via electrospraying with an emphasis on nano- and nanostructured particles: A review. KONA Powder and Particle Journal, 28, 91–115. 80. Yuwei, C., & Jianlong, W., (2011). Preparation and characterization of magnetic chitosan nanoparticles and its application for Cu (II) removal. Chemical Engineering Journal, 168(1), 286–292.

CHAPTER 10

ADVANCED BIONANOMATERIALS USED TO RECOVER POLLUTANTS FROM WASTEWATER NOSHIN AFSHAN, ALINA BARI, AYUB KHAN, and YAQOOB SHAH

ABSTRACT The pollution of water bodies through the accumulation of heavy metals is a common and serious environmental issue. A variety of harmful toxic chemicals contaminate water, specifically heavy metals, dyes, and microorganisms which adversely affect the ecological balance of humans and the ecosystem. Hence, there is a compelling need for new technologies to recover the toxic wastes from wastewater. Bionanomaterials, for example, bionanoparticles (BNP), bionanoframeworks, bionanochannels, and bionanocomposites being biocompatible, eco-friendly, highly reactive, programmable along with greater surface area have been widely used in several fields such as theranostics, drug delivery, ceramics, semiconductors, and nanoelectronics, nanomedicine, cosmetics, and recovery of total dispersed solid, heavy metals and radioactive metals from wastewater. The field of bionanotechnology has revolutionized wastewater treatment process as they have been employed to recover heavy metals including copper, nickel, lead, mercury, and arsenic (As); nutrients including phosphate, nitrate/nitrite, ammonia, cyanide, and suspended organic matter; microorganisms such as algae, bacteria, viruses, and radioactive metals like Pollutinum. In this chapter, a variety of bionanomaterials, their properties, and applications in different fields specifically to recover pollutants from wastewater rendering it reusable would be explained in detail. They have several advantages over the conventional materials for pollutants recovery, offering practical solutions to the water pollution problem worldwide. Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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10.1 INTRODUCTION Modern science has promoted human beings from the dark ages to modern times through rapid technological progress. Since science has been serving humanity, their relentless pursuit of more modern facilities has caused significant environmental damage [11]. The World Health Organization (WHO) pointed out that environmental pollution has been causing lethal effects. Almost 270,000 children are dead per annum, depriving the population of clean water and fresh air. Air pollution has been deteriorating at different rates worldwide, especially in countries with low-tech manufacturing industries [7]. Among different types of environmental pollution, water pollution caused by chemical pollutants has a significant impact on human health. Drinking water is a basic necessity for the living species. To ensure clean drinking water, it is necessary to strictly monitor the chemical pollutants such as toxins, heavy metals, and pollutants of organic and inorganic nature, whether caused naturally or as a result of human activities. Heavy metal ions like Hg2+, Pb2+, Cr3+, and Cu2+ harm human health if they enter the drinking water supply system. They become dispersed to the environment in various ways, including the runs from new mines and wastes from metal processing units, intentionally used chemical agents such as wood preservatives, and industrial processes such as tanning that uses metal components. A range of dangerous anions, including NO3–, SO42–, PO43–, F–, Cl–, C2O42–, enters the groundwater resources through the leakage of wastewater discharged from industries and chemical storage sites. Their presence in high concentration deteriorates the taste and color of the water. Such poisonous pollutants have been fatal even at low concentrations of a few parts per million and may cause such lethal diseases as cardiovascular, cancer, and hepatitis. For example, the blue baby syndrome, methemoglobinemia, has been caused by increased nitrate concentration and fluorosis by the accumulation of fluoride in drinking water [21]. In addition to inorganic poisons, different kinds of organic poisons have been discovered, including phenols, fertilizers, pesticides, HCs, biphenyls, plasticizers, oils, detergents, drugs, and greases. Moreover, environmental pollution arising from solid waste in the form of industrial waste is one of the world’s main issues today [11, 21]. Like its counterparts, the textile industry has continuously been growing, leading to significant contributions to global advances and eliminating a considerable amount of highly toxic colored contaminants that pollute the environment. Compared to natural

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dyes, synthetic dyes are cost-effective and stable to light, temperature, detergents, and microbial attack, with their profound applicability in the textile and dyeing units. The azo dyes constitute a considerable part of the synthetic dyes and are discharged almost up to 10–15% as industrial wastes in the water resources during the manufacturing process. They are highly toxic and carcinogenic, severely polluting the environment [20]. Due to the clean emissions of GHGes and economically less competitive, nuclear power generation has been an imperative renewable energy alternate globally. Widespread application of nuclear technological tools like nuclear energy generation, nuclear weapon testing, medical, and mining industries has liberated such radionuclides-based pollutants into the water resources as 137Cs, 90Sr, 144Ce, 152Eu 106Ru, 60Co, and 241Am. Moreover, the nuclear mishaps, such as the one in Fukushima in 2011, have caused lifelong problems for generations. It is evident from the literature that the most radionuclides polluting the water resources render very long half-beaks. Their long-term radiological and chemically toxic nature renders them a significant environmental hazard even in traces. In addition, radionuclides can directly damage the biological systems and produce reactive species that severely endanger all life forms, including humans, after reacting with the biomolecules via inhalation from radiation sources. The dissolved radionuclides are non-biodegradable with powerful environmental perseverance and bioaccumulation with the food chain [33]. Nowadays, environmental pollution caused by heavy metals, solids, and radioactive metals has become one of the most severe problems to be solved urgently. It has a significant impact on human health and social development globally [31]. The United States Environmental Protection Agency has organized some limits for various pollutants leading to their standard detection and monitoring to minimize their risks to human health and the environment [11]. Many attempts led to the development of some effective methods to monitor heavy metal ions in the environment, such as atomic absorption spectroscopy [23], chromatography [29], chemiluminescence, electrochemical analysis [32], and fluorescence spectroscopy [28] with excellent sensitivity and selectivity [31]. However, most of them require expensive instruments, complicated experimental techniques, and limited accuracy [30, 31]. Recently, the combined knowledge in different fields such as chemistry, physics, biology, and NT has paved the way towards sensitive imaging and ultra-sensitive detection modes. Since the last few decades, the development of nanoparticles (NPs) as functional probes for detecting chemical pollutants, including heavy metal ions, has promoted environmental protection.

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NPs range in size from 1–100 nm and render some unique properties such as solid physical restriction on electron-hole pairs and the greater surface area contributing to higher sensitivity and rapid response capability. They may change their physical properties such as magnetism, electronics, and optics controlling their shape, size, surface chemistry, and composition, thereby functioning as highly efficient molecular probes. For NP production employed for the pollutants recovery process, biosynthesis has given many promising outcomes, eliminating the limitations associated with traditional synthesis methods [11]. The nanocomposites (NCs), a class of NMs, have attracted widespread attention due to their unique chemical and physical specificities such as improved stability, easy preparation, affordable cost, and enhanced activity [9, 31]. In particular, Yan et al. developed a series of active nano-enzymes such as carbon nanomaterials (CNMs), alloys, metal oxides (MO), metal sulfides, metal-organic framework, and fabricated G-quadruplexes [9, 31]. It can enhance the catalytic activity of the NC-based nano-enzymes by controlling their size, morphology, structural components, crystal faces, and surface coatings. They have found many applications, especially in the chemical and biological sensing of heavy metal pollutants in the aquatic environment with the detection limit in nmol/L. Hence, various advanced bionanomaterials, their properties, and applications in different fields specifically to recover pollutants from wastewater rendering it reusable, have been focused around the globe [31]. A variety of bionanomaterials, their properties, and applications in different fields specifically to recover pollutants from wastewater rendering it reusable would be explained in this chapter. The bionanomaterials have several advantages over the conventional materials for pollutants recovery, offering practical solutions to the water pollution problem worldwide. 10.1.1 BIONANOMATERIALS Bionanomaterials are promising materials produced from various biological elements such as plants, bacteria, fungi, peptides, nucleic acids, etc. Bionanomaterials utilities in biomedicine have gained keen attention because they have been synthesized biologically and are biocompatible. Due to their miniature size, bionanomaterials exhibit remarkable properties that help them acquire potential in different domains such as pollutants recovery, aerospace engineering, materials science, pharmacology, biosensors, etc.

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Moreover, various characterization techniques have been used to study the properties of the synthesized bionanomaterials [26]. Bionanomaterial is defined as a molecular material consisting of biological molecules such as proteins, antibodies, enzymes, nucleic acids, lipids, poly-, and oligosaccharides, viruses, and secondary metabolites. It can also use to create complex devices through self-assembly in environmentally friendly and lightweight conditions. The objective is to produce such material by combining artificial or non-biological materials with natural compounds for non-biological use. Thus, many naturally occurring biodegradable polymers and NMs have widespread applications in biomedical, packaging, bioadsorption, pharmaceutics, industries, and agriculture [26]. 10.1.2  CATEGORIES OF BIONANOMATERIALS There are following categories of bionanomaterials: • • • •

Organic bionanomaterials; Biological bionanomaterials; Inorganic bionanomaterials; and Synthetic bionanomaterials

10.1.2.1  ORGANIC BIONANOMATERIALS The access of organic bionanomaterials in biomedicine has attracted close attention leading to their widespread application in various fields as bone or tissue regeneration and scaffold formation. To better serve humanity and the ecosystem, they should meet specific biodegradability, biocompatibility, and non-toxicity. They include silk fibroin, chitosan, and biodegradable polymers such as polylactic acid, and glycolic acid (PLGA). Although PLGA is considered a synthetic polymer, keeping in view its biocompatibility, it is now classified as an organic bionanomaterial. PLGA bionanomaterials can be easily manufactured from various natural and synthetic materials to produce nanofibers or nano-scaffolds used in tissue engineering and drug delivery applications. Silk fibroin is a natural polymer with a significant molecular weight extracted from spiders and silkworms. It demonstrates various biomedical applications such as regenerative medicine, effectively exhibiting controlled drug delivery at the cellular level. To enhance the scope of its applications, it can be functionalized adding different functional

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groups, for example, the functionalized silk fibroin acting as a nanocarrier loaded with cisplatin to prevent the cytotoxicity and side effects of drugs, not only helps to deliver drugs and genes to cancer cells rather it also regulates the drug release dynamics. Moreover, the linear polysaccharide-based bionanomaterial – chitosan – has played a potential role in bone formation therapy, such as developing tissue regeneration scaffold and promoting bone regeneration with the help of collagen [26]. The PLGA combined with chitosan produces nanostructures that can be used in dentistry and wound healing [5, 26]. Various cancer treatment drugs include cisplatin, paclitaxel, doxorubicin, triptorelin, xanthone, 9-nitrocamptothecin, dexamethasone, and 5-fluoropyrimidine, have been successfully included in PLGA, PLA, and PCL NPs. Polymer-based bionanomaterials have also become a new carrier for the drugs and their controlled release. Moreover, silica is considered the most diverse compound in the material family as it easily coexists with other minerals. Silica-based bionanomaterials have unique characteristics such as small-sized, greater surface area, strong absorption capacity, adjustable pore volume, and pore size, good hydrophilicity, and biocompatibility, which enable a variety of applications such as pollutants detection and their recovery [26]. 10.1.2.2  BIOLOGICAL BIONANOMATERIALS At present, biologically derived bionanomaterials have received significant attention from researchers in the field of biomedicine. They can be further divided into two types: natural and green bionanomaterials. Natural bionanomaterials include specific lipoproteins, DNA or RNA, and peptides, and green bionanomaterials have been derived from such sources as plants, bacteria, fungi, and viruses. The naturally derived bionanomaterials, lipoproteins, are hydrophobic biomolecules composed of lipids and proteins with spherical shapes in nanometer size. Lipoproteins are widely used in drug delivery and cancer diagnosis. Bionanomaterials based on lipoproteins have biocompatibility, biodegradability, and blood circulation stability, making them more suitable for biomedical applications such as gene therapy and imaging. Similarly, peptide bionanomaterials can be modified either by molecular self-assembly or combining with other NMs resulting in structural changes. Linking strands of specific oligonucleotide sequences, the small size (6–10 nm) of the central core of peptide bionanomaterials, have been widely used in fluorescence imaging and gene delivery. The peptide-based bionanomaterials exhibit antibacterial properties, drug delivery, and gene therapy [26].

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In addition, deoxyribonucleic acid (DNA) is a biomolecule composed of base pairs that can store the genetic information of an organism and is considered to be the most widely used biomolecule in NT. Its unique physical and chemical properties have been used in various biomedical applications. Different forms of DNA have been used in the field of biomedicine to produce sensors, imaging probes, and therapeutics. DNA-based biosensors have attracted much interest because they have been used in all fields of biology, environment, industry, and pharmaceuticals. They play various roles, such as biosensors for detecting solids and heavy metals, followed by their subsequent recovery, linking strand recognition motifs and probes [24]. Cancer is considered one of the leading causes of death worldwide, and treatment methods such as radiotherapy and chemotherapy have many side effects on the human body. Therefore, it is necessary to develop some alternative drugs for the treatment of cancer. DNA nanostructures render unique characteristics and are widely used to create various heterogeneous anticancer agents for targeted cancer therapy. Moreover, a variety of DNA nanostructures have been developed for chemotherapeutic drug loading platforms and aptamer-based delivery systems, which will precisely determine in-vivo drug uptake [26]. 10.1.2.3  INORGANIC BIONANOMATERIALS Various bionanomaterials are analogs of natural materials having inorganic nature, such as peptide nucleic acid (PNA), aptamer, and xeno-nucleic acid (XNA). PNA being synthetic bionanomaterial, is analog of either RNA or DNA, leading to achiral and uncharged mimics and retaining more excellent stability and specificity. Although it is usually considered to be DNA, it is composed of a neutral peptide backbone. For this reason, it lacks electrostatic repulsion, which helps it show a great affinity for the target. Such change in its skeleton gives it a unique set of physical and chemical properties such as resistance to enzymatic degradation in living cells, offering various applications. Its ability to quickly identify specific RNA or DNA sequences via Watson-Crick base pairing renders it to display unique ionic strength and thermal stability. It shows potential biomolecular tools, biosensors, antisense, antigen reagents, and molecular probes. The nucleic acid biosensors are one of the tested applications in genetics and biomedicine that use PNA exclusively. It can be used to develop high-performance biosensors suitable for DNA genotyping through research on specificity and sensitivity has yet to be explored [26].

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10.1.2.4  SYNTHETIC BIONANOMATERIALS Various metals and their oxides based on bionanomaterials used in the field of biomedicine are the most widely studied elements in bionanotechnology, and many NMs have essential uses in different fields. Metal and metal oxidebased NMs are easy to synthesize and characterize because they exhibit excellent properties that make them unique and different from bulk materials. Although they can be synthesized by chemical, physical, or biological means, biosynthetic bionanomaterials have attracted much attention because they are cost-effective, lack chemical toxins, and do not cause any side effects on the environment and living environment organisms [18, 26]. Since commonly used metal-based bionanomaterials include gold (Au), silver, iron, copper, zinc, and nickel, researchers have focused on different metals, such as cerium, selenium, and magnesium. The unique properties of metalbased bionanomaterials, such as size, shape, and conductivity, make them the most common bionanomaterials in biomedical applications because they can use them for diagnosis and treatment. When such bionanomaterials undergo fabrication with other compounds, their properties get refined, increasing their utility. Moreover, they have also been manipulating for solids and metals recovery [26]. 10.1.3  CHARACTERIZATION OF BIONANOMATERIALS The characteristics of bionanomaterials are based on their size and preparation methods, as they follow various techniques for their preparation. Their main characteristics are dimension, shape, texture, surface charge/area, porosity, texture, quantitative strength, surface functionality index, surface shape, and the extent of stability, crystalline nature, magnetism, and surface texture. Using them without characterization can result in variability and error in results. Due to the conditional variability of bionanomaterials, their application value would be limited if they proceed without characterization. Hence, various techniques have been designed for the characterization of bio-nanomaterials, which mainly include UV-VIS spectroscopy, atomic force microscopy, Fourier transformed IR spectroscopy (FTIR), transmission electron microscopy, potentiometric analysis, scanning electron microscopy (SEM), photoluminescence spectroscopy (PL), scanning probe microscopy (SPM), Raman spectroscopy and energy dispersive X-ray (EDX) analysis [8, 26].

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10.1.4  PROPERTIES OF BIONANOMATERIALS The basic properties of materials usually vary on the nanoscale. Thus, the properties of NPs might differ materially from the properties of atoms and heavy materials of the same substance. A brief outline of their properties is given in subsections. 10.1.4.1  ELECTRICAL PROPERTIES Such properties of bionanomaterials such as nanotubes, nanorods, and nanocomposites depend on their diameter and differ from the electrical properties of metal and semiconductor materials, primarily due to their electrical or photoconductivity. Depending upon their electrical properties, bionanomaterials improve the performance of electronic bio-nanogadgets and reduce power utilization [8]. 10.1.4.2  OPTICAL PROPERTIES The optical properties of bionanomaterials rely upon their dimension, shape, surface qualities, and factors, for example, doping-and conjugation with the encompassing substances [8]. 10.1.4.3  MECHANICAL PROPERTIES The bionanomaterials are exceptionally solid and may withstand intense strains since they have minor primary imperfections. Some of their unique mechanical properties were reviewed, stating that the bionanomaterials show new applications in surface engineering, tribology, and nanomanufacturing [8]. 10.1.4.4  MAGNETIC PROPERTIES The nanoscale particles exhibit a unique atomic structure with discrete electronic states. In addition to superparamagnetic behavior, they have unique properties for imaging, biological processing, refrigeration, and high-density magnetic storage media. For example, magnetic NCs (MNCs) are widely

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utilized for magnetic refrigeration, information storage, and ferrofluid mechanical energy transfer. Contrarily, such metals as platinum and Au, despite being non-magnetic, are magnetic at nanometer scale [8]. 10.1.5  IMPACT OF BIONANOMATERIALS IN ENVIRONMENTAL RECOVERY PROCESS Bionanomaterials have essential applications in food, cosmetics, machine learning, pharmaceutical, agricultural, electrical, optical, and power generation industries. They have a wide range of utilities in environmental remediation, thereby monitoring the pollutants and converting them from toxic to less/non-toxic forms. They are equally effective for the pollutants in all the media, such as in air, water, and soil [8]. 10.1.5.1  TOTAL DISPERSED SOLID, HEAVY METALS AND TRANSITION METALS IN WASTEWATER Water pollution by heavy metal ions, Solids, and transition metals has been a significant concern worldwide. Heavy metals like Hg, As, Pb, Cr, Co, Ni, Cu, and Cd, Solids like toxins, dyes, inorganic pollutants, textile effluents, and radioactive metals such as Uranium, Cobalt, Radium, and Polonium are highly toxic and carcinogenic even in traces. They do not undergo biodegradation and accumulate in the food chain, causing serious risks to the environment and human health. Thus, the advancement of sensitive and straightforward techniques has been a concern for researchers [11]. Effluents from textiles, leather, tanning, electroplating, galvanization, dyes, paints, metallurgical industries, and metal handling and refining activities contain many poisonous metal particles. My tails and effluents from the industries which deal with the environmentally excluded non-ferrous metals act as the primary resources of heavy metals. For example, gasoline-based materials are the primary source of lead. The electroplating industry and galvanized units are the main applications for zinc in paints, rubber, dyes, wood preservatives, ointment, etc. Copper mainly works in the electrical goods industry and copper production. The utilization of cadmium is expanding in modern applications, for example, electroplating, pigments, and batteries manufacturing [4].

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10.1.5.2  BIONANOMATERIALS AS SORBENTS FOR POLLUTANTS RECOVERY The adsorption interaction is the most broadly utilized technique for extracting various contaminants from water. Adsorption is the surface phenomenon of adsorbate deposition, which is pollutant onto the adsorbent surface (solid surface) using physical adsorption (van der Waals adsorption), chemical adsorption (adsorption activated by chemical bonds, electrostatic attraction, π-π interaction, etc.), or both of the physical and chemical adsorption (Chemisorption) mechanisms. It depends on the type of attractive forces in the adsorbent and the adsorbate. Though both are exothermic processes, Physical adsorption is faster forming multi-molecular layers, and chemical adsorption requires activation energy constantly forming a single layer [4]. Water treatment by adsorption uses solid materials called adsorbents to remove pollutants or adsorbate. The zeolite, silica gel, and Activated carbon were conventionally employed as adsorbents for the purification of water or gas and various catalytic applications. Up to dated general examples of adsorbents include minerals, organic or biological materials based on oxygen, carbon, or polymers. Owing to the element constitution and the functional groups attached, the adsorbent may be categorized as hydrophilic, non-polar, or hydrophobic. The commonly modified CNM and carbon-based NCs have been designed to enhance the adsorption capability of such pollutants as dyes, heavy metals, radioactive metals, and organic matter. CNMs serve as the highly advantageous sustainable source of adsorbents rendering greater surface area, high aspect ratio, enhanced functional ability, improved colloidal stability, easy regeneration, and good compatibility for different pollutants [4, 17]. 10.1.5.2.1  Bionanoadsorbents for Total Dispersed Solid Recovery 1. Extraction of Solid Waste and Dyes: The textile, paper, pharmaceutical, food, dye, and tanning industries are the primary purchasers of dyes. They contribute as the primary source of organic pollutants released in industrial wastewater. Such industrial pollutants and their degradation byproducts are carcinogenic, causing environmental pollution. Therefore, to control industrial pollution, various techniques such as nanofiltration (NF), electrochemical coagulation, adsorption, membrane processes, and reverse osmosis have been carried out to

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treat the wastewater dyes. A more efficient and economical method for removing the dye is adsorption that can be studied either in a static or dynamic operating model. In the static mode, the adsorption capacity generally depends upon the initial dye concentration. In the dynamic mode, besides the dye’s initial concentration, that depends upon the flow rate and the physical properties of the adsorbent, such as surface area, aspect ratio, and dimension. Dyes may be either cationic or anionic, and that is why the interaction between dye and nanocellulose depends on the functional groups attached with the nanocellulose and dye molecules. Usually, anionically functionalized nanocellulose through carboxylation and sulfonation has been employed to adsorb cationic dyes, including methylene blue (MB) and crystal violet. The cationic functionalized nanocellulose through amino modification has been utilized to extract anionic colors, for example, Congo red 4BS and K-4G yellow reactive. The strength of ion exchange and electrostatic attraction depends on the pH value because of the nature of functional groups attached with the adsorbate and adsorbent [4]. 2. Extraction of Organic Pollutants: When organic pollutants in domestic wastes, urban runoff, industrial wastewater, and farm waste streams enter freshwater resources, water pollution based on organic matter occurs. Insecticides, detergents, soaps, food additives, drugs, pesticides, paints, pigments, volatile organic compounds, and plastic wastes are well-known toxins in the environment and water resources. The low concentration of the organic pollutants, even in traces, may cause the water’s depletion of dissolved oxygen (DO). They are toxic and carcinogenic, making water non-drinkable and unsafe for a variety of applications. Hence, such organic pollutants removal from water bodies is crucial for environmental and human advancement. For this purpose, distillation, filtration, ultrafiltration, solvent extraction, adsorption, and oxidation strategies have been efficiently practiced—the adsorption strategy is the leading one for being cost-effective and extraordinarily efficient. The activated carbon and zeolites are the most widely used absorbents to recover organic wastes and toxins from effluents. Failure for regrowth and the significantly high expense of activated carbon limits its applicability [4]. Excellent adsorption efficiency, improved binding affinity, enhanced surface area, affordable cost, and regeneration of cellulose-based NPs

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render it an advantageous NM for adsorbing organic pollutants. It has been found that the modified cellulose NPs have been far stronger materials for the adsorption of organic pollutants than the virgin ones. For example, ether-based cellulose nanocrystals (CNC) NCs showed 40% Ethinyl estradiol adsorption in which the CNC/cyclodextrin matrix material absorbed as much as 80% of the phenolic group. The cellulose nanofibrils (CNF) modified materials, especially CNF/ hexadecyl amine, showed various phenolics’ adsorption ability. Such modifications assisted in extracting organic contaminants such as alachlor, linuron, and phenolic like atrazine’s found in the organic herbicides. Absorption is a bulk phenomenon in which contaminants have been dispersed (partitioned) into a large portion of the adsorbent retaining its microporous structure [4]. 3. Hydrocarbon and Water Separation Through Absorption: Aerogels have been effectively used for the recovery of HCs such as oil from water. The type of flow employed in such recovery process is unusually formed because of oil and chemical effluents and wastewater disposal from the petrochemical industries. Aerogels have been naturally occurring porous matrices rendering the low value of density, improved porosity, enhanced surface area, and finishing with inorganic, organic, and CNMs. Traditional absorbents such as polypropylene, zeolite, and activated carbon have been often utilized for treating oily wastewater. Nanocellulose-based aerogels have improved porous texture, greater surface area, and enhanced absorption selectivity for water and HC solvents compared to the traditional polypropylene absorbents. Various CNFs have been preferred over CNC to synthesize aerogels with the dissolution or dispersion of nanocellulose, sol-gels, and freeze-drying processes, which also maintain the existing 3-D microporous structure [4, 17]. Their selectivity for oil and water separation systems can be increased through hydrophobicity and lipophilicity enhancement through surface roughness or the fiber surface modification employing low-surface-energy materials. Their separation efficacy depends on the characteristics of the oil and the aerogels, including viscosity, density, surface tension, and morphology. The polar-polar interaction tempted by hydroxyl groups induces the high solvent absorption for such solvents as dimethyl sulfoxide (DMSO), ethanol, and water. For example, their absorption capacity for oils and solvents has been improved by increasing the density of oil

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and solvent and their fabrication through hydrophobic NMs. Their absorption capacity has been significantly improved compared to that of the synthetic polymers and CNFs based absorbents. The CNTs and graphene-based aerogels render higher absorption capacity as compared to the nanocellulose-based aerogels. However, the amphyllic aerogels show the highest absorption capacity for recovering HCs such as oils [4, 17]. Mechanical squeezing has preferably been applied to recover adsorbent from aerogels. Hence, the aerogels must be mechanically strong enough to go with several cycles of mechanical compression and expansion [4]. 10.1.5.2.2  Bionanoadsorbents for Heavy Metals Recovery Natural weather conditions and artificial processes (industry, agriculture, wastewater, mining, and metallurgy) contribute as the primary source of heavy metal ions such as mercury, As, cadmium, and chromium that pollute the surface water and groundwater resources. They are highly toxic, carcinogenic, non-biodegradable, and are quickly accumulated in the body. The most commonly employed techniques to recover heavy metal ions from the water resources include adsorption, ion exchange, membrane, and coagulation or flocculation. The absorption capacity depends on the pH of the medium and the electronegativity value of the metal ions. For example, at low pH, anionic groups such as carboxylate, sulfates, and phosphates attached with the nanocellulose undergo protonation, lowering metal ions’ adsorption. Contrarily, the increase in pH retards protonation, thereby speeding up the adsorption process. Nanocellulose in CNC and CNF can be revived through washing with ethylenediaminetetraacetic acid (EDTA) or dilute nitric acid, hydrochloric acid, or sulfuric acid. As the affinity of nanocellulose for metal ions increases, its efficiency to regenerate decreases [4, 6]. Since the NMs have efficiently been linked with the biomolecules like chitin and chitosan to develop novel bionanomaterials showing improved metal recovery efficiency, chitin works with the –SH group to increase its adsorption efficiency for heavy metals such as As (III) caused by the electrostatic interactions among the metal ions and the protonated-NH2 group present in the chitin nanofibers. Hence, the inorganic and organic interfaces are an excellent platform for extracting, absorbing, or assimilating the metal particles, for example-NH2 functional group for the heavy metals. Hence, the surface concentration of the –NH2 group is significant to regulate its

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functional efficiency. Moreover, inorganic, and organic coupling imparts stability and chelating capabilities leading to the trapping of metal ions for their efficient removal. The coupling characteristic is based on the organic phase thickness, location-based conditions, and particle morphology. However, the presence of bulky functional moieties on the surface of bionanomaterials assists their recovery using the ligand-metal complexes and electrostatic interactions. Since bionanomaterials have successfully experimented for the recovery of divalent, trivalent, and pentavalent heavy metal ions, the trials for the recovery of hexavalent heavy metal ions have been at their embryonic stage [10]. 10.1.5.2.3  Bionanoadsorbents for Radioactive Metals Recovery Due to their long-lasting chemical and radiological toxicity, the significant radionuclides in the aquatic ecosystem have acted as a significant environmental hazard. They can either directly damage the biological system or generate reactive species that react with biomolecules by inhaling nearby sources of radiation that seriously endanger life forms. In addition, radionuclides are non-biodegradable and are thought to have strong environmental sustainability and in vivo accumulation through the food chain [33]. To date, several traditional techniques have been reported for the recovery of soluble radionuclides, including ion exchange, adsorption, evaporation, and membrane separation [34]. In this regard, the main objective is to safely enhance the operational efficiency and separation rate at the minimum substrate dose concentration. Solid disposal and wastewater treatment practices are unsuitable for the disposal of radionuclides containing wastewater. Hence, advances in environmentally sustainable bionanomaterials such as CNC and CNF have offered various opportunities to develop the nextgeneration radioactive recovery technologies because they exhibit unique specificities such as greater surface-area, improved mechanical strength, and high strength aspect ratio, excellent surface functionalization, and largescale availability [33]. The ultrafine CNF, prepared by the oxidation of wood pulp, has been reported as a sound absorbent with profound applicability for recovering radioactive ions like UO22+ from wastewater. Adding the UO22+ suspension to the CNF leads to gel formation based on the coordination between the negatively charged carboxylate groups on the CNF with the positively charged UO22+ [33].

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In general, CNC, and CNF have been prepared from a range of cellulose NMs such as wood, plants, tunics, bacteria, and algae. Agricultural waste is one of the eco-friendly and economically viable materials transformed into useful absorbents. The raw materials such as pineapple peel, sugar cane, coconut fiber, and lime peel enriched with cellulose content have been converted into adsorbents serving as potential bionanomaterials for the treatment of radionuclides contaminated water. For example, the banana peel has been employed to recover Thorium and Uranium from radionuclides contaminated water [33]. 10.1.6  PHOTOCATALYSIS BY BIONANOMATERIALS Bionanomaterials and NPs have been progressively employed as photocatalysts. Being catalytically inactive in their bulk form, they may secure catalytic properties in their nanoscale counterparts. Those with good catalytic activity in the bulk form often exhibit enhanced catalytic activity in their nanoscale counterparts because nanostructures have a greater surface area, improved crystallinity, and upgraded exposed grain boundaries. The advances in NT and bionanotechnology have been dependent on NMs synthesis. They have inspired researchers to develop novel and highly effective synthetic strategies [13]. Bionnanomaterials efficiently act as photocatalysts accelerating lightinduced reactions. This technique has widespread applications in the photocatalytic treatment of water recovery and photocatalytic decomposition of the pollutants in water. During photocatalysis, the photocatalyst is irradiated with ultraviolet (UV) or visible (VIS) radiation that has an energy level equal to or greater than the bandgap. The electrons in the VB get excited as they move towards the conduction band (CB) and leave holes in the VB. The holes and electrons produced in this way initiate oxidation and reduction reactions facilitating water recovery [3]. Photocatalytic decomposition of dissolved water contaminants through irradiation technique is a physicochemical process that has already been extensively studied for wastewater treatment. It deals with photocatalyst dispersal in the polluted water followed by the subsequent irradiation with a light source of the specific wavelength. The water samples get monitored to determine the degradation of dissolved water pollutants or the recovery of clean water and to regenerate the photocatalyst from treated water [3].

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10.1.6.1  PROPERTIES OF PHOTOCATALYSTS Factors to consider when choosing a material for photocatalytic applications include the bandgap of the material and the radiation source, with energy more significant than the energy gap between the conduction and VBs of the semiconductor. The structural and electronic properties of photocatalysts also affect the formation of electron-hole pairs and their potential for recombination. A high degree of crystallinity is desirable for the photocatalyst because the defects present on the surface of the material function as the recombination center of the photogenerated electron-hole pairs, thereby slowing the rate of catalysis. Bio-nanoparticles typically have a large surface area and small dimensions, which reduces the diffusion length of photogenerated electron-hole pairs and improves catalytic efficiency. Doping with co-catalysts such as NiO, Pt, RuO2 further increases the number of active sites on the surface, improving the photocatalytic activity (PCA). Therefore, semiconducting NPs turned out to be extensively employed as effective photocatalysts for water fission along with dye degradation reactions [3]. Photocatalytic reactions are usually initiated by photo-generation of electron-hole pairs. Thus, their lifetime, mobility, and recombination are pivotal factors in determining their operational efficacy. In the case of the highly crystalline structure of the photocatalyst, the lifetime and mobility of the electron-hole pairs get improved because of lesser surface defects enhancing their PCA. In greater mobility, it becomes easy for them to cover the energy gap and accelerate photocatalytic degradation. If the charge separation is higher, recombination is prevented from undergoing enhancement in the PCA [3]. 10.1.6.2  HETEROGENEOUS PHOTOCATALYSIS The rapidly growing population and ever-increasing industrialization have rendered wastewater a severe issue leading to the advanced oxidation processes (AOPs), which have the potential for total mineralization of the toxic metal ions and organic pollutants. It is a leading field of research with significant applications in solar energy conversion, air pollution mitigation, and removal of pollutants from water. The mechanism deals with the semiconductor’s capability to generate electron-hole pairs as charge carriers under light irradiation, followed by the free radical generation resulting in

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their degradation into CO2 and H2O [1]. Hence, their most attractive features include: • The pollutants undergo complete degradation into CO2 and other inorganic substances; • The process proceeds at ambient conditions; • The presences of oxygen and ultra-bandgap energy directly obtained from nature are the primary conditions for its initiation; • It may support the catalyst on a range of inert matrices such as glasses, CNTs, polymers, and graphene oxides; • The photocatalysts are low-cost, biocompatible, non-toxic, and reusable. 10.1.6.3  PHOTOCATALYSIS OF ORGANIC MATTER IN WATER This technique has been a significant cause of the AOP, which catalyzes photocatalytic degradation of a range of organic contaminants in water, such as textile pigmentation and dyes. It has been the economically best and highly effective wastewater treatment technique. Through photocatalysis, toxic organic dyes in wastewater can be easily removed utilizing either solar or UV radiation [4]. Holes acting as oxidizing agents react with water or hydroxyl ions to produce hydroxyl radicals with more significant oxidation potential and high reactivity. They react with organic contaminants through addition, a combination of radicals, hydride abstraction or electron transfer to form reactive species such as H2O2 and superoxide, which catalyze chemical degradation and mineralization [4, 14]. In contrast, the excited electrons formed in the conductive band produce hydroxyl free radicals and interact with O2 forming the superoxide free radicals, which may induce the oxidation of organic pollutants. However, the enhanced rate of electron-hole fusion, low aggregation tendency, weak adsorption capacity, difficult separation of the photocatalyst, and slow photocatalytic efficiency act as the main controlling factors reducing the rate of organic degradation in water [4]. Therefore, alternative photocatalysts such as NC have been developed based on silica, zeolites, and carbonated materials such as graphene oxide (GO) to improve the PCA through enhancement static sites and interface area for the adsorption of organic contaminants [4, 16]. Moreover, the defective NC structure is expected to prevent the electron-hole pair recombination. Moreover, the cellulose-based NMs combine with the conventional metaloxide semiconductors forming hybrid NCs such as nanocellulose-metal

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oxide photocatalysts. Since they consist of enhanced surface area containing more active sites and reaction wavelength in the visible region, it improves the photocatalytic recycling and functional efficiency [4, 15]. 10.1.7  ROLE OF BIONANOMATERIALS IN CLEAN AND GREEN ENVIRONMENT Bionanomaterials serve as an excellent platform to monitor and recover the environmental pollutants from different domains such as air, municipal, and industrial wastewater, soil, and food. With the decrease in the bio nanoparticles, their surface area to volume ratio increases leading to the enhanced reaction rate and lower pollutant concentration. Hence, the bionanomaterials enable a recovery process for the pollutants to render the air and water clean. They may remove large and easy-to-settling inorganic solids (0.01 mm), suspended solids containing organic and inorganic substances (0.1 mm–35 μm), organic matter, nutrients, and pathogenic microorganisms [27]. 10.1.7.1 BIONANOCOMPOSITES Bionanocomposites are the conjugates of biopolymers, including polysaccharides, polypeptides, aliphatic polyesters, poly nucleic acids, and fillers such as clay hydroxyapatite and metal NPs. They exhibit various characteristics, including solubility in water, improved stability, good biocompatibility, and enhanced biodegradation, which govern their preparation procedure, function, and applicability mainly in materials science, biology, biomedical science, and NT [2]. The renewable and biodegradable bionanocomposites have been considered “green bionanocomposites” that are eco-friendly, cost-effective; retain improved surface reactivity, and high surface-to-volume ratio. Since they render more significant antimicrobial potential than their micro- or macro-scale equivalents, they have been considered an ideal antimicrobial platform. Though nanofillers may improve mechanical, barrier, and thermal properties, their doping with biopolymers such as starch and PLA imparts superior characteristics to the bionanocomposites compared to the NCs. Hence, they exhibit excellent mechanical strength, enhanced biodegradation, and improved biocompatibility, making them the best candidates for food packaging and biomedical applications such as vaccinations, tissue engineering, drug delivery, and wound dressing. Some of the significant

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bionanocomposites used to pack equipment include cellulose, poly (butylene succinate), polyhydroxy butyrate, and polylactic acid (PLA) [2]. 10.1.7.2 APTASENSORS Bionanomaterials-based aptasensors have found many applications in biological samples, such as toxins, endocrine disrupting chemicals (EDCs), contaminants, drugs, and insecticides in soil, food, and water samples [19]. Mycotoxins acting as fungicides contaminate milk, wine, coffee, grains, and their derivatives such as wheat, beer, or baby food. Aptasensorsare extensively used to detect mycotoxins, including Anatoxin-a, Fumonisin B1, T2-toxin, and Brevetoxin-2 in wine, corn, and wheat peanuts, straw, drinking water, milk, and shellfish with detection limits ranging from nanomolar to femtomolar [27]. Since EDCs such as 17β-estradiol, bisphenol-A, and polychlorinated biphenyls (PCBs) interfere with living beings, various aptasensors have been developed to detect EDCs in different tap water samples, lake water, wastewater, milk, and blood [19]. Due to the excessive use of antibiotics and pesticides in industrial and agricultural livestock farming, the environment, including food and water resources, gets highly polluted. Aptasensors have successfully been designed to detect oxytetracycline in barbed tap water, tetracycline in honey, kanamycin, and streptomycin in milk, iprobenfos in rice, and acetamiprid in soil, water, cucumber, and cabbage [19]. 10.2  TOXICITY OF BIONANOMATERIALS The area of bionanotechnology and its widespread applications in almost every field of life has been posing a severe hazard to human health and the ecosystem. Since bionanomaterials have a tiny dimension, their impact on the human body has been found through several pathways such as uptake, skin penetration, and inhalation. It is for this reason that their diagnosis and removal from the body are challenging. Once they enter the bloodstream, they can cause neurological disorders and severe health problems such as heart attacks and kidney failure. Their presence in the air and water can affect soil fertility, marine life, unrecorded water reservoirs, cloud formation, and stratospheric temperature. Their toxicity has also been influenced by their physicochemical characteristics such as dimension, surface area, outline, charge, and conjugates [25].

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10.2.1  TOXIC EFFECTS ON ECOSYSTEM Since the increasing globalization of bionanomaterials is seriously harmful to the environment, their release destroys the beauty and vitality of nature. They can penetrate from agricultural fields and water reservoirs, adversely affecting water purity and soil fertility. It leads to the in-vivo accumulation of bionanomaterials in the food chain, which can pass from one generation to the next [25]. Their presence in the Earth’s atmosphere can also induce some environmental processes; for example, they play an essential part in forming the dirt clouds composed of dispersed solid and carbon-based NMs derived from plastic waste and fossil fuel burning and soot enriched with industrial fumes. Such clouds can settle on glaciers, increasing the absorption of sunlight and melting glaciers. Therefore, it must be control their release into the ecosystem immediately to retain the balance in the ecosystem and also to keep it clean [25]. 10.2.2  TOXIC EFFECT ON HEALTH Long-term exposure to bionanomaterials causes severe threats to human life. They enter the human body from various respiratory, dermal, oral, ocular, and gastrointestinal systems. Depending on their size, they might be assembled in various organs, including the liver, respiratory system, brain, kidneys, and heart. Bionanomaterials found in the environment are dangerous to humans and are also hazardous to other animals, which help to maintain the balance in the ecosystem. They enter the animal body through plants, crops, grasses, polluted water, and eating the prey, and become accumulated in the different organs such as liver, kidneys, and bloodstream. For example, bio NPs ranging from a few nanometers to tens nanometers were found to accumulate in the alveoli of mice and human lungs. Those only a few nanometers in size may enter the blood circulating from the alveoli accumulated in the human organs through the bloodstream. The human organs suffering from NP deposition become reactive oxygen species (ROS) production houses experiencing inflammation. They have been found responsible for causing such respiratory diseases as asthma and chronic bronchitis [22, 25]. Since they may enter the human body via a dermal pathway through cosmetics containing NPs such as TiO2 in sunscreen, clothing containing NPs in their fabric, and face masks with NPs coatings, they might irritate when in contact with the skin. Since the skin and respiratory tract have been highly

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susceptible to ultrafine NPs, they can easily pass through the skin layers to enter the bloodstream. In addition to neurological disorders, they may also cause severe infection to the eyes, intestines, and gastrointestinal tract (GIT). Hence, there must be strong legislation and set standards regarding their applicability in various products [25]. 10.3  FUTURE SCOPE Besides various advantages of the engineered bionanomaterials such as high adsorption capacity, enhanced selectivity, and improved kinetic efficiency for the extraction and recovery of heavy metals, transition metals, and radioactive metals from water resources, there are some technical glitches like stability, cost, reusability, and toxicity which must be taken into consideration [10]. Their fabrication by introducing such functional groups as amine, hydroxyl, carboxylic acid, organic polymers, and biopolymers has improved their adsorption capability and stability. Furthermore, the following green engineering principles to design bionanomaterials will undoubtedly increase their beneficial implications. It is also advised to implement bionanotechnology with little change to the existing infrastructure in the near future. As bionanotechnology continues to advance, there is a growing focus on addressing two critical issues related to sustainability over the next few decades [12]: • How can bionanotechnology help address the challenges and provide opportunities to improve local and global sustainability? and • Can bionanotechnology be developed continuously? 10.4  SUMMARY Since the conventional technologies are unsuitable for commercial applications due to low efficiency, high energy consumption, and toxic byproducts, bionanotechnology has led to improvements in pollutants removal technologies. Additional studies are still required to: i) further increase the adsorption capacity of advanced bionanomaterials, ii) lower their production cost, and iii) produce non-toxic and eco-friendly bionanomaterials for pollutants recovery processes. To overcome the previously reported challenges, it is necessary to pave new avenues for the design, synthesis, and applications of simple, affordable, highly potent bionanomaterials integrated

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into commercial applications. The alarming threat of environmental pollution and global warming are the key challenges that may be overcome with non-toxic bionanoscience development. Bionanotechnology has been expected to eliminate all the disruptions and challenges of the conventional technology sectors. This chapter discusses various challenges to a clean and green environment and how to overcome these challenges by employing bionanomaterials. Moreover, the future applications of bionanomaterials and trends in shaping a healthy ecosystem have also been focused on their limitations that have positive and mild negative environmental factors. Due to the development of bionanotechnology applications in the biomedical field and minimizing their reimbursement cost, more advantageous medical treatments may improve human health. They have been widely utilized as absorbents for the disposal of wastes and pollutants from water due to their unique properties, making them the best suitable candidates for future technological development in water treatment. Hence, bionanotechnology has been found as a developing field that may improve what is already known. Many organizations continuously promote safe, green, and potent NT-based programs for a clean environment. ACKNOWLEDGMENT We pay special thanks to Mr. Kashif Javed, Department of Information Technology, Masood Textile Mills Faisalabad, Punjab, Pakistan, for his contribution and for providing all the technical assistance. KEYWORDS • • • • • • •

deoxyribonucleic acid Fourier transformed IR spectroscopy peptide nucleic acid photoluminescence spectroscopy polylactic acid, glycolic acid scanning electron microscopy xeno-nucleic acid

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REFERENCES 1. Ahmed, S. N., & Haider, W., (2018). Heterogeneous photocatalysis and its potential applications in water and wastewater treatment: A review. Nanotechnology, 29(34), 1–30. 2. Cankaya, N., (2021). Synthesis and structural properties of chitin/clay bio-nanocomposites. Cellulose Chemical Technology, 55(5, 6), 659–665. 3. Jain, K., Patel, A. S., Pardhi, V. P., & Flora, S. J. S., (2021). Nanotechnology in wastewater management: A new paradigm towards wastewater treatment. Molecules, 26(6), 1–26. 4. Choudhury, R. R., Sahoo, S. K., & Gohil, J. M., (2020). Potential of bioinspired cellulose nanomaterials and nanocomposite membranes thereof for water treatment and fuel cell applications. Cellulose, 27, 6719–6746. 5. Chronopoulou, L., Nocca, G., Castagnola, M., Paludetti, G., Ortaggi, G., & Sciubba, F., (2016). Chitosan based nanoparticles functionalized with peptidomimetic derivatives for oral drug delivery. New Biotechnology, 33(1), 23–31. 6. Dong, C., Zhang, F., Pang, Z., & Yang, G., (2016). Efficient and selective adsorption of multi-metal ions using sulfonated cellulose as adsorbent. Carbohydrate Polymers, 151, 230–236. 7. García-Mayagoitia, S., Perez-Hernandez, H., Medina-Perez, G., Campos-Montiel, R. G., & Fernandez-Luqueno, F., (2020). Bio-nanomaterials in the air pollution treatment. In: Kuhl, M. L., (ed.), Nanomaterials for Air Remediation, Micro, and Nanotechnologies (pp. 227–248). Elsevier Inc. 8. Garg, V. K., & Kataria, N., (2016). Nanomaterial-based sorbents for the removal of heavy metal ions from water. In: Gautam, R. K., & Chattopadhyaya, M. C., (eds.), Advanced Nanomaterials for Wastewater Remediation, (p. 179). CRC Press, Taylor & Francis Group. 9. Huang, Y., Ren, J., & Qu, X., (2019). Nanozymes: Classification, catalytic mechanisms, activity regulation, and applications. Chemical Reviews, 119(6), 4357–4412. 10. Jawed, A., Saxena, V., & Pandey, L. M., (2020). Engineered nanomaterials and their surface functionalization for the removal of heavy metals: A review. Journal of Water Process Engineering, 33, 1–20. 11. Joshi, P., & Kumar, D., (2018). Role of bionanomaterial-based devices in water detoxification. In: Hussain, C. M., & Mishra, A. K., (eds.), Nanotechnology in Environmental Science (pp. 543–578). Wiley-VCH Verlag GmbH & Co. KGaA. 12. Fraceto, L. F., De Lima, R., Oliveira, H. C., Avila, D. S., & Chen, B., (2018). Future trends in nanotechnology aiming environmental applications. Energy, Ecology, and Environment, 3, 69–71. 13. Kratosova, G., Holisova, V., Konvickova, Z., Ingle, A. P., Gaikwad, S., & Skrlova, K., (2019). From biotechnology principles to functional and low-cost metallic bionanocatalysts. Biotechnology Advances, 37(1), 154–176. 14. Shafali, Singh, S., & Kansal, S. K., (2021). Nanostructured photocatalysts for degradation of environmental pollutants. In: Pant, K. K., Gupta, S. K., & Ahmad, E., (eds.), Catalysis for Clean Energy and Environmental Sustainability (pp. 823–863). Springer, Cham. 15. Lebogang, L., Bosigo, R., Lefatshe, K., & Muiva, C., (2019). Ag3PO4/nanocellulose composite for effective sunlight driven photodegradation of organic dyes in wastewater. Materials Chemistry and Physics, 236, 1–8.

Advanced Bionanomaterials Used to Recover Pollutants 295 16. Liu, S., Low, Z. X., Hegab, H. M., Xie, Z., Ou, R., & Yang, G., (2019). Enhancement of desalination performance of thin-film nanocomposite membrane by cellulose nanofibers. Journal of Membrane Science, 592, 1–7. 17. Long, L. Y., Weng, Y. X., & Wang, Y. Z., (2018). Cellulose aerogels: Synthesis, applications, and prospects. Polymers, 10(6), 1–28. 18. Nayak, V., Singh, K. R., Singh, A. K., & Singh, R. P., (2021). Potentialities of selenium nanoparticles in biomedical science. New Journal of Chemistry, 45(6), 2849–2878. 19. Nguyen, V. T., Kwon, Y. S., & Gu, M. B., (2017). Aptamer-based environmental biosensors for small molecule contaminants. Current Opinion in Biotechnology, 45, 15–23. 20. Pandit, P. R., Kumar, D., Pandya, L., Kumar, R., Patel, Z., Bhairappanavar, S. B., & Das, J., (2020). Bio-nano-approaches: Green and sustainable treatment technology for textile effluent challenges. In: Shah, M., & Banerjee, A., (eds.), Combined Application of Physico-Chemical & Microbiological Processes for Industrial Effluent Treatment Plant (pp. 339–363). Singapore: Springer Nature Pte Ltd. 21. Paul, B., & Tiwari, A., (2015). A brief review on the application of gold nanoparticles as sensors in multi-dimensional aspects. IOSR Journal of Environmental Science, Toxicology, and Food Technology, 1, 1–7. 22. Pietroiusti, A., Stockmann-Juvala, H., Lucaroni, F., & Savolainen, K., (2018). Nanomaterial exposure, toxicity, and impact on human health. Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology, 10(5), 1–21. 23. Ramdani, S., Amar, A., Belhsaien, K., El Hajjaji, S., Ghalem, S., Zouahri, A., & Douaik, A., (2018). Assessment of heavy metal pollution and ecological risk of roadside soils in Tlemcen (Algeria) using flame atomic absorption spectrometry. Analytical Letters, 51(15), 2468–2487. 24. Rasheed, P. A., & Sandhyarani, N., (2017). Electrochemical DNA sensors based on the use of gold nanoparticles: A review on recent developments. Microchimica Acta, 184(4), 981–1000. 25. Bundschuh, M., Filser, J., Luderwald, S., McKee, M. S., Metreveli, G., Schaumann, G. E., Schulz, R., & Wagner, S., (2018). Nanoparticles in the environment: Where do we come from, where do we go to?. Environmental Science European, 30(6), 1–17. 26. Singh, K. R. B., Nayak, V., & Singh, R. P., (2021). Introduction to bionanomaterials: An overview. In: Singh, R. P., & Singh, K. R. B., (eds.), Bionanomaterials, Fundamentals, and Biomedical Applications (pp. 1–21). IOP Publishing Ltd. 27. Sonker, A. S., Richa, R., Pathak, J., Rajneesh, R., Pandey, A., Chatterjee, A., & Sinha, R. P., (2017). Bionanotechnology: Past, present, and future. In: Sinha, R. P., & Richa, (eds.), New Approaches in Biological Research (pp. 99–147). New York, USA: Nova Science Pub Inc. 28. Wei, G., Yan, Z., Tian, J., Zhao, G., Guang, S., & Xu, H., (2020). Efficient polymer pendant approach toward high stable organic fluorophore for sensing ultratrace Hg2+ with improved biological compatibility and cell permeability. Analytical Chemistry, 92(4), 3293–3301. 29. Wu, H. Z., & Meng, L. F., (2019). Liquid chromatography-UV determination of heavy metal ions in environmental samples using dispersive liquid-liquid microextraction coupled with magnetic nanoparticles. Applied Ecology and Environmental Research, 17(2), 1571–1584. 30. Yan, Z., Wang, C., Tang, Y., Zhu, Y., Cao, Q., Yang, T., & Hu, L., (2020). π-conjugated molecules identified for reversible and visual detection of F– in aqueous: Effect of

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Sustainable Nanomaterials for Biosystems Engineering

heterocycle unit on sensing performance. SpectrochimicaActa Part A: Molecular and Biomolecular Spectroscopy, 224, 1–7. 31. Yan, Z., Yuan, H., Zhao, Q., Xing, L., Zheng, X., & Wang, W., (2020). Recent developments of nanoenzyme-based colorimetric sensors for heavy metal detection and the interaction mechanism. Analyst, 145(9), 3173–3187. 32. Yao, W., Liu, Y., Li, D., Zhang, Q., Zhong, S., Cheng, H., & Yan, Z., (2020). Synergistically enhanced electrochemical performance of Ni-rich cathode materials for lithium-ion batteries by K and Ti co-modification. The Journal of Physical Chemistry C, 124(4), 2346–2356. 33. Zhang, X., & Liu, Y., (2020). Nanomaterials for radioactive wastewater decontamination. Environmental Science: Nano, 7(4), 1008–1040. 34. Zhang, X., Gu, P., & Liu, Y., (2019). Decontamination of radioactive wastewater: State of the art and challenges forward. Chemosphere, 215, 543–553.

CHAPTER 11

ROLE OF NANOMATERIALS IN THE TREATMENT OF POLLUTED CAUVERY RIVER WATER IN TIRUCHIRAPPALLI DISTRICT (TAMIL NADU) R. ARULNANGAI and KAMAL AHMAD QURESHI

ABSTRACT Water has an important role in human health and well-being. Human beings now have access to safe drinking water as a basic right. Around 780 million people do not have access to safe drinking water, and 2.5 billion do not have basic sanitation. As a result, every year, around 6–8 million people die as a result of water-related diseases and disasters. Various contaminants, including chemical and microbiological pollutants, have an impact on the safety of drinking water. The Cauvery River is one of the country’s most important interstate rivers. Furthermore, no data from monitoring the entire river and defining its spatial characteristics based on water quality, carbon load, bacterial community structure, and greenhouse gas (GHG) concentrations such as pCO2 and pCH4 in the water has been found. As a result, the current study focuses on pollution monitoring along the Cauvery River, as well as its effects on GHGes (pCO2 and pCH4) and bacterial ecology, as well as their interactions. Water samples were taken from three distinct locations in the Tiruchirapalli District. Physicochemical analysis was performed on the samples. Most physicochemical parameters, such as PH, EC, TDS, COD, and BOD, were found to be significantly beyond the WHO (2011) acceptable limit. The investigation’s water quality index (WQI) scores were reported to be greater than (167.13). The findings show that the Cauvery water is unsafe Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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for drinking in the majority of the area. To protect and safeguard important water resources from pollution for future generations, prompt remedial action is required. Due to their unique qualities like as increased surface area, ability to work at low concentration, and others, nanomaterials (NMs) have a huge potential to clean polluted water (including metal toxic substance, different organic and inorganic contaminants) extremely well. Although the use of nanostructured catalytic membranes, nanosorbents, and nanophotocatalysts to remove pollutants from water is environmentally beneficial and effective, it requires more energy and expenditure to clean the water. There are numerous obstacles and issues with regard to water treatment. To avoid environmental and health problems, some precautions are also essential. For commercialization, new modern water treatment equipment should be adaptable, low-cost, and efficient. 11.1 INTRODUCTION Water is the most critical resource for life. Rivers are vast natural water bodies that discharge into the sea [18]. Rivers are critical carriers of water and nutrients to locations all over the world, although containing just around 0.0001% of the total amount of water in the planet at any given moment [39]. Rivers are at the heart of many of society’s environmental concerns, and they are studied by a diverse group of experts, including hydrologists, engineers, ecologists, geologists, and geo-morphologists. The health of humans, plants, and other animals is affected by river water quality, which is a major concern for all stakeholders. As a result, poor water quality has far-reaching effects for humans, other creatures, and plant life. Aquatic resources have been utilized as clearance grounds for dumping waste, including technical pollutants since the birth of human civilization, contaminating aquatic bodies as a result of unplanned rapid urbanization and industrialization [12]. In our country, because of industrial growth and urbanizing living style, the pollutant water becoming an alarming situation, nearly 70% of Indian river are polluted river water quality is critical because these water resources are used for a variety of purposes, including “drinking, domestic, residential water supplies, agriculture (irrigation), hydroelectric power plants, transportation, infrastructure, tourism, recreation, human or economic uses of water.” As a result, the nature and health of any aquatic community are a reflection of water quality for its best application, such as drinking, immigration, industrial purposes, and comprehending the complicated process nitration

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between the climate and biological processes in the water. The reliability of the water for various purposes depends on the chemical and physical quality of water. Nanotechnology has proven to be a great success in addressing water purification issues and has the potential to advance in the future. NM technologies such as ‘nanosorbents, nanostructured catalytic membranes, and others’ are very efficient, requiring less time, energy, and are environmentally benign, but they are not inexpensive, and they have yet to be utilized commercially to cleanse wastewater on a big scale. In the process of water treatment, the growing NM now faces some problems. NMs offer a variety of water treatment options, and they contain a variety of compounds that are distinguished by their particle morphology. The advancement of commercial NM uses is much too rapid, and NM production is rising globally. NMs are used to purify polluted water in a variety of ways, including photocatalytic, adsorption, and nanosorbents. To be more effective, these strategies will need to be tweaked. 11.2  SOURCES OF POLLUTION In the rivers stretch, there are three significant sources of water contamination. The main source of pollution rise from the industry, agriculture, and domestic sources. Because of the transit of commodities, industries, and towns have traditionally been placed along river stretches around the world. They have also been a convenient area to discharge waste. Floods in rivers may be extremely fruitful because of abundant valuable substances which are settled in the soil when the river gets overflows; agricultural activities have tended to be centered along the rivers. Fertilizers and insecticides are used by farmers on their crops to improve output and protect production. However, rain can washout these materials from the soil, causing them to reach rivers. If a river receives a large amount of fertilizer or farm waste, the concentration of nutrients (nitrate and phosphate) in the river water rises dramatically. At the same time, it is utilized by algae for its growth and replication, turning the nature of water into green. Eutrophication, or huge growth of microalgae, causes pollution. When algae die, bacteria break them down, swiftly multiplying and eating up O2 in the river which reduce the lifetime of aquatic organism [17]. The effluents (cyanide, zinc, lead, copper, cadmium, and mercury) from the industries reaches into the rivers modulate the pH level of water which decrease the availability of organism and also cause death. This kind of

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pollutants may also kill birds, fish, and even mammals by interfering in the food chain [29]. Furthermore, increased developments of towns and cities, creates more pollutants which affect the quality of water and aquatic organism. The geochemical processes, release of processed and unprocessed wastewater into river bodies allow heavy metals to enter aquatic bodies and soil. The chapter investigates the nature of Cauvery water in the Tiruchirappalli District and the possibilities of treating the polluted water using NMs. 11.3  CAUVERY RIVER The Cauvery River originate from Western Ghats and flow towards eastward via ‘Karnataka, Tamil Nadu, Kerala, and Pondicherry’ which finally draining into the sea. The river is around 800 kilometers long from its source to its mouth in the Bay of Bengal. Karnataka has 320 kilometers, Tamil Nadu has 416 kilometers, and both ‘Karnataka and Tamil Nadu’ share a 64-kilometer border. The Cauvery basin has an area of 81,155 km2, or about 24.7% of the country’s overall geographical area. The basin is rectangular in shape, having a maximum length and width of 360 km and 200 km, respectively. The flow of the Cauvery River is determined by seasonal rains, which have been noted to be scarce. Domestic and agricultural runoffs, in addition to industrial effluents, are allowed to freely mingle with river water. As a result, the water quality in the Cauvery River must be monitored and examined on a regular basis. The Cauvery River is one of Southern India’s perennial rivers. As a result of increased human activity, its river basin has steadily deteriorated over the last few decades, resulting in water quality deterioration and ecological and biodiversity risks. A huge number of people rely on the Cauvery River and its tributaries for drinking, irrigation, and fishing water. 11.4  CHARACTERISTICS OF STUDY AREA In South India, the Cauvery River is a magnificent river. It is one of the most significant rivers in the area. The river, commonly known as the Kaveri, is considered to be one of the holiest rivers in India. The Cauvery River got its start in the Western Ghats Mountain Range, at Talakaveri. Talakaveri is located in Karnataka’s Kodagu district, and the river flows in a southeasterly direction through the states of Karnataka and Tamil Nadu. The river runs

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from the Deccan Plateau in the south to the lowlands in the southeast, eventually emptying into the Bay of Bengal. 11.4.1  STUDY AREA 1 (SA 1) Musiri is a panchayat town in the Tamil Nadu state of India’s Tiruchirappalli district. It is 82 meters above sea level on average. Agriculture is the main source of income in this town. Paddy, sugar cane, bananas, and vegetables are among the crops. Weaving of Korai grass mats/Chatai mats is done here. A 1.45-kilometer (0.90-mile) bridge spans the river Kaveri, connecting the town to Kulithalai. 11.4.2  STUDY AREA 2 (SA 2) Kulithalai is 11.16 square kilometers in size (4.31 sq mi). Agriculture is the main occupation in the town, which is located in the fertile Cauvery delta region. Kulithalai is situated at 10.56°N 78.29°E, with a contour that runs north-south and east-west. Kulithalai is situated on the Cauvery River’s banks. 11.4.3  STUDY AREA 3 (SA 3) The Grand Anicut (also known as Kallanai) dam is a historic structure. It is constructed (in running water) across the Kaveri River, which flows from Tiruchirapalli to Thanjavur. It is the world’s fourth-oldest water diversion or water-regulator structure, and India’s oldest still in use. At a point 20 miles (32 kilometers) west of Kallanai, the Kaveri river splits in two. Before uniting at Kallanai, the two rivers form the island of Srirangam. The Kollidam (Coleroon) is the northern channel, while the Kaveri is the southern channel, which empties into the Bay of Bengal at Poompuhar. The seaports of Nagapattinam and Karaikal are located on the delta’s seaward face. Several studies on the Cauvery River have looked into the relationship between water-sediment quality and heavy metal distribution, but data on pharmaceutical chemical dispersion and bacterial community structures is sparse. This study emphasizes the influence of anthropogenic activities on aquatic ecosystems, their impact on humans, and the need for pollution control.

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11.5  WATER QUALITY METRICS 11.5.1  pH pH is a critical metric for determining whether water is acidic or basic. The water sample has a pH level of 7.62–7.87. The river water acidity is the greatest in the globe. A number of factors influence the pH of water. The higher pH values indicate that the change in physicochemical circumstances had a stronger influence. The limit set by the WHO is (6.5–8.5). The bulk of river water samples are somewhat alkaline due to the presence of carbonates and bicarbonates. The more productive the water is, the greater the pH range (7.0). All chemical and biological responses are influenced by the pH of water. 11.5.2  WATER TEMPERATURE The temperature rises in the summer in all seasons and in all regions. Temperature is a numerical expression of how hot or cold something is. The water sample had a temperature range of 26.7° to 31.2°, which was significantly below the WHO recommended limit (20°–35°). 11.5.3  ELECTRICAL CONDUCTIVITY (EC) EC is a way for measuring water quality and a key indicator of water’s ability to transmit electric current. The ability of water to transport electric current is known as EC. The EC Values are in the range of 628.6 to 766.3. Crop germination is hampered by the high EC (2,500 micro-ohms/cm3), resulting in a decreased yield. The maximum acceptable amount of EC in water is set by the World Health Organization (WHO) (600 micro ohms/ cm3) (Table 11.1). TABLE 11.1  Analysis of pH, T°, EC in Water Samples Collected from Study Area Study Area

pH

Temperature

Electrical Conductivity

S1

7.87

31.2

706.4

S2

7.62

29.8

628.6

S3

7.79

26.7

766.3

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11.5.4  TOTAL DISSOLVED SOLIDS (TDS) Total dissolved solids (TDS) is a measurement of the amount of solids dissolved in water which includes – salts, organic compounds, and other elements ranging from micronutrients to toxic compounds. The TDS permissible limit is set at (300–600 mg/L). The high level TDS value in drinking water (1,700 mgL) causes gastrointestinal irritation in humans and may have a laxative effect, especially during transit. Bathing and washing becomes unsatisfactory as a result. 11.5.5 TURBIDITY According to WHO, the turbidity permissible limit for drinking water is 5 NTU. The turbidity range in the collected water samples are found to be above 5 NTU. This may be due to the mud and silt which was washed into rivers and streams (Table 11.2). TABLE 11.2  Evaluation of Turbidity and TDS Levels in Water Samples Study Area

Turbidity

TDS

SA1

5.1

612.6

SA2

5.7

774.7

SA3

5.9

646.9

11.5.6 SODIUM Flame photometry is an atomic emission method for detecting metal salts in solution, primarily Na, K, Li, Ca, and Ba. The hot flame vaporizes the solvent, atomizes the metals, and causes a valance electron to jump to a higher state. The sodium levels were found to range between 119 mg/dL and 232 mg/dL. The salt levels in all river water tests are higher than the WHO’s permissible limits [19, 20]. 11.5.7 POTASSIUM Potassium is a delicate silvery-white metal that can be easily sliced with a knife. Potassium metals react with ambient oxygen to produce flaky

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white potassium peroxide within seconds of exposure. Potassium levels are reported to be between 11.2 and 14.9 parts per million. Potassium levels considerably in increased range compared to WHO’s permitted range in all river water tests [10, 14]. 11.5.8 CHLORIDE The presence of chloride in water implies that the water is being polluted and is deteriorating. Higher chloride concentrations in samples collected from the study area are harmful to living organisms and cause medical concerns. The maximum amount of chloride allowed in drinking water is 250 mg/L. It can be found in all sorts of water. Chloride levels beyond a certain threshold are thought to be signs of pollution from ‘organic wastes,’ whether it is either ‘animal or industrial base.’ The Chloride ion causes a problem in irrigation, and they’re not good for aquatic life. The WHO recommends a chloride level of 250 parts per million. The chloride levels were determined to be in the 163–325 ppm range. Chloride can be found in bottled water. The chloride content of groundwater is discovered to be higher than expected. 11.5.9 FLUORIDE Fluoride creates a great concern for human health, the amount of fluoride is a significant part of hydro geochemistry. F-concentrations in drinking water should not exceed 1.50 mg/L. Dental caries is caused by low fluoride levels (less than 0.60 mg/l), whereas fluorosis is caused by high fluoride levels (more than 1.20 mg/l). As a result, a safe limit of F-content in drinking water should be between 0.60 mg/l and 1.20 mg/l. A maximum of 1.0 to 1.5 mg/l was set by the Bureau of Indian Standards (BIS). Fluoride levels were substantially between 0.7 and 1.9 and did not indicate any notable seasonal or annual averages trend in their values. There was no significant association with any of the factors. 11.5.10 SULFATE Sulfate is a naturally occurring chemical in drinking water. The intake of water having high levels of sulfate has been linked to diarrhea, raising health concerns about sulfate in drinking water. When sulfate concentrations exceed

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250 mg/l, water takes on a bitter or medicinal flavor. Drinking the water may become unpleasant as a result of this. Plumbing, particularly copper piping may be corroded by high sulfate levels. The plumbing materials with resistant to corrosion, such as pipes made with plastic, are commonly used with high sulfate levels. The values ranging from 85.2 to 125.1 mg/L. Sulfate has a positive relationship with “phosphates, nitrates, BOD, and COD,” as well as a negative relationship with DO. The sulfate concentration of ‘natural waters’ is a significant concern when influential their fitness for community and industrialized use. Phosphates, nitrates, BOD, and COD all have a positive association with sulfate, but DO has a negative association. 11.5.11 PHOSPHATE The increased amount phosphate levels in river bodies are attributable to agricultural runoff, as it is surrounded by irrigated fields. It could reach the uppermost layer of water as a result of human waste and run-off, which algae and other aquatic plants consume as nutrients. When the amount of ‘phosphorus and nitrogen’ molecules in water resources rises, this is known as eutrophication. All of the sites’ phosphorus and nitrate levels displayed monsoon peaks and summer troughs. A study area, there was a considerable upward trend, which can be attributed to sewage water including agricultural pollutants, particularly paddy fragments. Both demonstrated a positive association with each other, as well as a substantial positive association with BOD, COD, and a negative correlation with DO (Table 11.3). TABLE 11.3  Analysis of Na, K, Cl, F, SO4, PO4 in Water Samples Collected from Study Area Study Area Na

K

Cl

F

SO4

PO4

SA1

14.9

163.5

1.9

85.2

0.15

119.2

SA2

232.0

11.2

266.8

0.7

125.1

0.19

SA3

218.8

13.9

325.6

1.3

90.7

0.14

11.5.12  DISSOLVED OXYGEN The dissolved oxygen (DO) test determines how much life-sustaining oxygen is present in the dissolved state. Generally, the aquatic organism

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in the water bodies have access to DO. When organic form of micro and macronutrients is added to sewage, dissolved form of oxygen levels in the water body may fall due to highest range microorganism metabolic activity [13]. This process necessitates the use of specific BOD bottles to separate the interior environment from ambient oxygen. D.O. stands for the dissolved gaseous form of oxygen. Breathing is necessary for fish and other aquatic creatures. D.O. enters water as a by-product of algae and plant photosynthesis, as well as by atmospheric diffusion. The DO concentration was found to be in the range of 5–7.5 ppm. For DO, the WHO has established an acceptable limit of 5 ppm. Due to bioaccumulation and biomagnification, its shortage has a direct impact on the ecosystem of a river. The O2 range in samples collected from the study area is influenced by various factors such as “physical, chemical, biological, and microbiological activities.” DO concentration changes according to the geographical location and seasonally depends upon industrial development, human, and thermal activities. For most aquatic animals, O2 is the main significant gas; respiration requires free oxygen (O2) or DO. The average DO concentration represents the regular value of river water [4]. The enhanced algal output, which creates O2 through photosynthesis and active use in bacterial breakdown of organic materials, resulted in the highest DO levels. The “Turbidity, EC, TDS, sulfate, phosphate, nitrates, BOD, and COD” are all demonstrated a strong negative association with DO, although “pH, hardness, sodium, and potassium” had a substantial positive relationship. 11.5.13 BOD BOD–a measurement for organic material contamination in water that is measured in milligrams per liter. Both biological breakdown of organic molecules and the oxidation of certain inorganic components require DO. BOD refers to the amount of oxygen required by living organisms involved in the use, degradation, or stabilization of organic water. BOD levels are estimated to be between 12.3 and 19.2 parts per million. All of the groundwater samples had BOD levels that were higher than the WHO’s recommended limit of 6 ppm. The biological oxygen requirement is the amount of oxygen that aerobic organisms require in water. The biodegradation of organic molecules raises the oxygen stress in the water, raising the BOD [2]. Natural waters having

Role of Nanomaterials in the Treatment of Polluted Cauvery River Water 307

a BOD of less than 5 mg/L are considered clean. BOD has a direct impact on the concentration of oxygen dissolved in water bodies. The faster the oxygen in the stream is lost, the higher the BOD. Higher forms of aquatic life have a lesser oxygen supply as a result of this. High BOD has comparable effects to lesser amount of DO in water dependent animals: they get agitated, suffocated, and eventually die. “Leaves and woody debris, dead plants and animals, animal manure, effluents from pulp and paper mills, wastewater treatment facilities, feedlots, and food-processing companies, defective septic systems, and urban stormwater runoff” are all potential sources of BOD. Similar findings were reported by Ahipathy and Puttaiah [3], who found that Open defecation along the river into the upstream river resulted in greater BOD values, respectively, while BOD values gradually fell in the downstream areas of the mixing zone. The annual averages revealed a little upward trend, with BOD levels, indicating the lack of substantial organic resources in the studied area. According to comparative study, ‘BOD’ has a noteworthy optimistic correlation with “turbidity, conductance, TDS, alkalinity, chlorides, sulfates, phosphates, nitrates, and COD,” and a strong depressing connection with pH, Hardness, Sodium, and Potassium. 11.5.14  CHEMICAL OXYGEN DEMAND To evaluate the findings of chemical substances in the water samples, the Chemical Oxygen Demand (COD) was calculated. If the COD is high, the water will most likely be considered as polluted due to the chemical component. Both BOD and COD are important markers of a surface water supply’s environmental health. They’re routinely employed in wastewater treatment, but they’re only used in general water treatment on rare occasions. COD concentrations ranged from 13 to 25 parts per million. All of the groundwater samples had COD levels that were higher than the WHO’s recommended limit of 10 ppm. ‘COD’ is a measurement of the oxidized process of reduced compounds in samples (COD). It’s frequently used for indirect determination of the quantity of organic chemicals in water. The amount of organic compounds in water is measured by COD, which is a metric. COD can thus be used to detect organic contamination in upstream water [15]. When used with the BOD test, the COD test can help detect hazardous situations and the notification of physiologically-resistant organic substances [38].

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11.5.15  TOTAL AND FECAL COLIFORMS In the current study, total and fecal coliforms had higher counts, which could be attributed to the discharge of fecal-containing household trash into the river, as well as open defecation along the riverbank. At S1, S2, S3, the annual averages indicated an upward trend. Total and Faecal coliforms counts were higher. As a result, (total and fecal coliforms) in sample water exceeded the allowed level at all locations, making it unfit for drinking without pretreatment (Table 11.4). TABLE 11.4  Determination of DO, BOD, COD, TC, and FC in Water Samples Collected from Study Area Study Area

DO

BOD

COD

TC

FC

SA1

5.5

12.3

16.3

334

132

SA 2

6.2

15.5

25.9

415

169

SA 3

7.5

19.2

13.9

428

145

11.6  WATER QUALITY INDEX One of the most successful instruments for communicating information about water quality to concerned consumers and policymakers is the WQI. After water quality data has been gathered through sampling and analysis, it must be translated into an easily understandable format. Water Quality Indices are a solution that aims to give a “single value” to a source’s water quality based on one or more systems that translate the list of elements and their concentrations contained in sample/samples into a single value. The WQI is a type of average that is calculated by converting a set of variables to a single value using a common scale. A WQI is a univariate expression that combines many sub-indices of constituents (quality variables) to summarize information. The group should include the dataset’s most important parameters so that the index may accurately capture the overall situation and reflect change. When the WQI is calculated and used, it becomes a useful tool for examining trends and highlighting specific environmental situations, as well as assisting government decision-makers in evaluating the effectiveness of regulatory programs [28, 39]. WQI is a rating system that calculates the combined impact of distinct water quality parameters on overall water quality. It is calculated from a human consumption standpoint. The steps in the calculation are as follows: The weightage of the parameter is calculated first. Each of the water quality

Role of Nanomaterials in the Treatment of Polluted Cauvery River Water 309

metrics’ quality rating is determined a second time. Third, the overall indices are the sum of those sub-indices. The ith parameter is the weightage. Wi=kSi, where ‘Wi’ is the ‘weightage unit,’ ‘Si’ is the ‘recommended standard’ for the ITH parameter (I=1–10), and ‘k’ is the ‘proportionality constant.’ The formula Qi=100vSi is used to get an individual’s quality rating. Where Qi is the ith parameter’s sub-index, I is the ith parameter’s monitored value in mgI, and Si is the ith parameter’s standard or permitted limit. The following is how the WQI is calculated: WQI=n(i=1) (QiWi)n(i=1) WQI=n(i=1) WQI=n(i=1) WQI=n(i=1) WQ Wi Where “Qi” is the “parameter’s sub inde”x. “n” is the “number of parameters” taken into account. The significant ‘pollution index value’ is usually 100. The estimated WQI value ranges from 167.13 in this study, and hence can be classified into four classes, from excellent water to inappropriate water. The salts of weak acids are mostly responsible for the alkalinity of natural waters, but “weak or strong bases” may also play a role. The most prevalent type of alkaline is bicarbonate, but carbonate and hydroxide alkaline nature are also present. 11.7  NANOMATERIALS: WATER TREATMENT AND PURIFICATION ‘NMs’ are quickly gaining traction as viable alternatives to traditional water treatment methods, which, despite their effectiveness, are frequently prohibitively costly and prolonged. This may be especially advantageous for countries like India and Bangladesh, where the value of implementing any new removal methodology might turn into a key criterion in assessing its achievement. NMs–are used to replace traditional equipment that demand more raw items, require more power to manufacture, or are well known ecologically damaging. Green chemistry methodology causes a significant decrease in waste creation, less harmful chemical synthesis, and an intrinsically safer chemistry in general when used to make NPs. However, more amounts of data is needed to back up these concepts, and whether exchanging regularly used materials with NPs does truly result in decreased the consumption of energy and material and also prevent side effects. There is also much discussion concerning the safety of NPs and their possible environmental impact. There is a strong belief that nanotechnology (NT) will play a big role in provided that clean water to underdeveloped countries in a cost-effective, long-term manner. However, the possible negative consequences of NPs must also be considered.

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When a NP’s catalytic activity is utilized to degrade contaminants, for example, it can be beneficial, but when taken up by a cell, it can cause toxicity. As a result, NT’s Janus face may prove to be a barrier to its general acceptance. However, as previously said, NT has the potential to significantly reduce costs and hence become more effective than present methods for removing toxins from water in the long run. Nano-particles can be utilized as potent absorbents, separation media, catalysts for photochemical destruction of pollutants, nano-sized zerovalent ion for metal and organic component removal from water [26]. 11.8  MECHANISM OF REMOVING POLLUTANTS FROM WASTEWATER BY NANOMATERIALS Nano-particles are particularly expensive as sorbents due to two key factors. They have substantially bigger exterior areas than macro level particles in terms of weight. It may be enhanced by the addition of reactor groups to improve their affinity for marked chemicals [35]. Workers are increasingly taking advantage of these features to create extremely discriminating and effective adsorbents for removing both “organic and inorganic pollutants” from polluted water. Many molecules have qualities that are proportional to their dimension. “Hematite” particles with a size of 7 nm, i.e., adsorbed Copper ions at low pH levels than particles with a diameter of 88 nm, demonstrating that iron oxide particles with decreasing diameter have increased surface reactivity [24] (Figure 11.1). 11.8.1 NANOFILTRATION Nanofiltration (NF), for example, is emerging as a crucial contributor to purify the water [37]. “Nanofiltration membranes” also called NF membranes are commonly employed in drinking water and water treatment. It’s a lowpressure membrane separation procedure for materials with a diameter of 0.001–0.1 micrometers. The ‘NF’ membranes are pressure driven membranes with pore diameters ranging from 0.2 to 4 nm with features similar to reverse osmosis and ultrafiltration membranes. Turbidity, bacteria, and inorganic ions such as Ca and Na have all been removed using NF membranes. This membrane is used for groundwater soften (decrease water hardness), surface H2O removal of dissolved organic matter and trace contaminants, water treatment in removal of both organic, inorganic pollutants and organic

Role of Nanomaterials in the Treatment of Polluted Cauvery River Water 311

carbon, and pre-treatment in saltwater desalination. The application of NF to remove cations, natural organic matter, biological contaminants, organic pollutants, nitrates, and arsenic (As) from groundwater and surface water was investigated by Bruggen and Vandecasteele [5]. NF also has application in removal of minute amounts of U (VI) from seawater, according to FavreReguillon et al. [7].

FIGURE 11.1  Nanomaterial-based membrane.

The use of NF to desalinate water was studied by Mohsen et al. [21]. They discovered that combining NF with reverse osmosis might efficiently make brackish type of water drinkable. The quality of water may be increased by utilizing nano-filtration process in a major water distribution system [25]. Nanotube filters made up of carbon are also becoming more popular in water purification. The construction of CNT filters was recently described by Srivastava et al. [32]. Hollow cylinders with radially oriented CNT walls make up these innovative filtration membranes. They demonstrated that the nanofilters were successful at removing microorganisms from contaminated water (E. coli and S. aureus). Ultrasonication as well as autoclaving are also effective ways to clean CNT filters. Nanoceramic filters are made up of a blend of ‘nanoalumina fiber and micro glass’ with a strong ‘+’-ve charge that can hold ‘-’vely charged particles. Virus and bacteria are effectively removed using nanoceramic filters. They can chemisorb dissolved heavy metals and have a high capacity for particles with less blockage [31].

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11.9  REMOVAL OF NANOPARTICLES The use of nanoparticles (NPs) in environmental applications will almost always result in NPs being released into the environment. Understanding their mobility, bioavailability, toxicity, and persistence in the ecosystem is essential for assessing their possible environmental concerns. The potential for aquatic and terrestrial species to be exposed to NPs in water and soil remains unknown. The widespread use of manufactured NPs in a number of industrial process including their potential for water purification and treatment, raise the question of how these NPs can be removed from the urban water cycle. “Sedimentation and filtration” are two popular conventional methods for removing particle matter during wastewater treatment. However, because NPs are small, their sedimentation velocities are minimal, and significant sedimentation does not occur as extensive as larger aggregates do not build up [9, 36]. Traditional ways of removing NPs from water, such as flocculation, may be inefficient, implying the need for novel solutions. Until recently, microbes were removed from water using membrane filtration (e.g., NF, and reverse osmosis) (Minnesota). As a result, this method can be used to remove NPs as well. Because the vast majority of NPs utilized in technical applications are functionalized in nature, studies using pure NPs may not be appropriate for assessing the behavior of the actual particles. To minimize agglomeration and hence increase particle mobility, functionalization is widely utilized. Unfortunately, nothing is known about the effect of functionalization on the behavior of NPs in the environment. 11.10  NANOMATERIALS APPLICATIONS IN TREATING POLLUTED WATER In terms of water treatment, NT can be used to identify and remove a variety of pollutants. “TiO2, ZnO, ceramic membranes, nanowire membranes, polymer membranes, CNTs, submicron nanopowder, metal (oxides), magnetic nanoparticles (MNPs), and nanostructured boron-doped diamond” are used in various methods such as “Photocatalysis, NF, Adsorption, and Electrochemical oxidation” to solve or greatly reduce water quality problems in natural environments. [19, 22]. When nanosized particles are utilized as “adsorbents, nanosized zerovalent ions, or NF membranes,” pollutants are removed from sample water, whereas nano-size particles used as enhancer for “chemical or photochemical

Role of Nanomaterials in the Treatment of Polluted Cauvery River Water 313

oxidation” because contaminants to be destroyed [24]. “Dendrimers, metalcontaining NPs, zeolites, and carbonaceous NMs” are the four types of nano-scale materials that are being examined as efficient equipment for water filtration by scientists (Figure 11.2) [35].

FIGURE 11.2  Dendrimers.

The following is a list of the various types of NMs used in water treatment that are or can be used via NT. Dendrite polymers include “random hyperbranched polymers, dendrigraft polymers, dendrons, and dendrimers.” They’re spherical macromolecules with a thick shell consisting of a core, branching sites, and terminal groups that form a well-defined surface [8, 27]. Titanium dioxide (TiO2), zinc oxide (ZnO), and cerium oxide (CeO) are examples of metal oxide NPs (natural or engineered) (CeO2). They exhibit a high degree of reactivity and photolytic activity [16, 23]. Because of their enormous surface area and the ability to boost their affinity by employing

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various functionalized groups, they are regarded as ideal adsorbents for water filtration [33]. To create zeolite NPs, pulsed laser fragmentation of zeolite LTA microparticles or hydrothermal activation of fly ash can be utilized. Metal ion exchange medium and good sorbents for metal ion removal are both used with zeolites. Zeolites have reportedly been used to remove heavy metals such as Cr(III), Ni(II), Zn(II), Cu(II), and Cd(II) from metal electroplating and acid mine waters [1]. Carbon-based NPs operate as sorbents in aqueous solutions because they have a high capacity and selectivity for organic solutes. “Fullerenes/Buckyballs (Carbon 60, Carbon 20, Carbon 70); CNTs; nanodiamonds; nanowire”s are a few examples of carbonaceous nanoparticles. “Buckyballs, ellipsoids, tubes (nanotubes), 1 nm wires (nanowires), and hexagonal shapes” are all examples (nanodiamonds). They are highly thermally and electrically conductive. Carbon-based NMs are constant, have low reactivity, are completely made of carbon, and are powerful antioxidants (Figure 11.3) [6].

FIGURE 11.3  Application of nanoparticles in water purification.

Nanosized silver, gold (Au), palladium, and other metal NPs are examples. Colloidal silver, spun silver, nanosilver powder, and polymeric silver are all examples of nanosilver (engineered) forms. They range in size from 10 to 200 nanometers [22, 30]. They had increased surface reactivity and excellent antibacterial capabilities because they are finished up of numerous atoms of silver in the form of ‘silver ions.’ Medicine, water purification, and antibacterial

Role of Nanomaterials in the Treatment of Polluted Cauvery River Water 315

applications are all possible. They’re used in a wide range of commercial items. Golden nano-sized rods have been employed for the detection of polynucleotides such as cysteine and glutathione, colorimetrically [34]. For the presence of coliforms, silver (I) and silver related compounds have been employed as antibacterial agents [11]. Au NPs coated with palladium are 2,200 times more effective than palladium alone at removing tri-chloroethane (TCE) from groundwater. Nanoscale zero-valent iron (Nzvi), emulsified zero-valent iron (EZVI), and bimetallic nanoscale particles are all examples of zero-valent metals (engineered) nanoparticles (BNPs). BNPs are made up of iron and a metal catalyst including–Au, nickel, palladium, or platinum. Their diameter varies depending on the nanomaterial type that contains the zero-valent metal, but it is usually between 100 and 200 nanometers. They have a high surface reactive that may be adjusted by changing the type of reduction and its reduction conditions. 11.11 SUMMARY Water samples were analyzed from three study areas located in and around Tiruchirappalli District. Physicochemical analysis stated that the range of PH, EC, TDS, COD, and BOD, were found to be significantly beyond the WHO (2011) acceptable limit. WQI value is utilized in this work to assess the quality of river Cauvery water. The findings show that the Cauvery river water is unsafe for drinking and domestic use in the study area. As a result, regular water quality assessments based on water parameter analysis must be followed, and in this study, we suggest the UAE of NMs for purify the polluted water based on their applications. The main causes of pollution in river water are industrialization and population growth. However, a consistent supply of clean water is required. To provide a continuous supply of water for the required functions, several approaches are used. NT is also being considered as a technique of wastewater cleanup that is both cost-effective and environmentally acceptable. NPs of various sizes, metal oxides (MO), zerovalent ions, and NF membranes have all been shown to be effective in the detection, removal, and/or annihilation of pollutants. Nano-engineered materials have huge potential for water revolutions, especially in the fields of decentralized water treatment, point-of-use technologies, and seriously degradable pollutants. Furthermore, modified NMs that are effective, efficient, easy to handle, and ecologically benign are urgently needed. Pricing and commercialization of

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these water treatment technologies must also be considered. The diverse applications of NMs have the potential to make a significant contribution to the world’s domestic water supply. KEYWORDS • • • • • • • •

Bureau of Indian standards chemical oxygen demand dissolved oxygen electrical conductivity greenhouse gas nanofiltration total dissolved solids water quality index

REFERENCES 1. Alvarez-Ayuso, E., Garcıa-Sánchez, A., & Querol, X., (2003). Purification of metal electroplating waste waters using zeolites. Water Research, 37(20), 4855–4862. 2. Abida, A. H., (2008). Study on the quality of water in some streams of Cauvery River. E-Journal of Chemistry, 5(2), 377–384. 3. Ahipathy, M. V., & Puttaiah, E. T., (2006). Ecological characteristics of Vrishabhavathy River in Bangalore (India). Environmental Geology, 49(8), 1217–1222. 4. APHA (American Public Health Association), (2005). Standard Methods for the Examination of Water and Wastewater (21st edn.). American Water Works Association/ Water Environment Federation, Washington DC. 5. Bruggen, V. B., & Vandecasteele, C., (2003). Removal of pollutants from surface water and groundwater by nanofiltration: Overview of possible applications in the drinking water industry. Environmental Pollution, 122(3), 435–445. 6. EPA (US Environmental Protection Agency), (2007). Senior Policy Council. Nanotechnology White Paper. http://www.epa.gov/osa/pdfs/nanotech/epananotechnologywhitepaper-0207 (accessed on 9 July 2022). 7. Favre-Reguillon, A., Lebuzit, G., Foos, J., Guy, A., Draye, M., & Lemaire, M., (2003). Selective concentration of uranium from seawater by nanofiltration. Industrial & Engineering Chemistry Research, 42(23), 5900–5904. 8. Frechet, J. M., & Tomalia, D. A., (2001). Dendrimers and Other Dendritic Polymers. Wiley and Sons, New York.

Role of Nanomaterials in the Treatment of Polluted Cauvery River Water 317 9. Frimmel, F. H., & Niessner, R., (2014). Nanoparticles in the Water Cycle. Berlin, Heidelberg: Springer. 10. Haslam, S. M., (1996). Enhancing river vegetation: Conservation, development, and restoration. Hydrobiologia, 340(1), 345–348. 11. Jain, P., & Pradeep, T., (2005). Potential of silver nanoparticle-coated polyurethane foam as an antibacterial water filter. Biotechnology and Bioengineering, 90(1), 59–63. 12. Jindal, R., & Sharma, C., (2011). Studies on water quality of Sutlej River around Ludhiana with reference to physicochemical parameters. Environmental Monitoring and Assessment, 174(1), 417–425. 13. Kataria, H. C., & Ambhore, S., (2010). Physicochemical analysis of drinking water of Gandhi Nagar area of Bhopal with special reference to pollution. Biomedical & Pharmacology Journal, 3(1), 257–258. 14. Kataria, H. C., Iqbal, S. A., & Shandilya, A. K., (1995). Limno-chemical studies of Tawa Reservoir. International Journal of Environment and Pollution, 16(11), 841–846. 15. King, J. M., Scheepers, A. C. T., Fisher, R. C., Reinecke, M. K., & Smith, L. B., (2003). River rehabilitation: Literature review, case studies and emerging principles. Water Research Commission Report, 1161(1), 03. 16. Klaine, S. J., Alvarez, P. J., Batley, G. E., Fernandes, T. F., Handy, R. D., Lyon, D. Y.. & Lead, J. R., (2008). Nanomaterials in the environment: Behavior, fate, bioavailability, and effects. Environmental Toxicology and Chemistry: An International Journal, 27(9), 1825–1851. 17. Klavinš, M., Briede, A., Rodinov, V., Kokorite, I., Parele, E., & Klavina, I., (2000). Heavy metals in rivers of Latvia. Science of the Total Environment, 262(1, 2), 175–183. 18. Kumar, A., & Dua, A., (2009). Water quality index for assessment of water quality of river Ravi at Madhopur (India). Global Journal of Environmental Sciences, 8(1). 19. Mamadou, S. D., & Savage, N., (2005). Nanoparticles and water quality. J. Nano. Res., 7, 325–330. 20. Minnesota Rural Water Association, (2013). Advancing the Science of Water: AwwaRF and Membrane Process. Retrieved from: https://www.mrwa.com/mn-water-worksmanual (accessed on 9 July 2022). 21. Mohsen, M. S., Jaber, J. O., & Afonso, M. D., (2003). Desalination of brackish water by nanofiltration and reverse osmosis. Desalination, 157(1–3), 167. 22. Mueller, N. C., & Nowack, B. (2010). Nanoparticles for remediation: solving big problems with little particles. Elements, 6(6), 395–400. 23. Nowack, B., & Bucheli, T. D., (2007). Occurrence, behavior, and effects of nanoparticles in the environment. Environmental Pollution, 150(1), 5–22. 24. Nowack, B., (2008). Pollution prevention and treatment using nanotechnology. Nanotechnology, 2, 1–15. 25. Peltier, S., Cotte, M., Gatel, D., Herremans, L., & Cavard, J., (2003). Nanofiltration: Improvements of water quality in a large distribution system. Water Science and Technology: Water Supply, 3(1, 2), 193–200. 26. Peng, X., Luan, Z., Ding, J., Di, Z., Li, Y., & Tian, B., (2005). Ceria nanoparticles supported on carbon nanotubes for the removal of arsenate from water. Materials Letters, 59(4), 399–403. 27. Rajakumar, S., Velmurugan, P., Shanthi, K., Ayyasamy, P. M., & Lakshmanaperumalsamy, P., (2007). Water quality of Kodaikanal Lake, Tamilnadu in relation to physicochemical

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and bacteriological characteristics. Lake and Coastal Wetlands: Conservation, Restoration, and Management, 339–346. 28. Ramakrishnaiah, C. R., Sadashivaiah, C., & Ranganna, G., (2009). Assessment of water quality index for the groundwater in Tumkur Taluk, Karnataka State, India. E-Journal of Chemistry, 6(2), 523–530. 29. Roberta, B., Garibaldi, L., Leoni, B., Quadroni, S., & Galassi, S., (2012). Zooplankton as an early warning system of persistent organic pollutants contamination in a deep lake (Lake Iseo, Northern Italy). Journal of Limnology, 71(2), 335–338. 30. Roco, M. C., (2003). Broader societal issues of nanotechnology. Journal of Nanoparticle Research, 5(3), 181–189. 31. Shah, M. A., & Ahmad, T., (2010). Principles of Nanoscience and Nanotechnology. Alpha Science International, New Delhi, India. 32. Srivastava, A., Srivastava, O. N., Talapatra, S., Vajtai, R., & Ajayan, P. M., (2004). Carbon nanotube filters. Nature Materials, 3(9), 610–614. 33. Stoimenov, P. K., Klinger, R. L., Marchin, G. L., & Klabunde, K. J., (2002). Metal oxide nanoparticles as bactericidal agents. Langmuir, 18(17), 6679–6686. 34. Sudeep, P. K., Joseph, S. S., & Thomas, K. G., (2005). Selective detection of cysteine and glutathione using gold nanorods. Journal of the American Chemical Society, 127(18), 6516–6517. 35. Tiwari, D. K., Behari, J., & Sen, P., (2008). Application of nanoparticles in wastewater treatment. World Applied Sciences Journal, 3(3), 417–433. 36. US Bureau of Reclamation and Sandia National Laboratories, (2003). Desalination and Water Purification Technology Roadmap a Report of the Executive Committee Water Purification. p. 83. Available at https://www.usbr.gov/research/dwpr/reportpdfs/ report095.pdf 37. USEPA, (1997). Manual on Monitoring Water Quality. EPA 841-B-97-003. 38. Wetzel, R. G., (2001). Limnology: Lake and River Ecosystems (p. 1006). Academic Press, New York.

CHAPTER 12

POTENTIAL NANOMATERIALS FOR BIOREMEDIATION AND BIODEGRADATION VIJAYA GEETHA BOSE, SHREENIDHI KRISHNAMURTHY SUBRAMANIYAN, SARANYA SRI SANTHANAM, SHREAYA BHASKAR, and SOWMIA NARAYAN SRIDHAR

ABSTRACT Owing to economic prosperity and development standards for mankind, new technologies are being introduced every day to keep up the ecological balance. Every nation, both developed and developing, is looking for simple, efficient, and green methods to control and maintain contamination levels. Recent flourishing strategies include bioremediation by using plants, microbes, and nanomaterials (NMs). The last century has seen the slow progress of nanotechnology (NT) and its sub-disciplines. It offers sustainability of resources. With few understandable and doable steps, the NMs can be synthesized, and they are found to be effective, starting from wound healing processes to the degradation of complex pollutants to the simpler forms. At the end of the day, it’s the safety and security of every living that is being considered and NMs are found to give that response. This chapter explores potential possibilities of the NMs that can be incorporated for the bioremediation and biodegradation processes.

Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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12.1 INTRODUCTION The industrial revolution of the 19th century has brought about a lot of changes with respect to various aspects of human existence. With furtherance in human lifestyle, there have been lots of fatal effects caused to the environment, thereby causing degradation of the eco biome to a greater extent [5]. Continuous extraction of resources has detrimental effects on pollution of land, water, air, etc. Reports published by WHO in 2018 estimated the global mortality rates due to various types of pollution estimated to be around 7 million; therefore, to curb the increasing pollution level and continuous ecological degradation, there is an instantaneous need of remediation. Hence there arises the need for nano-bioremediation using various nanoparticles (NPs) to keep the pollution levels under control [61]. Nanoparticles are microparticles in the size of less than 100 nm. These particles can alter the physio-chemical properties of matter. NPs exist in various sizes and have various applications. There are two different categories of NPs, namely organic and inorganic NPs and semiconductor NPs. A few examples of organic NPs are: carbon NPs, such as graphene and fullerene; whereas the inorganic NPs include Au and silver and semiconductor NPs comprise of zinc oxides (ZnO) and titanium dioxides (TiO2) [4]. Nanoparticles are usually synthesized using various conventional techniques, but the employment of biological methods of synthesis is highly beneficial as it’s cost-effective, an eco-friendly approach and helps reduce toxicity to a greater extent [7, 40]. From the S-layer proteins rife in the bacteria Bacillus spahericus JG-A12 and the cells from which the NPs are admixed, have specialized abilities of the bioremediation of Uranium from wastewater [18]. NanoBioremediation (NBR) is the process of removal of environmental adulterant using bacteria, fungi, and plants involving NT and biotechnology (Figure 12.1). The term NT was firstly coined by Norio Taniguchi in 1974 [58]. The contemporary methodologies used for amendatory sites comprise of chemical, physical methods of remediation techniques, incineration, and bioremediation. Bioremediation proved to be a very economical and feasible option to remove environmental toxins [52]. NT has enhanced phytoremediation productivity. NPs are used for remediation of water, air, soil, heavy metals, inorganic, and organic toxins from the atmosphere. Studies carried out on organic contaminants such as molinate and chlorpyrifos have the potential to degenerate nanosized zero-valent ions [65]. NBR is an enzymebased approach of bioremediation used along with phytoremediation to yield the best results [50].

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FIGURE 12.1  Prevalent bioremediation techniques.

New technologies are being employed to aid the disposal of sewage sludge, and complying to the stringent environmental regulations above are a few techniques being employed for the same [33]. Due to their eccentric activity toward intractable impurities, many nanomaterials are under research and development (R&D) for treatment of water, soil, and air pollution treatment. This chapter discusses various potential NMs, which have the capability in NBR. 12.2  TYPES OF NANOPARTICLES UTILIZED IN NANOBIOREMEDIATION With regards to the quintessence of exploiting various classes of NMs, the cutting edge advancement in the fields has been employed to achieve optimal utilization. Researchers have articulated various novel materials for remediation, which are discussed in the upcoming sections.

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12.2.1 NANOCRYSTALS The pivotal reason for the NP approach is due to the infinite availability and the scope of Surface area per unit mass of the material utilized, which is increased at a nanoscale. Nanomaterials (NMs) indicate a feasible quantum effect. The viability of their chemical reactions at nanolevels are by virtue of their decreased activation energy demand in action and higher surfaceto-mass ratio in the nanoscale. Toxic materials can be easily detected by the help of NPs using the technique of surface plasmon resonance (SPR). As the shape and size of the particles are the primary disquiets, various categories of NMs distinct in shape and sizes can be utilized for the eradication of toxins from the environs [45]. In the nano-bioremediation appeal, sorption processes are considered essential. Sorption involves both the perspectives of adsorption and absorption. Moreover, a further distinction can be made. As both the subsets of adsorption processes are trajected in the miniscule scale, by the flexibility of their usage, the contaminants or the potent toxins may be immobilized, sequestered, and concentrated. By this, the efficiency of using a combined approach on individual particles could be embodied to scale up the overall function of the remedials [60]. With the initial principles set at these criteria, the formulations of the various NPs vary accordingly. In accordance to work by Xiao et al. [62], the zinc sulfide nanocrystals biofabricated by Shewanella oneidensis were so fabricated at the dimensions of 5 nm approximately with the chemical formulations of sodium thiosulfate as well as lactate. Under their centrifugation studies and the optimization of the NPs with the requisite monikers, the test spectral analysis was done alongside the solutions of zinc sulfate. On further analysis, the generated NPs from the bacteria indicated a guiding result of the degradation of metal residues along with Rhodamin B (RhB) degradation. On reducing the scale of the NPs to a minimal use, the further usage of the particles can be done to remediate the contaminants. By exploiting the magnetic phenomenon of the Metal ions as well, the bio remedial aspect had been procured. In accordance with the work by Tanaka et al. [36], by the employment of a magnetostatic bacteria Magnetospirillum magneticum, the overall concentration of the tellurite toxicity was successfully controlled, known that the metal ions’ ill effects. Under the similar note, nanocrystals of chitin with their efficient solubility in water by the interference of sodium hypochlorite (NaClO) in the TEMPO mediated medium were developed by Fan et al. [64]. As chitin renders as an important principle in marine ecosystems regarding the renewability of the polymers,

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the NPs so created could be amalgamated to better requirements by this and so on. 12.2.2  NANOPARTICLES AND METALLIC NANOPARTICLES Similar to nanocrystals, the inclusion of NPs engineered in a separate chemical cascade upon incorporation with that of the compost or microorganism also is a similar venture of NBR. In the work espoused by Galdames [24], the inclusivity of the Municipal Solid Waste (MSW) alongside the usage of the zero-valent iron particles reduced the overall metal toxicity in the soil samples assayed. By this, the combined effort of NPs used with their electronic fidelity could also be generated and used as an incur for treatment of ecotoxicity. Under the similar umbrella of NPs employment; the NPs used for the remediation of the petroleum hydrocarbons (HCs); a varied number of approaches had been procured for the remedial under the review by Babita [2]. As the degradation and the reconciliation of the petroleum molecules and conjugates is a relatively slow process, various enzymes had been considered for the faster degradation as well as to deteriorate the harmful hydrophobic constituents. One such pivotal usage of NPs is the encapsulation of the potent fertilizing molecules within a NP capsule done by either direct encapsulation methods, coating by a thin polymerous film and/or by direct formulation by emulsions. Gliricidia sepium nanocomposite (NCs) had also been engineered to prolong the sustenance of urea as well as ureahydroxyapatite composites. In this manner the bioremedial of the conjugated hydrophobic molecules were done. For ameliorating the action of nanofertilizers, employing the combined idiolects of nanozeolites as well as nanoclays are standardized. This process is done mostly by the basic application of encapsulation processes. The usage of White Rot Fungi (WRF) as reviewed by Kai [25] for the remediation of metallic NP in the contaminated water had been listed. The agglutinated NPs from fungi such as Phaenerochaete chrysosporium, Trametes versicolor, Pleurotus sajor-caju, Pycnoporus sanguineus, Schizophyllum commune, Phaenerochaete chrysosporium, Pleurotus ostreatus, Stereum hirsutum, Phaenerochaete chrysosporium, Trametes versicolor, Phaenerochaete chrysosporium were used for NP production of varied geometry with the precipitated metal ions (such as: Au, Cd, Se, CdS) were done. As WRFs are used widely in wastewater treatment processes, their immobilization with their associated bio-adsorbent tendency towards these metal ions play a better efficiency measure in the eradication of toxins. Another important

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judiciary of NPs is the inference of metallic molecules such as Au, silver, Lead sulfide, Manganese Dioxide and Cadmium NPs using microorganisms in the marine biomes. With this green synthesis of the metallic NPs from the marine microbes, an elucidate biofactory for NPs could be concluded [42]. 12.2.3  NANOCOMPOSITES AND CARBON NPS Another approximation of NBR is by the furnishing of biosurfactants. As biosurfactants assist in the increased emulsification action of higher HCs by the oil contaminants, one such significant study by El-Sheshtaway [19] utilized the halophilic bacterial strains obtained from Luria broth. As the optimal bacterial strains exhibited the higher crude oil degradation indicative from Bushnell Hass Mineral Salt Medium (BHMS) the selective organisms underwent the protocols of gas chromatographic as well as HPLC analysis to assay the higher rate of degradation. The precursors such as ferric nitrate and zinc chloride aided in the NP production which were later assayed for the emulsification activity scrutiny. On this essay, as the most optimal degradation of the paraffins in the crude oil samples gave a notable observation of how the biosurfactant amalgamation could be exploited for NBR. A similar notary is the usage of NCs by Biochar coupling with microorganisms under the genus of Rhodopseudomonas by Shiying [47]. Under this study, the NCs so derived by the conjugation of the immobilized PSB bacterium alongside the ferric oxide/biochar composite gave an implication of the ammonium and phosphate ions under wastewater treatment. On the basis of the adsorptive action of activated carbon by multi-wall carbon nanotubes by Fe-Ni supported particles are used exclusively for wastewater treatment [35]. The developed catalyst in the nanoscale by using Fe-Ni/AC packaging at room temperature increases the purging activity. The potential application of the sorption of metronidazole and levofloxacin in the formulation of such nanotubes offered a better substance for the better use of such NPs [28]. 12.3  GENERAL MECHANISM OBSERVED IN THE PHENOMENON OF NANO-BIOREMEDIATION Upon manifesting the NPs into the host system quite a diverse range of effects are generally viewed as the repercussion as the Nps are set into the biomass. Under the discourses of plant effects, eco-toxicity, genomic toxicities the influence under which the NPs underlay into the said subjugation are quite

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discreet in different norms. In the cases of plants, the NPs are notably to be indulged in increasing the formation of Reactive Oxygen Species (ROS) thereby inciting an antioxidative nature in the plants as well as having genomic determinants such as significant shifts of the mitotic index of the genome and the chromosomal digressions observed within. The known NPs likely causing these changes are mostly Cerium Oxide, Aluminium Oxide Cupric Oxide, ZnO, and other oxides of reactive metals that are quite present in the prevalent contamination. But, these effects could harbor as a potential to remediate as a growth promoter and other peculiarities such as the usage of Ag-NPs for the upregulation of glutathione reductases and synthesis, and glutathione transferases genes thereby acting as a factor as to how NPs could be engineered for a better causative [44]. Another significant effect of the NPs in the animal cells and their general viability are quite exclusive with their toxic effects. By the work advocated by Daniele [23], an exclusive elucidation of the malefic effects were put forth which are as follows: revamping of the enzymatic activities – alterations of the neurotransmitters: In The field of neurobiology, the action and the mediation of the neurotransmitters play a concorded role in the regulations of cell to cell communication and overall fidelity of the cell’s interaction. Namely, the neurotransmitters such as Acetylcholine esterase. It was observed that the NPs could be the harbinger of hindering cell communication by impeding the AChE expression and converting it to Butyrylcholine esterase. Cell Death induction – via Apoptosis and Necrosis influenced: Necrotic cells as they are deprived, harbor phosphatidylserine externalization of the surrounding cells which are likely detected by the double staining methods. As these effects of NPs on a gross scale have been reviewed, their remediation is further subdivided on the basis of the aerobic and the anaerobic states that are to be underwent as the contaminants are to be expelled. The general conception through which the bioremediation occurs is that, as the microorganisms are set into contact with the said contaminant, they are insinuated by an intracellular attack including quite extensive energizing of varied enzymes. One such contributory enzyme that is observed under this notion is the role of Cytochrome P450 most conducive in the general treatment protocols when the microbial degradation is considered [20]. In recent times as the importance of environmental treatment measures and the incitement of how efficient the NPs could be the hitchhiker for a better ailment, the most predominantly used NPs that proctor a better solution are the incorporation of metal NPs in the treatment processes. Most organisms that have a higher proximity and deployment of metals such as Iron, Copper, Zinc, Silver, and Au using microorganisms that procure

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an associative ailment. As well as the utilization of zerovalent ions in the due treatment processes [8]. By definitive morphological differences, surface areas variations and, the charges and crystallographic specificities of the zerovalent metals assist in stabilizing the toxic substances prevalent by their hindrances and action as dehalogenation of the toxic organic compounds [6]. In incorporating these diverse phenomena of their strategic denominations in the treatment processes and the mechanisms of the pollutants’ influence in the biomes, varied modification, attenuation, and alterations are made in order to unravel and better tangent in the norms of Nanobioremediation. 12.3.1  THE MOST PREVALENT NANO-REMEDIATION TECHNIQUE 12.3.1.1 NANO-PHYTOREMEDIATION With a continuous surge in the soil pollution, particularly in the agriculture field, solid waste, etc., there has been a need to remediate toxins, heavy metals, and various organic wastes had to be amended [27]. Heavy metals like Cadmium, Chromium are known to cause deleterious effects to human health, so the need to remove the toxin pollutants played a vital role. Usage of chemical methods of bioremediation would have deleterious effects on the environment as well as human health hence the use of natural methods of remediation would help protect the environment from further degradation [48]. An alternative to application of chemicals is phytoremediation. Phytoremediation is the utilization of plants to directly or indirectly remove contaminants present in the soil [13]. NPs manifest a lot of unique properties in correspondence to bulk material and also possess small size thereby making them capable of absorbing large volumes [49]. Nano-phytoremediation is the best choice as its cost-effective as they use plants and associated microorganisms for excision of toxins from the soil. Studies substantiate that the employment of nanosized zerovalent irons (ZVI) can be utilized to remove organic contaminants such as atrazine, chlorpyrifos, and molinate [50]. Criterion for NP selection to be used for phytoremediation are: • • • •

The NPs used should be nontoxic; The selected NPs should be capable of promoting plant growth; They should increase the plant growth hormones; The NP should have the potential to cohere the toxins and increase the bioavailability of the plant.

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The plant chosen as a candidate for nano-phytoremediation technique to eliminate the toxins in the soil is based on the application of NPs and phytoremediation methods. This technology manifests the potential of the technique in phytoremediation. In comparison to other techniques, plants exhibited quickened removal of pollutants from the soil and water [34]. In this technique of nano-phytoremediation; NPs interrelate with plants and exhibit various morphological and physical changes. The extent of changes varies on the basis of the type of NP used, the dosage, the species of the plant manipulated [17]. The efficacy of NPs is based on the size, shape, and the reaction on the plants [30]. Recent studies substantiate that the usage of Ag-NPs increases plant growth and development. The usage of Ag-NPs are known to increase the phytohormones production in plants, thereby allowing plants to persist in case of stress and also increase the absorption rates of nutrients and water [29]. Alongside Ag-NPs, salicylic acid NPs are known to increase the phytoremediation efficacy and alleviate plants under As stress [54]. Shortcomings of nano-phytoremediation are as follows [55]: • Identification of environmentally stable NMs is a cumbersome process; • Nano-phytoremediation is very scanty; • Nano-Phytoremediation is applicable to only areas with moderate pollution levels thereby making it difficult for multi-dimensional applications; • Robust experiments are required to be carried out to substantiate the results of nano-phytoremediation; • There is a need to increase the bioavailability of plants as nanomaterials aggregate thereby causing reduced mobility. 12.4  EXTENSIVE APPLICATION OF NANOPARTICLES IN THE ENVIRONMENT With the widespread knowledge and the boundless possibilities by which the NPs have been studied in the recent time, their capacious applications have been commodious for betterment and ease of production for developmental aspects inclusive (Figure 12.2). Apart from their indulgences and their executive usages in the relative fields of technology related fields, NPs have had a collective contribution in varied aspects in the field of life sciences. Due to their miniscule amendments and differential properties observed and at nanoscale, they are incorporated

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in fields of agriculture, microbiology, medicine, and energy production via natural administrations (Figure 12.3).

FIGURE 12.2  Common applications of NPs in life sciences.

FIGURE 12.3  Features of nano-bioremediation that relies on the applicability of nanobiotechnology.

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12.4.1  SOIL CONTAMINATION REMEDIATION BY NANOPARTICLES Soil is a vital natural resource that contributes to the majority of the economy. The 70% of India’s economy relies on farming. Soil remediation was conducted by excavation accompanied by landfilling incineration, but this technique requires several months to produce toxic gases and products as well. By the imminent usage of green bioremediation technology, the decree of the environment and the capacity of the chemical processes has been found out to be quite a cestui que trust for betterment and development [31]. Continuously releasing chemicals from the factories, houses blend with the surrounding soil. By removing heavy metals, plants are also capable of remediating soil toxins. Plants absorb heavy metals through the plant cell transport channel and accumulate in the vacuole, but not commercially applied as much as microbial degradation due to less biomass and bioavailability to the upper components of the plants for pollutants. It also leads to the remediation of organic and inorganic pollutants by native microflora in soil. After a long period of time, compared to non-contaminated soil, many microflora present in contaminated sites have a strong tolerance ability, these microbes chelate the heavy metal present in greater amounts, and also they transmuted the amassed metals of the subsequent salt/ions prevalent, into NPs in the soil. These biosynthesized NPs can be removed from the microbe and used for industrial purposes or can increase the activity of soil and plant development [38]. Zero valent iron can be used widely for soil recovery. The use of highly chlorinated pesticides varies day after day in soil and farm soil pH [46]. This iron is used to minimize the chlorinated compounds in the field. Malathion is a broad range of organophosphate (Ops) insecticides used in cultivation that are not systemic [51]. The soil condition, the soil binding ability and the presence of sunlight and moisture influence the half-life of Malathion from 1–25 days. 12.4.2  WATER CONTAMINATION REMEDIATION BY NANOPARTICLES Rapid and important developments have been made in the treatment of wastewater in an attempt to resolve the issue of water contamination, including photocatalytic oxidation, adsorption/separation, disinfection, recycling of

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membranes and bioremediation [43]. The constant divulgence of NSAIDs such as diclofenac (DCF) into the household drainage and sewage treatments have been found to be noxious to aquatic organisms. Physiological and biochemical changes were observed in the wreaked fish that are exposed to such Xeno chemicals [61]. Oil spills have been cleaned up by the usage of nanoscale calcium peroxide (CaO2) whereas for the soil and underground water remediation nanoscale zero-valent ions have been utilized. Lindane efficiently degrades biopolymer-stabilized iron NPs [41]. The traditional remediation technologies have both in situ and ex situ methodologies where soil washing and pump-and-treat operations are classified under ex situ whereas the in situ method comprises thermal treatment and chemical oxidation and the employment of iron reactive barriers [26]. Because of their low cost, high adsorption capability, easy separation and improved stability, these NMs concocted by iron oxide bodies provide a propitious treatment of industrial scale wastewater [21]. Photocatalysis could be used to purify groundwater in a pump-and-treat process. In situ technologies for the treatment of contaminated groundwater [59] are: • injection of nZVI to form a reactive barrier; • injection of mobile nZVI to form a plume of nZVI; • introduction of NP into the soil to absorb or degrade contaminants. One of the advanced physicochemical technologies used in the photodegradation of organic compounds, photocatalysis, has gained a lot of attention in recent years [1]. One of the world’s most abundant metals is the zero-valent iron metal (ZVI) [16]. Fe ion acts as a reduction agent [11], chlorinated HCs with equal oxidizing ability to oxygen will contend as an electron acceptor with DO, zero-valent iron NPs widely used for dechlorination. Filters of CNTs have successfully recorded to eliminate pathogenic microbes. Srivastava [56] demonstrated that the filters were successful in eliminating bacteria from polluted water (Escherichia coli and Staphylococcus aureus) and Poliovirus Sabin 1 is a type of poliovirus. The efficient development of alumina ultrafine membranes using alumina (A-alumoxanes) NPs was reported by DeFriend, Wiesner, and Barron [15] (7–25 nm). When Fe and Mn are doped with alumina NPs, permeability, and selectivity are increased. Finally, by Meyer, Wood, Bachas, and Bhattacharyya [37], the Fe in bimetallic condition successfully prepares reactive membranes by integrating bimetallic Fe0/Pt0 NPs into acetate films. Biosynthesized silver nanoparticles (Ag-NPs) serve as a biocide in the presence of silver nitrate as well. Son, Youk,

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Lee, and Park [52] reported that Staphylococcus aureus, Escherichia coli, Klebsiella pneumonia, and Pseudomonas aeruginosa are effective against Ag-NPs embedded in cellulose acetate fibers. Dendrimers NPs polymers are soft and used to purify drinking water from organic and inorganic solutes and poisonous metal ions free from microbes. The extremely water-soluble ligand for toxic metal ions, radionuclides, and inorganic anions ranges from 1–20 nm [39]. As delivery vehicles or scaffolds for antimicrobial agents such as silver (I) and quaternary ammonium chlorides, dendritic polymers have also been successfully used. As delivery vehicles or scaffolds for antimicrobial agents such as silver (I) and quaternary ammonium chlorides, these dendritic polymers have also been successfully used [9]. 12.4.3  HYDROCARBON CONTAMINATION REMEDIATION BY NANOPARTICLES For chlorinated HCs, the embedded metal domains are effective. As efficacious biocides against both gram-negative as well as gram-positive (such as Bacillus megaterium and Escherichia coli) and bacterial spores, Magnesium oxide (MgO) is availed, for the removal of pathogenic microbes (Bacillus subtilis). Using the novel yeast strain, Candida digboiensis TERI ASN6, fungal degradation of oily sludge-contaminated soil was able to degrade 40 mg of eicosane in 50 ml of medium minimal salts in 10 days and 72% of heneicosane at pH 3 in 192 h [53]. Monocarboxylic acid intermediates were formed by the alkanes’ degradation mechanisms, whereas the oxygenated pyrenol intermediates are produced by the Pyrenees – the polycyclic aromatic HCs in acidic oily sludge uniquity. Candida digboiensis, ascribing to their robust nature, by the constant disclosure to the pollutants in the oily sludge have the potential of degrading the contaminants present in the levied environment. Thus, the TERI ASN6 strain of the bacteria C. digboiensis has a high potential for bioremediation of HCs. A biosparging device at oilfield services facilities was planned and applied to a co-contaminated As-HC aquifer, Odessa, Texas, USA, during 1997–2001 [12]. Bioreactor-based bioremediation of HC contaminated marine sediments bio-stimulated with monopotassium phosphate (K2HPO4), ammonium nitrate (NH4NO3), ammonium sulfate ((NH4)2SO4), NPK, urea was reported by Chikere [10]. The application for biostimulation was only presented in a group analysis in which microparticles were obtained from the fusion of PBS with urea and subsequent radiation for use in the Pseudomonas aeruginosa biostimulation test to extract Total Petroleum HCs in bench scale studies [3].

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After 30 days of testing, this study resulted in 35.8% oil removal with 25 kGy-irradiated microparticles. 12.4.4  HEAVY METALS CONTAMINATION REMEDIATION BY NANOPARTICLES Mining fields, refineries, and manufacturing areas are the major sources of the toxins, releasing numerous heavy metal radionuclides such as Cadmium, Nickel, Lead, and polycyclic aromatic HCs. The farming technique involves the removal by sequestration of heavy metal contaminants, while later technology degrades organic contaminants, leaving products such as Carbon dioxide and water without damage. Heavy metal contamination is now one of the world’s most serious environmental concerns [23]. In ecological niches, heavy metal contamination from both natural and anthropogenic sources results in the accumulation of metals [32]. Different methods such as photocatalytic oxidation, organic coagulants, electrochemical, bioremediation, ion-exchange resins, reverse osmosis and adsorption have been used to detoxify heavy metals [22]. The new process for heavy metal removal is the nano-based adsorbent. Iron NPs strip nanoadsorbents based on Arsenic (III), Copper (II) Lead (II), Mercury (II), Cadmium (II) Iron oxides, such as hematite, maghemite, and magnetite are used to remove heavy metals from water/wastewater [14]. Heavy metals are separated by the magnetic force of nanoadsorbent iron NPs. The key component is soil mercury and Mercury chloride is present abundantly, which is a major cause of soil pollution. Another cause of mercury exposure and the seed treatment of its derivatives is dental fillings. A variety of bacteria have been reported to demonstrate the ability to withstand high metal concentrations and to reduce the volatile elementary form. 12.5  FUTURE PERSPECTIVES The promising and developmental aspect of NT with their recent researches underwent and their involvement in the environmental betterment and health advances, provide the imperative advances that could be attained in innovative solutions. As this chapter deals with the aspect of NPs their types, mitigators, differential structurizations and the individual dictions in the remediation aspects. As minute and miniscule the pollutants and contaminants in the environment had been assayed in recent studies, this could thus propose the

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necessity of integrated fields of life and technical sciences. As the imperceptibly of the contaminants’ cascades are, this provides the chances of repercussions that could be engineered to provide a sustained, non-toxic makeovers. The identification of the right NPs for bioremediation is a cumbersome process; hence in the future, this process could be eased by carrying out in-silico studies to identify the appropriate NPs for the pollutants, thereby saving the cost and labor involved. In the future, the efficiency and duration of bioremediation will be improved by the modification and adaptation of NT. The breathing of the expected opportunities, the cross-disciplinary nature, and the potential for creativity. The enormous benefits and the statistics of NT has been the vital reason for rapid development of the field. NBR is expected to increase its use in the near future due to its powerful potential and will play a critical role in sustainable development. Nano-phytoremediation though beneficial, is very moderately paced but is highly valuable as it protects and prevents the environment from further deleterious effects. This remediation being modest vigor provides new opportunities to improve the efficacy of the technique to achieve better results. 12.6 SUMMARY The ever promising beacon of technology has always given the scope for answers in the remote challenges that are posed on the continuous unravels of evolving living standards. As inquisitive and comprehensive the field may have endured, the rise of pollutants and the inevitable exposure of the natural environment to their kins have undergone significant evolving tactics. As this chapter provides the base on which the need for bioremediation is necessary so does it provide an induction on how new ventures of innovation could be convoluted with varied orders of material sciences. Progressively this chapter details with the strategies under which the NPs are engineered from gross perspectives to a specific target. Henceforth, the carpet of how new upcoming technologies could be brought about, by laying a foundation of what is the target to be studied under. Even if this branch of study appears to be theoretical and divergent, it is absolutely necessary to have a fundamental knowledge of the mechanisms and interconnections. With this note, the chapter advanced to the domains of how the nanotech particles and their forges could be utilized. By their individual inscriptions of the target remedials and their usage, this chapter concluded with the promising note as to how the motives could be paced forth and briefing the future perspectives of this intuitive field of unique potentials.

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KEYWORDS • • • • • • • •

Bushnell Hass mineral salt medium nanomaterials nanobioremediation nanoparticles reactive oxygen species rhodamin B white rot fungi zero-valent iron

REFERENCES 1. Akhavan, O., & Azimirad, R., (2009). Photocatalytic property of Fe2O3 nanograin chains coated by TiO2 nanolayer in visible light irradiation. Applied Catalysis A, 369(1, 2), 77–82. https://doi.org/10.1016/j.apcata.2009.09.001. 2. Kumari, B., & Singh, D. P., (2016). A review on multifaceted application of nanoparticles in the field of bioremediation of petroleum hydrocarbons. Ecological Engineering, 97, 98–105. https://doi.org/10.1016/j.ecoleng.2016.08.006. 3. Caetano, R. M. J., Bedor, P. B. A., De Jesus, E. F. O., Leite, S. G. F., & Souza, F. G. Jr., (2018). Oil biodegradation systems based on γ irradiated poly (butylene succinate). Macromolecular Symposia, 380(1). https://doi.org/10.1002/masy.201800123, PubMed: 1800123. 4. Castiglione, M., & Cremonini, R., (2009). Nanoparticles and Higher Plants, (Vol. 62, pp. 161–165). Caryologia. 5. Cecchin, I., Reddy, K. R., Thomé, A., Tessaro, E. F., & Schnaid, F., (2017). Nanobioremediation: Integration of nanoparticles and bioremediation for sustainable remediation of chlorinated organic contaminants in soils. International Biodeterioration and Biodegradation, 119, 419–428. https://doi.org/10.1016/j.ibiod.2016.09.027. 6. Cecchin, I., Reginatto, C., Thomé, A., Colla, L. M., & Reddy, K. R., (2016). Influence of physicochemical factors on biodiesel retention in basaltic residual soil. Journal of Environmental Engineering, 142(4), 04015093. https://doi.org/10.1061/(ASCE)EE.19437870.0001060. 7. Chaudhari, A., (2013). Biogenic synthesis of nanoparticles and potential applications an eco-friendly approach. Journal of Nanomedicine and Nanotechnology, 4, 165. https:// doi.org/10.4172/2157-7439.1000165. 8. Chauhan, R., Hari, O. S., Yadav, N., & Sehrawat, (2020). Nanobioremediation: A new and a versatile tool for sustainable environmental clean up—Overview. Journal of Materials and Environmental Science, 11(4), 564–573.

Potential Nanomaterials for Bioremediation 335 9. Chen, C. Z., & Cooper, S. L., (2002). Interactions between dendrimer biocides and bacterial membranes. Biomaterials, 23(16), 3359–3368. https://doi.org/10.1016/s01429612 (02)00036-4. 10. Chikere, C. B., Chikere, B. O., & Okpokwasili, G. C., (2012). Bioreactor-based bioremediation of hydrocarbon-polluted Niger Delta marine sediment, Nigeria. 3 Biotech, 2(1), 53–66. https://doi.org/10.1007/s13205-011-0030-8. 11. Chuang, F. W., Larson, R. A., & Wessman, M. S., (1995). Zerovalent iron-promoted dechlorination of polychlorinated biphenyls. Environmental Science and Technology, 29(9), 2460–2463. https://doi.org/10.1021/es00009a044. 12. Cooley, A., Rexroad, R., Morrisette, J., Cobb, J. A., & Blackert, D., (2009). Biosparging and monitored natural attenuation of hydrocarbon, chlorinated solvent, and arsenicimpacted groundwater. In: 10th International in Situ and On-Situ Bioremediation Symposium (pp. 5–8). Baltimore, MD. 13. Cunningham, S. D., & Ow, D. W., (1996). Promises and prospects of phytoremediation. Plant Physiology, 110(3), 715–719. https://doi.org/10.1104/pp.110.3.715. 14. Dave, P. N., & Chopda, L. V., (2014). Application of iron oxide nanomaterials for the removal of heavy metals. Journal of Nanotechnology, 2014, 1–14. https://doi. org/10.1155/2014/398569. 15. Defriend, K. A., Wiesner, M. R., & Barron, A. R., (2003). Alumina and aluminate ultrafiltration membranes derived from alumina nanoparticles. Journal of Membrane Science, 224(1, 2), 11–28. https://doi.org/10.1016/S0376-7388(03)00344-2. 16. Deng, N., Luo, F., Wu, F., Xiao, M., & Wum, X., (2000). Discoloration of aqueous reactive dye solutions in the UV/Fe0 system. Water Research, 34(8), 2408–2411. https:// doi.org/10.1016/S0043-1354(00)00099-3. 17. Dimkpa, C. O., Mclean, J. E., Latta, D. E., Manangón, E., Britt, D. W., Johnson, W. P., Boyanov, M. I., & Anderson, A. J., (2012). CuO and ZnO nanoparticles: Phytotoxicity, metal speciation, and induction of oxidative stress in sand-grown wheat. Journal of Nanoparticle Research, 14(9), 1–15. https://doi.org/10.1007/s11051-012-1125-9. 18. Durán, N., Marcato, P. D., De Souza, G. I. H., Alves, O. L., & Esposito, E., (2007). Antibacterial effect of silver nanoparticles produced by fungal processes on textile fabrics and their effluent treatment. Journal of Biomedical Nanotechnology, 3(2), 203–208. https://doi.org/10.1166/jbn.2007.022. 19. El-Sheshtawy, H. S., Khalil, N. M., Ahmed, W., & Abdallah, R. I., (2014). Monitoring of oil pollution at Gemsa Bay and bioremediation capacity of bacterial isolates with biosurfactants and nanoparticles. Marine Pollution Bulletin, 87(1, 2), 191–200. https:// doi.org/10.1016/j.marpolbul.2014.07.059. 20. Enamala, M., Shruthi, D., Sarkar, S., Chavali, M., Vasavi, I., & Kuppam, C., (2019). Chapter 3. Assessing interactions of microalgae in synthesizing nanoparticles. In: Rauta, P. R., Mohanta, Y. K., & Nayak, D., (eds.), Nanotechnology in Biology and Medicine Research Advancements and Future Perspectives (p. 291). CRC Press. 21. Fan, F. L., Qin, Z., Bai, J., Rong, W. D., Fan, F. Y., Tian, W., Wu, X. L., et al., (2012). Rapid removal of uranium from aqueous solutions using magnetic Fe3O4 and SiO2 composite particles. Journal of Environmental Radioactivity, 106, 40–46. https://doi. org/10.1016/j.jenvrad.2011.11.003. 22. Fu, F., & Wang, Q., (2011). Removal of heavy metal ions from wastewaters: A review. Journal of Environmental Management, 92(3), 407–418. https://doi.org/10.1016/j. jenvman.2010.11.011.

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Sustainable Nanomaterials for Biosystems Engineering

23. Fujita, M., Ide, Y., Sato, D., Kench, P. S., Kuwahara, Y., Yokoki, H., & Kayanne, H., (2014). Heavy metal contamination of coastal lagoon sediments: Fongafale islet, Funafuti atoll, Tuvalu. Chemosphere, 95, 628–634. https://doi.org/10.1016/j. chemosphere.2013.10.023. 24. Galdames, A., Mendoza, A., Orueta, M., De Soto, G. I. S., Sánchez, M., Virto, I., & Vilas, J. L., (2017). Development of new remediation technologies for contaminated soils based on the application of zero-valent iron nanoparticles and bioremediation with composite. Resource-Efficient Technologies, 3(2), 166–176. https://doi.org/10.1016/j. reffit.2017.03.008. 25. He, K., Chen, G., Zeng, G., Huang, Z., Guo, Z., Huang, T., Peng, M., et al., (2017). Applications of white rot fungi in bioremediation with nanoparticles and biosynthesis of metallic nanoparticles. Applied Microbiology and Biotechnology, 101(12), 4853–4862. https://doi.org/10.1007/s00253-017-8328-z. 26. Hodson, M. E., (2010). The need for sustainable soil remediation. Elements, 6(6), 363–368. https://doi.org/10.2113/gselements.6.6.363. 27. Kanwar, J. S., (1994). Relevance of soil management in sustainable agriculture in dryland areas. Journal of the Indian Society of Soil Science, 16, 1–11. 28. Kariim, I., Abdulkareem, A. S., & Abubakre, O. K., (2020). Development and characterization of MWCNTs from activated carbon as adsorbent for metronidazole and levofloxacin sorption from pharmaceutical wastewater: Kinetics, isotherms, and thermodynamic studies. Scientific African, 7, e00242. https://doi.org/10.1016/j. sciaf.2019.e00242. 29. Khan, N., & Bano, A., (2016). Modulation of phytoremediation and plant growth by the treatment with PGPR, ag nanoparticle and untreated municipal wastewater. International Journal of Phytoremediation, 18(12), 1258–1269. https://doi.org/10.108 0/15226514.2016.1203287. 30. Khodakovskaya, M. V., De Silva, K., Biris, A. S., Dervishi, E., & Villagarcia, H., (2012). Carbon nanotubes induce growth enhancement of tobacco cells. ACS Nano, 6(3), 2128–2135. https://doi.org/10.1021/nn204643g. 31. Kidwai, M., & Mohan, R., (2005). Green chemistry: An innovative technology. Foundations of Chemistry, 7(3), 269–287. https://doi.org/10.1007/s10698-004-2783-1. 32. Kuo, C., & Genthner, B. R. S., (1996). Effect of added heavy metal ions on biotransformation and biodegradation of 2-chlorophenol and 3-chlorobenzoate in anaerobic bacterial consortia. Applied and Environmental Microbiology, 62(7), 2317–2323. https://doi.org/10.1128/aem.62.7.2317-2323.1996. 33. Li, Y. Y., & Li, B., (2011). Study on fungi-bacteria consortium bioremediation of petroleum contaminated mangrove sediments amended with mixed biosurfactants. Advanced Materials Research, 183–185, 1163–1167. https://doi.org/10.4028/www. scientific.net/AMR.183-185.1163. 34. Ma, X., & Wang, C., (2010). Fullerene nanoparticles affect the fate and uptake of trichloroethylene in phytoremediation systems. Environmental Engineering Science, 27(11), 989–992. https://doi.org/10.1089/ees.2010.0141. 35. Mandeep, S. P., & Shukla, P., (2020). Microbial nanotechnology for bioremediation of industrial wastewater. Frontiers in Microbiology, 11, 590631. https://doi.org/10.3389/ fmicb.2020.590631. 36. Tanaka, M., Arakaki, A., Staniland, S. S., & Matsunaga, T., (2010). Simultaneously discrete biomineralization of magnetite and tellurium nanocrystals in magnetotactic

Potential Nanomaterials for Bioremediation 337 bacteria. Applied and Environmental Microbiology, 76(16), 5526–5532. https://doi. org/10.1128/AEM.00589-10. 37. Meyer, D. E., Wood, K., Bachas, L. G., & Bhattacharyya, D., (2004). Degradation of chlorinated organics by membrane-immobilized nanosized metals. Environmental Progress, 23(3), 232–242. https://doi.org/10.1002/ep.10031. 38. Mishra, A., Kumari, M., Pandey, S., Chaudhry, V., Gupta, K. C., & Nautiyal, C. S., (2014). Biocatalytic and antimicrobial activities of gold nanoparticles synthesized by Trichoderma sp. Bioresource Technology, 166, 235–242. https://doi.org/10.1016/j. biortech.2014.04.085. 39. Okhovat, N., Hashemi, M., & Golpayegani, A. A., (2015). Photocatalytic decomposition of metronidazole in aqueous solutions using titanium dioxide nanoparticles. Journal of Materials and Environmental Science, 6(3), 792–799. 40. Ottaviani, M. F., Favuzza, P., Bigazzi, M., Turro, N. J., Jockusch, S., Tomalia, D. A., & Rizwan, A., (2000). A TEM and EPR investigation of the competitive binding of uranyl ions to starburst dendrimers and liposomes: Potential use of dendrimers as uranyl ion sponges. Langmuir, 16(19), 7368–7372. https://doi.org/10.1021/la000355w. 41. Paknikar, K. M., Nagpal, V., Pethkar, A. V., & Rajwade, J. M., (2005). Degradation of lindane from aqueous solutions using iron sulfide nanoparticles stabilized by biopolymers. Science and Technology of Advanced Materials, 6(3, 4), 370–374. https:// doi.org/10.1016/j.stam.2005.02.016. 42. Manivasagan, P., Nam, S. Y., & Oh, J., (2016). Marine microorganisms as potential biofactories for synthesis of metallic nanoparticles. Critical Reviews in Microbiology, 42(6), 1007–1019. https://doi.org/10.3109/1040841X.2015.1137860. 43. Pang, Y., Zeng, G. M., Tang, L., Zhang, Y., Liu, Y. Y., Lei, X. X., Wu, M. S., et al., (2011). Cr(VI) Reduction by Pseudomonas aeruginosa immobilized in a polyvinyl alcohol/sodium alginate matrix containing multi-walled carbon nanotubes. Bioresource Technology, 102(22), 10733–10736. https://doi.org/10.1016/j.biortech.2011.08.078. 44. Rawat, M., Yadukrishnan, P., & Kumar, N., (2018). Chapter 14. Mechanisms of action of nanoparticles in living systems. In: Pankaj, & Anita, S., (eds.), Microbial Biotechnology in Environmental Monitoring and Cleanup (pp. 220–236). IGI Global Publishing. 45. Rizwan, M., Singh, M., Mitra, C. K., & Morve, R. K., (2014). Ecofriendly application of nanomaterials: Nanobioremediation. Journal of Nanoparticles, 2014, 1–7. https://doi. org/10.1155/2014/431787, PubMed: 431787. 46. Sayles, G. D., You, G., Wang, M., & Kupferle, M. J., (1997). DDT, DDD, and DDE dechlorination by zerovalent iron. Environmental Science and Technology, 31(12), 3448–3454. https://doi.org/10.1021/es9701669. 47. Shiying, H., Zhong, L., Duan, J., Feng, Y., Yang, B., & Yang, L., (2018). Bioremediation of wastewater by iron oxide-biochar nanocomposites loaded with photosynthetic bacteria. Frontiers in Microbiology, 8, 823–833. 48. Singh, B., Shan, Y. H., Beeebout, S. E. J., Singh, Y., & Buresh, R. J., (2008). Crop residue management for lowland rice-based cropping systems in Asia. Advances in Agronomy, 98, 118–199. 49. Singh, B. K., (2009). Organophosphorus-degrading bacteria: Ecology and industrial applications. Nature Reviews. Microbiology, 7(2), 156–164. https://doi.org/10.1038/ nrmicro2050.

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50. Singh, B. K., & Walker, A., (2006). Microbial degradation of organophosphorus compounds. FEMS Microbiology Reviews, 30(3), 428–471. https://doi.org/10.1111/ j.1574-6976.2006.00018.x. 51. Singhal, R. K., Gangadhar, B., Basu, H., Manisha, V., Naidu, G. R. K., & Reddy, A. V. R., (2012). Remediation of malathion contaminated soil using zero-valent iron nanoparticles. American Journal of Analytical Chemistry, 03(1), 76–82. https://doi. org/10.4236/ajac.2012.31011. 52. Son, W. K., Youk, J. H., Lee, T. S., & Park, W. H., (2004). Preparation of antimicrobial ultrafine cellulose acetate fibers with silver nanoparticles. Macromolecular Rapid Communications, 25(18), 1632–1637. https://doi.org/10.1002/marc.200400323. 53. Sood, N., Patle, S., & Lal, B., (2010). Bioremediation of acidic oily sludge-contaminated soil by the novel yeast strain candida digboiensis TERI ASN6. Environmental Science and Pollution Research International, 17(3), 603–610. https://doi.org/10.1007/ s11356-009-0239-9. 54. Souri, Z., Karimi, N., Sarmadi, M., & Rostami, E., (2017). Salicylic acid nanoparticle (Sanps) improves growth and phytoremediation efficiency of Isatis cappadocica Desv. under arsenic stress. IET Nanobiotechnology, 11(6), 650–655. https://doi.org/10.1049/ iet-nbt.2016.0202. 55. Srivastav, A., Yadav, K. K., Yadav, S., Gupta, N., Singh, J. K., Katiyar, R., & Kumar, V., (2018). Chapter 16. Nano-phytoremediation of pollutants from contaminated soil environment: Current scenario and future prospects. In: Ansari, A., Gill, S., Gill, R. R., Lanza, G., & Newman, L., (eds.), Phytoremediation (pp. 383–401). Springer Nature Publishing. 56. Srivastava, A., Srivastava, O. N., Talapatra, S., Vajtai, R., & Ajayan, P. M., (2004). Carbon nanotube filters. Nature Materials, 3(9), 610–614. https://doi.org/10.1038/ nmat1192. 57. Taniguchi, N., (1974). On the basic concept of nanotechnology. Proceedings of the International Conference on Production Engineering (Vol. 2, pp. 18–23). Tokyo 58. Tratnyek, P. G., & Johnson, R. L., (2006). Nanotechnologies for environmental cleanup. Nano-Today, 1(2), 44–48. https://doi.org/10.1016/S1748-0132(06)70048-2. 59. Tripathi, S., Sanjeevi, R., Jayaraman, A., Chauhan, D., & Rathoure, A., (2018). Chapter 12. Nano-bioremediation: Nanotechnology and bioremediation. In: Rathoure, A. K., (ed.), Biostimulation Remediation Technologies for Groundwater Contaminants (pp. 202–219). IGI Global Publishing. 60. Vázquez-Núñez, E., Molina-Guerrero, C. E., Peña-Castro, J. M., FernándezLuqueño, F., & De La Rosa-Álvarez, M. G., (2020). Use of nanotechnology for the bioremediation of contaminants: A review. Processes, 8(7), 826. https://doi. org/10.3390/pr8070826. 61. Geetha, V., Sujata, R., Shreenidhi, K. S., & Sundararaman, T. R., (2018). Histopathological and HPLC analysis in the hepatic tissue of Pangasius sp. exposed to diclofenac. Polish Journal of Environmental Studies, 27(6), 2493–2498. https://doi. org/10.15244/pjoes/75829. 62. Xiao, X., Ma, X. B., Yuan, H., Liu, P. C., Lei, Y. B., Xu, H., Du, D. L., et al., (2015). Photocatalytic properties of zinc sulfide nanocrystals biofabricated by metal-reducing bacterium Shewanella oneidensis MR-1. Journal of Hazardous Materials, 288, 134–139. https://doi.org/10.1016/j.jhazmat.2015.02.009.

Potential Nanomaterials for Bioremediation 339 63. Yadav, K. K., Singh, J. K., Gupta, N., & Kumar, V., (2017). A review of nanobioremediation technologies for environmental cleanup: A novel biological approach. Journal of Materials and Environmental Science, 8(2), 740–757. 64. Fan, Y., Saito, T., & Isogai, A., (2008). Chitin nanocrystals prepared by TEMPOmediated oxidation of Α-chitin. Biomacromolecules, 9(1), 192–198. https://doi.org/ 10.1021/bm700966g. 65. Zhang, W. X., (2003). Nanoscale iron particles for environmental remediation: An overview. Journal of Nanoparticle Research, 5(4), 323–332.

CHAPTER 13

SMART NANOMATERIALS FOR BIOREMEDIATION AND BIODEGRADATION: LABORATORY AND ON-SITE APPLICATIONS AND FUTURE TRENDS ZEYNEP YILMAZ-SERCINOGLU, SELCEN DURMAZ-SAM, FULDEN ULUCAN-KARNAK, and CANSU İLKE KURU

ABSTRACT Industrial development together with the advances in technology have been used solely to overcome nature and to utilize its resources for a long while. Even after pollution and/or its consequences started to threaten lives and biodiversity went on a decline, there was no sufficient control over the industrial and municipal operations. However, a major change in the global perspective of industrial/technological progress has become a necessity–environment can not be sacrificed for development. Although it has not been achieved either by governments or industry itself, many countries try to prevent pollution at the source with the enforcement of regulations or to recuperate the environmental pollution in the light of current scientific research. The bioremediation methodology, which is among the biotechnological improvement methods, is efficient, economical, versatile, and recognized as an environmentally friendly solution. Bioremediation – recovery of pollution created by biodegradable pollutants with the aid of environmentally safe materials and methods–is one of the current subjects of research and application due to its advantages over available Sustainable Nanomaterials for Biosystems Engineering: Trends in Renewable Energy, Environment, and Agriculture. Junaid Ahmad Malik, Megh R. Goyal, Mohamed Jaffer M. Sadiq (Eds.) © 2023 Apple Academic Press, Inc. Co-published with CRC Press (Taylor & Francis)

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physicochemical techniques. Biodegradation of pollutants is executed on-site, whenever possible, but when toxic concentrations of pollutants are a concern for indigenous organisms or there is a high risk of spreading for pollution, then special facilities designed for that purpose are necessary. Increasing the bioavailability of contaminants and decreasing the treatment times especially at in-situ applications have been two major concerns of bioremediation. The latest advancement in bioremediation includes the utilization of specially designed nano-sized materials, which may also help overcome those issues. Various nanomaterials (NMs) have been proposed as promising agents to enhance the biological removal of agrochemicals, pharmaceuticals, hydrocarbons (HCs), radionuclides, and other heavy metals from the environment. Nevertheless, investigation of those NMs in terms of their cytotoxicity and understanding their fate under varying environmental conditions after bioremediation are essential. 13.1 INTRODUCTION Biodegradation is defined as the transformation of materials into simpler organic molecules within biological routes of organisms. Bioremediation, on the other hand, is the utilization of biological entities, including but not limited to microorganisms, in the removal of pollutants from the environment. In other words, biodegradation of polluting materials is the objective of bioremediation. There is, unfortunately, a wide range of contaminants that can be found in nature due to anthropogenic activities and many of them are artificial compounds that are quite bizarre to indigenous organisms. Biomineralization of contaminating materials into inorganic substances is the ultimate way for clean-up, however that is something hard to achieve in particular when dealing with complex, non-conventional molecules. Bioremediation can be employed on the site of contamination (in-situ) whenever it is practical in terms of contamination type, degree, and extent, existence of degrading organisms or environmental conditions. Biostimulation of natural organisms becomes a convenient practice for the improval of biodegradation rates by supplying essential organic/inorganic compounds. As the pollution level cannot be manageable in-situ, then the treatment of contaminated water/soil is performed in special facilities that were constructed to sustain better control of bioremediation (ex-situ). Various factors affect the biodegradation of contaminants in the environment [35]. The type of contaminant is an important factor because they are in numerous types in various structures. The more similar the

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contaminant structure to natural organic compounds, the better chance they have for biodegradation by organisms. Concentration of the contaminants is another main factor because the toxicity of a contaminant over an organism is defined by its concentration. High pollutant concentrations may induce enzyme inhibitions/repressions leading to the inactivation or death of organisms, including those that are able to degrade them. The third factor is the type of organisms that are metabolically capable of the breakdown of those pollutants. Organisms may use them as carbon and/or electron sources, or sometimes neither is valid but they still degrade them to some extent through side reactions, which is called co-metabolism. Bioaugmentation has become a research subject, particularly for some anthropogenic compounds that native organisms are inefficient in their removal. Non-native or genetically modified organisms, that have been cultivated in the laboratory, can be introduced on the site of contamination to enhance bioremediation. And last but not least, environmental factors including physical, geological, and chemical properties of the polluted site influence both the rate and fate of biodegradation [31] (Figure 13.1).

FIGURE 13.1  Processes of removal of pollutants via nanomaterials. Source: Reprinted from Ref. [29]. https://creativecommons.org/licenses/by/4.0/

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Bioavailability of pollutants to degrading organisms is another parameter that impacts the efficiency of breakdown. Bioavailable portion defines the effective concentration of contaminant that was left over after flux and partitioning [5]. Once the chemical is released in the environment, it starts to dissipate and partition among different phases and compartments (such as water, soil, soil pore water, biota, and sediment) until an equilibrium is reached. Partitioning depends on both chemical properties and environmental conditions. Ionic compounds, highly polar organic molecules, or low molecular-size compounds typically have high solubilities in water, which increase their contact with aqueous organisms, and in turn their degradation prospect. On the other hand, volatile compounds can escape into the air before being degraded and bring about an additional air pollution problem which potentially turns into a soil or water pollution in regions where they are carried away. Moreover, pollutants introduced into soil many years ago and left off without any remediation attempt tend to age (weathering), which reduces their bioavailability to organisms together with the potential for bioremediation. It was suggested that during aging molecules got sorbed slowly into organic matter and/or minute pores in soil from where their desorption would be exceedingly slow [7]. NMs exhibit distinctive properties in comparison with their bulky counterparts that makes them convenient in many different fields to serve as catalysts of various reactions, surface coatings, antibacterial agents, fire retardants, aids in imaging, cancer detection and drug delivery. More recently NMs have been utilized in the removal of various pollutants including HCs, textile dyes, xenobiotics, predominantly under laboratory conditions. Nanotechnology (NT) has the potential to become a resort in bioremediation practices specifically with regard to reduction of biodegradation period under natural conditions only after their impact on natural organisms as well as their fate after release are revealed in more detail. This chapter presents current applications of nanoparticles (NPs) in bioremediation/biodegradation studies, starting with those related to the removal of petroleum products. 13.2  BIOREMEDIATION OF PETROLEUM PRODUCTS Crude oil derivatives have been exploited in domestic and industrial operations to the greatest extent as an energy source. Crude oil is made up of mainly HCs, which can be divided into four classes; saturated HCs (propane, butane, etc.), aromatic HCs (benzene, toluene, etc.), the asphaltenes (phenols,

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ketones, etc.), and the resins (pyridines, sulfoxides, amide derivatives, etc.) [62]. Major part of the petroleum is, however, comprised of saturated HCs, which are followed by aromatics [56]. HCs in petroleum and its products are the main sources of pollution in water and soil globally. While natural (e.g., during earthquakes) or accidental (e.g., during exploration or transportation) spills keep introducing crude oil or its products into the environment, a wide range of HCs in them are long known to be biodegradable under aerobic conditions by microorganisms such as bacteria, archaea, fungi, and some algae that are found in almost all ecosystems. And more recently anaerobic degradation routes have also been discovered when nitrate, sulfate, Mn(IV), Fe(III), and/or CO2 are utilized as terminal electron acceptors [18]. The degree of biodegradation depends primarily on the composition and amount of crude oil/its products available to inhabiting organisms on the pollution site as well as temperature [56]. 13.2.1  BTEX, PAHS, PHENOLS Monoaromatic HCs are collectively known as Benzene, Toluene, Ethylbenzene, and Xylene (BTEX). They are commonly found in gasoline and have high volatility, and solubility [18]. They are released into the environment not only in the form of crude oil or its refinements but also through discharges from metal, paint, textile, and chemical manufacturing industries. BTEX compounds are among 123 priority pollutants established by the United States Environmental Protection Agency (US EPA) owing to their toxicity. They are more abundant in nature and more soluble than Polycyclic Aromatic Hydrocarbons (PAHs) and have been reported to be present mostly in groundwater [27]. PAHs, on the other hand, are constituents of petroleum and its products to a lesser extent than BTEX compounds. 16 PAH compounds are classified as priority pollutants by US EPA due to their mutagenic/carcinogenic potential. PAHs are hydrophobic in nature therefore they tend to partition between inorganic materials, debris, sediment, and dust. Phenol composes a small portion of crude oil but it is also manufactured chemically and used in the synthesis of nylon and other synthetic fibers [57]. BTEX and PAH compounds have been reported to be biodegradable under aerobic and anaerobic conditions by bacterial and fungal strains. Yet, aerobic degradation has an advantage owing to higher attainable breakdown rates, which cause a significant reduction in the duration of in-situ bioremediation applications. Nevertheless, depletion of oxygen (O2) in the polluted soil, water, and groundwater becomes a serious concern for biota that depend

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on O2, hence biodegradation ceases. Efficient and persistent ways of O2 introduction other than air/O2 sparging have been investigated to overcome deoxygenation during biodegradation of contaminants. Compounds acting in a similar way to Fenton’s reagent and producing O2 together with hydroxyl radicals (OH•) such as hydrogen peroxide (H2O2), calcium peroxide (CaO2), magnesium peroxide (MgO2), and potassium permanganate (KMnO4) have been implemented for the oxidation of sorbed molecules while introducing O2 steadily [20]. O2 releasing compounds can be applied to permeable reactive barriers (PRBs) made of permeable materials to remediate groundwater in-situ. Recently individual or composite nano-sized particles of those O2 releasing compounds have been under investigation to achieve longer half-lives and/or wider distributions specifically in groundwater and therefore to enhance O2 persistence and availability to regions further away from the application site. Nevertheless, they would give rise to oxidative stress on innate microorganisms as anticipated. Synthesized and used alginate encapsulated CaO2 nanoparticles (CaO2-NPs) in the removal of benzene from the groundwater and sandy soil both retrieved from a well near a petroleum industry. Batch experiments with benzene-contaminated groundwater and encapsulated / non-encapsulated CaO2-NPs at an initial pH of 7.4 and 15°C showed that encapsulation decreased the negative effects of CaO2-NPs on microorganisms by reducing the pH changes and radical productions experienced after NP introduction, in addition to sustaining steady dissolved oxygen (DO) levels. And in turn 100% benzene (50 mg/L) removal was achieved while only 63% of benzene was biodegraded in the presence of non-encapsulated NPs within the same period (60 days). In the same study, sand-packed columns containing those NPs in the form of PRBs were also utilized at a continuous velocity of 0.2 m/ day. Markedly, higher microbial counts together with 100% benzene removal efficiency were obtained in the column with encapsulated CaO2-NPs in comparatively less time (30 days) [51]. In a more recent study by Oehlmann et al. [52] non-encapsulated MgO2NPs were applied in both batch and column studies to remove toluene from the groundwater and sand retrieved from the same site as their previous study. Batch studies revealed that MgO2-NPs decomposed at a faster rate (in 20 days) than CaO2-NPs in water. Due to that re-introduction of MgO2NPs were put into practice in the column study. Columns, designed in a similar fashion to their previous study [51], were fed with either untreated or sterilized and sodium azide added groundwater to mimic biotic and abiotic conditions, respectively. Complete removal of toluene (50 mg/L)

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was accomplished in the biotic column while that was only 60% for the abiotic column of MgO2-NPs. Similarly, CaO2-NPs, which were capable of stable release of O2 for almost 70 days at neutral pH, on naphthalene removal from groundwater. Batch studies with groundwater containing 20 mg/L naphthalene revealed that CaO2-NPs at 400 mg/L or a higher concentration are required to remove all naphthalene in 20 days or less, however a dramatic decrease in microbial count was observed at higher naphthalene concentration than 400 mg/L. Columns packed with and without CaO2-NPs in a PRB made of pumice particles (45% by volume) were operated by the same team for 350 days to treat groundwater having 20 mg/L naphthalene and 4 mg/L of DO. Indigenous microorganisms in the column without the presence of CaO2-NPs and PRB (natural attenuation column) were able to remediate only 19.7% of the contaminant in 350 days while those supplied with O2 releasing NPs in the other column achieved complete removal starting from the 50th day of operation with the help of additional injections of CaO2-NPs whenever DO levels dropped below 8 mg/L [29]. A great deal of remediation research contains laboratory studies of NPs coupled with immobilized cells, enzymes, (bio)polymers, or biosurfactants. Immobilization of biodegrading organisms or their enzymes exclusively onto magnetic nanoparticles (MNPs) facilitates the recovery and reuse by the courtesy of their separability with a magnet. In one of those studies [37] BTEX compounds (30 mg/L) and phenol (100 mg/L) in petroleum wastewater from a petrochemical wastewater treatment plant were treated in batch experiments with the bacterium Comamonas sp. JB immobilized onto commercial Fe2O3 (a and r types) and Fe3O4-NPs with the help of gellan gum. The highest biodegradation activities were obtained when bacterial cells were immobilized on r-Fe2O3-NPs. For instance, complete breakdown of 100 mg/L phenol and 30 mg/L benzene and toluene were maintained within 6 h, 12 h and 16 h, respectively. Furthermore, bacterium-r-Fe2O3-NP composites retained their activity for 5 cycles by consuming all HCs completely within 20 h when phenol and BTEX compounds were supplied at identical initial concentrations to the previous part of the study. In another study, synthesized silica-coated Fe-NPs, functionalized their surface with APTES (3-aminopropyltriethoxysilane), then immobilized tyrosinase from Agaricus bisporus (edible mushrooms) on them, and finally employed those complex NPs in batch trials for phenol removal from wastewater prepared to contain 250 mg/L phenol in a well water [2]. Though treatment time for this particular part of the study was not specified by the authors phenol removal efficiency reportedly decreased from 100% (1st cycle) to 52% after 6 cycles

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of reuse. Correlatively, laccase enzyme was immobilized by Austin et al. [8] onto Cu (II) ion chelated chitosan based copolymer NPs, which enabled to retain 50% of its activity after 8 cycles, and used in the treatment of synthetic phenol solution (20 mg/L). Although laccase had limited oxidation power over phenol, 82% removal efficiency was attained within 4 h with the use of immobilized NPs while it took 12 h for free laccase to oxidate 80% of phenol. The incorporation of both laccase and a biosurfactant (outer membrane protein A (Omp A) of Escherichia coli) onto polyether amine modified Fe3O4-NPs to act on oil/water interface of heavy crude oil emulsions, which are generated in large volumes by oil refineries. When 5,000 ppm of bionanocomposites were employed in the demulsification of 1% (w/w) oil/water emulsions in collaboration with an external magnetic field they declared to obtain 88% HC removal efficiency [59]. Heterogeneous photocatalysis of fiberglass coated TiO2-C-Ag nanoparticles with the enzymatic activity of crude enzymes of two different fungal species entrapped in alginate hydrogels for the treatment of synthetic wastewater containing phenanthrene (a PAH molecule) together with the solubilizing agents of Tween 80 and DMSO. Glass bead and fiberglass packed fixed-bed column was impregnated with enzyme-entrapped hydrogels and used as a pre-treatment step. A second column contained coated NCs and was irradiated by 2 external UV-A lamps to induce photocatalysis. The combined work of columns resulted in 94% removal of 28 mg/L phenanthrene after 11 hours with the supply of O2 at a rate of 0.125 mL/min. The aforementioned studies are promising with regard to ex-situ applications of NT [30]. 13.2.2  PLASTIC MATERIALS Plastics are literally everywhere in consequence of their versatile and convenient properties including durability, hydrophobicity, moldability, elasticity, and capabilities of corrosion resistance, thermal, and electrical insulation. A wide range of plastics can be derived from fossil fuels. However, there has been a growing attention towards the development and use of biobased and/or biodegradable plastics made of cellulose, starch, polylactic acid (PLA), and polyhydroxyalkanoates (PHA) [43]. Plastics are grouped under two primary polymers as thermoplastics and thermosets. Thermoplastics, such as polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl chloride (PVC), soften when heated therefore they are recyclable. Thermoset plastics, on the other hand, cannot soften once casted.

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Epoxide (EP) and polyurethane (PU) belong to this group [1]. Additionally, bisphenol A (BPA) and phthalates, being the most prevalent plasticizers, are added in plastic polymers to enhance their physical characteristics and when they leach into the environment, they tend to accumulate in organisms and cause developmental and reproductive issues in a wide range of species including humans [48, 54]. According to the report of the Association of Plastics Manufacturers (Plastics Europe) 368 million tons of new plastics were produced in 2019 worldwide, 51% of which belonged to Asian countries mainly China (31%) [25]. As they have a wide application range and in turn are being utilized abundantly, plastic pollution has become a global problem both on land and in the marine environment. Micro and nanoplastics present in commercial products or arising from weathering of macro plastics are particularly important because they can be transported easily to the atmosphere, sediments, oceans, or accumulate in organisms owing to their petty sizes. Furthermore, they have a potential to attract other chemical contaminants, hydrophobic ones in particular such as metals, PAHs, and dichlorodiphenyltrichloroethane (DDT), due to their shape and/ or high surface area, which complicates potential removal processes [48]. Resistance to biodegradation also accounts for the widespread use of plastics. However, the more plastics build up in the environment, the more organisms adapt their metabolism to their biodegradation. Therefore, a great deal of studies have concentrated on the isolation and identification of novel organisms or enzymes that are capable of degradation of major plastic polymers [76], while others have employed genetic/protein engineering tools to construct superior strains/enzymes [10]. First part of an interesting study by Yang et al. [72] revealed that mealworms (larvae of Tenebrio Molitor Linnaeus), when fed solely with Styrofoam (a polystyrene product), converted 47.7% of polystyrene carbon into CO2 and incorporated only 0.5% into the fat tissue while the rest was excreted in the form of depolymerized products. Consecutive study by the same authors brought the impact of gut microflora of mealworms to light that depolymerization and mineralization of polystyrene was mainly achieved by that gut consortium [73]. These findings are encouragingly pointing out that microorganisms hold a great potential to be the primary precursors of plastic biodegradation in nature. Enhanced photocatalysis with the aid of titanium oxide nanoparticles (TiO2-NPs) have been reported by different authors after UV light exposure of plastics for many days at O2 presence when NPs were incorporated during their manufacture [50, 53, 74]. Nevertheless, TiO2 incorporation makes plastics vulnerable to UV radiation and limits their lifetime prematurely.

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To overcome this problem by developing a switchable photocatalyst, which constituted of TiO2-NPs encapsulated by Ca- or Sr-polyphosphate. When the plastic material containing this composite ends up in sea, Na+ and Mg2+ ions in seawater displace with Ca2+ and Sr2+ ions in the polyphosphate shell, bringing about the dissolution of the shell and in turn the release of TiO2-NPs. Thereafter, radicals created by TiO2-NPs start to attack the organic matter [71]. Besides those mentioned, there is a limited number of studies that include NT as an aid for plastic biodegradation, mainly because many NPs exhibit antimicrobial effects. For instance, a carbon-based NP made of 60 carbons (fullerene-60) was employed for the biodegradation of powdered low-density polyethylene (LDPE) by two different bacterial consortia [3]. Authors concluded that fullerene-60 made an additive effect on LDPE removal when it was supplied at its minimum inhibitory concentration (0.01% (w/v)) in the minimal culture medium of bacteria at neutral pH, albeit growth curves for both consortia were subsided. In a more recent study by Baena-Baldiris et al. [9] silver NPs (AgNPs) in collaboration with Rhodococcus jostii PEVJ9 cells improved the biodegradation of di(2-ethylhexyl) phthalate (DEHP), which is the most dominant plasticizer. When supplied with AgNO3, extracellular esterase enzyme of bacterial cells reduced Ag+ ions into AgNPs on the cell surface and their existence promoted the bioavailability and assimilation of DEHP as a carbon source. 13.3  BIOREMEDIATION OF PERSISTENT ORGANIC POLLUTANTS AND PHARMACEUTICALS 13.3.1  TEXTILE DYES Azo dyes are utilized in widespread application areas like textile and pharma industries (including cosmetics), and also in the printing sector due to their cost-effectiveness, broad range of colors, and stability, and they include approximately 65% of carbon-based dyes [36]. More than 50% of the dyes used in the textile industry ends up in effluents as remainings of colorization. Dyes in this effluent threatens both the aquatic environment and due to bioaccumulation effect, human health, since they are resistant to thermal and photodegradation [32]. Conventional dye removal methods have low efficiency [11]. Integration of NMs/NPs in dye removal processes can increase the remediation capability, speed up degradation, and reduce process cost. In a recent study [55], Pseudomonas aeruginosa was cultivated to produce AgNPs. Those AgNPs were tested on the degradation of Bromothymol

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blue and Fantacell dyes. AgNPs were embedded on Sodium Alginate/Poly Acrylamide polymers (Na-Alg/Poly-AAm) to produce (Na-Alg/Poly-AAm) Ag NPs. According to the results, (Na-Alg/Poly-AAm) with AgNPs had more remediation potential than (Na-Alg/Poly-AAm) polymer alone. Maximum reduction of Fantacell dye was achieved in 45 minutes with a percentage of 87%, while that of Bromothymol blue was 87% after 150 minutes. In another study [40], adsorption profiles of methylene blue (MB) with Fe3O4/ ZrO2, enhanced with nanographene platelets (NGP) and graphene, were investigated. Adsorption of MB increased both with NGP and graphene addition to the Fe3O4/ZrO2. But graphane promoted the adsorption of MB more than NGP. Synthesized manganese oxide and iron oxide (FexOy) NPs (MnNPs) using aqueous extract of Acorus calamus rhizome. MB and Congo red dyes were successfully reduced by photocatalytic activities of iron oxide NPs and mixture of iron and manganese NPs, while MnNPs indicated moderate activity. Aqueous plant extract (Dimocarpus longan, DL) and FeCl3 were also used to produce iron NPs (FeNPs) [78]. FeNPs could be used for degradation of methyl orange dye in a broad pH range and were stable even after 28 days of storage [36]. Magnetic cross-linked enzyme aggregates (CLEAs) of laccase were bonded by amino-functionalized MNPs to increase laccase activity and stability and environmental application was tested with a laboratory scale perfusion basket reactor (BR) to assess its potential for continuous decolorization of dyes. Remazol brilliant blue R was decolorized with 61–96% efficiency. In BR, decolorization was more than 90% and the CLEA activity was stored more than 10 h of continuous operation. Those results increases the industrial significance of CLEAs [41]. Magnetic cobalt–iron oxide nanoparticles (CoFeNPs) were modified with dodecylamine and hydrazine, CoFeNPs1 and CoFeNPs2, respectively. Six negatively charged azoic dyes were investigated to understand their removal efficiency from water via CoFeNPs. Effect of time, size of CoFeNPs, type of anchored amine, and structure of the dye on removal efficiency were compared. CoFeNPs2 was superior to CoFeNPs1 under similar conditions in the removal concept of each dye (CoFeNPs2’s percent dye removals were between 68.0% and 98.9%, while equilibrium adsorption capacities (qe) were 6.6–23.5 mg g–1). Amine-functionalized CoFeNPs could be potential cost-effective adsorbents. Detailed desorption studies corroborated the remarkable reusability of both CoFeNPs, which revealed the industrial potential of CoFeNPs [58].

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13.3.2  BIOREMEDIATION OF PESTICIDES Pesticide is a general term to define the chemicals which are used to kill pests. Pesticides include insecticides, avicides, fungicides, herbicides, bactericides, rodenticides, and virucides which acts on insects, plants, birds, rodents, fungi, bacteria, and viruses, respectively. Just like “medicine,” the dosage of pesticide is important. It should be both low enough to be non-toxic to the environment and also high enough to control pests. Unfortunately, unconscious utilization of pesticides poses a critical health concern for all living organisms in the environment. Physiochemical properties of the pesticide, environmental conditions such as light, humidity or heat and also the availability of organisms that are capable of degrading pesticides are important parameters for degradation of pesticides [9]. Removal or remediation of pesticides can also be mediated by NT. NPs, NCs, immobilization of enzymes on NPs are some of the approaches [69]. Chlorpyrifos (pesticide) is a broadly used pesticide and shows acute toxicity. Iron MNPs were used to immobilize laccase for increasing its catalytic properties. The stability of the immobilized laccase was protected up to 100 h. Degraded metabolic products of chlorpyrifos were confirmed by HPLC. Immobilized laccase outperformed free laccase [63]. In a larger scale study (fixed-bed column) [68], PU foam coated onto polyurethane foam (CPU) was coated with AgNPs, AgNPs fused into either polyurethane foam (FPU), or glass beads (GB) and their chlorpyrifos removal efficiencies were compared. AgNPs used in this study were synthesized using hibiscus leaf extract (Synthetic NPs, SNP). Comparison with commercial AgNPs (CNP) revealed that CNP-CPU and CNP-FPU were slightly better in removing chlorpyrifos than SNP-CPU and SNP-FPU, whereas SNP-GB was better in removing chlorpyrifos than CNP-GB. Among all tested composites, CNP-FPU had the highest degradation percentage by 96% and this composite was recommended as a potential portable module at an industrial scale. Calcium tungstate (CaWO4) NPs to degrade cynophos. Cynophos is used an insecticide and avicide in agriculture. Cynophos has inhibitory action on acetylcholinesterase (AChE) which is an important enzyme in neural and muscular system regulating signal transduction [66]. It has both toxical effects to all living organisms in the environment. In this study, they monitored the degradation product of cynophos, dimethyl phosphorothioic acid (DMPA), by 31P nuclear magnetic resonance (31PNMR) technique. Under optimized conditions, 31PNMR spectra showed that cyanophos were degraded to DMPA with a yield of 92% through CaWO4 NPs [75].

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Synthesized NC of GO/CuFe2O4–CdS to be used as a photocatalyst for the breakdown of imidacloprid, an insecticide, in water. Pseudo-first order kinetics was seen in the degradation of imidacloprid. Rate of degradation was compared with other current photocatalysts in the literature [79]. Results showed that GO/CuFe2O4–CdS had higher Kapp value (0.0623 min–1) than other NCs. In a recent study [45], increasing one-pot organophosphates (OPs) chemoenzymatic degradation to p-aminophenol (PAP) was aimed. In order to achieve they immobilized His-tagged organophosphohydrolase (OpdA) with Yolk-Shell Co/C@SiO2@Ni/C NPs (OpdA@Co/C@SiO2@ Ni/C NPs). Complete degradation of PAp to PAP was achieved by Co/C@ SiO2 and Co/C@SiO2@Ni/C within 9 and 6 minutes, respectively. OpdA@ Co/C@SiO2@Ni/C NPs retained their catalytic efficacy more than 60% when reused for 7 cycles. In addition OpdA@Co/C@SiO2@Ni/C showed enhance pH and thermal stability compared to the free form of PDA. 13.3.3  BIOREMEDIATION OF PHARMACEUTICALS Pharmaceuticals are evaluated as contaminants that negatively affect not only humans but also aquatic life, even at very low concentrations. Removing of these contaminants were carried out with conventional treatment procedures, but they are not enough. Eliminating of these pharmaceuticals were performed commonly with photocatalysis that is an advanced oxidation process (AOP) [6]. There are also researches for environment-friendly removal methods that include catalysis by microorganisms. Biodegradation term can be explained as metabolizing of pharmaceutical compounds by microorganisms both under aerobic or anaerobic conditions in wastewater treatment plants or in the environment [4]. 13.3.4  BIOREMEDIATION OF ENDOCRINE DISRUPTORS Endocrine disruptors (EDs) mimic sex steroids of in vertebrates without harming or changing the endocrine system [12]. The most common EDs can be compiled as synthetic products used in plasticizers such as BPA and phthalates, fungicides, pesticides, and rodenticides, and a range of building and isolation materials (metals and polychlorinated biphenyl). Common sources of EDs can be summarized as plants, fish, plastics, pesticides, herbicides, pharmaceutical compounds and personal care products. EDs can enhance or reduce hormone synthesis and interact with hormone signaling

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pathways of healthy tissues [26]. The main classes of EDs are comprised of as pesticides, phthalates, natural hormones, bisphenol, parabens, phenols, and synthetic hormones [70]. In Table 13.1, emerging EDs in water matrices are listed. TABLE 13.1  EDs in Water Matrices [44] Family

Molecule

Neonicotinoids

Acetamiprid, clothianidin, nithiazine, imidacloprid, Insecticide nitenpyram, thiacloprid, thiamethoxam

Phenolic compounds

Bisphenol A (BPA), octylphenol, 4-nonylphenol (NP)

Plasticizers

Triclosan (TCS)

Antibacterial agent

BP1, BP3, BP4

Cosmetics

Benzophenones

Use

Natural hormones E1, E2, E3

Natural hormones

Phthalate

Di(2-ethylhexyl) phthalate (DEHP), dimethyl phthalate (DMP), diethyl phthalate (DEP)

Plasticizers

Heavy metal

Cadmium (Cd)

Batteries

Drugs

17α-ethynylestradiol, levonorgestrel

Contraceptive pills

DEHP is known as a plasticizer and an endocrine disrupting chemical (EDCs). DEHP can disrupt endocrine system even at low concentrations (its LD50 ranging between 26 and 34 g/kg) [24]. A study of the developing of AgNPs self-assembled monolayer onto Rhodococcus jostii PEVJ9. This system can be used for the degradation of DEHP and resulted with the degradation yield of 100% within 72 hours [9]. White rot fungi (WRF) can degrade lignin and most of the lignin analogs. Despite the degradation mechanisms of EDs are not clear enough, some professionals have suggested that those mechanisms are might be cleavage of C-ring in the benzo-c-pyrone system, O-methylation, O-demethylation, hydroxylation, dehydroxylation, glycosylation, deglycosylation, cyclization, hydrogenation, dehydrogenation, and carbonyl reduction [34]. White-rot fungi metabolism and their combinational applications with NMs can be interpreted as promising tools for EDs removal. Phanerochaete chrysosporium, the most intensively studied white rot fungus, has been evaluated as an effective bioremediation agent. Developed nitrogen-doped TiO2 NPs (PTNs) and loaded them on P. chrysosporium to develop capacity of remediation for Cd (II) and 4-dichlorophenol (2,4-DCP). The removal efficiencies were 84.2% and 78.9% for Cd (II) and 2,4-DCP, respectively. After the degradation of 2,4-DCP, o-chlorotoluene, and 4-hexene-1-ol were occurred. These results

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confirmed that PTNs can be used for removal of Cd (II) and 2,4-DCP from wastewater simultaneously [14]. Developed magnetic nanocomposites (MNCs) (NiFe2O4@COFs). These MNCs were consisted of a magnetic core (NiFe2O4) and a shell (COFs). They used NiFe2O4@COF MNCs as an adsorbent/extractant in the effervescent reaction-enhanced microextraction (MNER-EM) operations for the first time in literature. MORE-EM/HPLC-FLD method had a good linear range (0.1 ~ 0.5–200 µg.L–1), under optimized conditions. This method had also low limits of detection (0.019–0.096 µg.L–1), 83.4–106.2% recoveries and high precision (RSDs of 3.11–5.73%) for all six EDs in tap, barreled, and river water, activated beverage, human urine and serum samples. As a result of the study, developed NiFe2O4@COF MNCs can be a good substitute for conventional magnetic separation/adsorbent materials [64]. BPA, NP, and TCS degradation reactions are catalyzed by manganese peroxidase (MnP) with and without single-walled carbon nanotube (SWCNT) and/or graphene (GRA) [15]. Binding substrates to MnP have been affected by single SWCNT or GRA differently. This study helped to understand possible GRA, SWCNT or SWCNT+GRA contribution to three EDs biodegradation processes mediated by MnP. Adsorption of metal EDs (Pb2+, Cd2+, and Hg2+) via carbonaceous and carbon nanotubes (CNT) and graphene oxide (GO) [80]. Biochars (produced at 300°C and 600°C), commercial bamboo active carbon, GO, and commercial CNT were used in the experiments. Cd2+, Pb2+, and Hg2+ are the most retained cations respectively. The cost analysis of these systems revealed that utilization of carbonaceous materials could be an effective method for environmental remediation in large scale. 13.3.5  BIOREMEDIATION OF ANTIBIOTICS Antibiotics have been used in broad applications, and their emergence in the environment has both created risks on human health and brought about environmental pollution. There are several routes leading to the contamination of ground and surface waters with antibiotics. Domestic, pharmaceutical, hospital, agricultural, aquacultural, and accidental leakages and effluents can cause the pollution of water and soil [13]. Chemical structure of antibiotics affect their potential effects on the environment and durabilities. Antibiotics that have low molecular weight (