Multifunctional hybrid nanomaterials for sustainable agri-food and ecosystems 9780128213599, 0128213590

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Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems

Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems

Edited by

Kamel A. Abd-Elsalam

Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States © 2020 Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions. This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein). Notices Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary. Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein. Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: 978-0-12-821354-4 For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Matthew Deans Acquisitions Editor: Simon Holt Editorial Project Manager: Mariana C. Henriques Production Project Manager: Nirmala Arumugam Cover Designer: Mark Rogers Typeset by SPi Global, India

Contributors Kamel A. Abd-Elsalam Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt M. Evy Alice Abigail Department of Chemical Engineering, Hindustan Institute of Technology and Science, Chennai, India Shagufta Afreen CAS Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, China Farah K. Ahmed Biotechnology English Program, Faculty of Agriculture, Ain Shams University, Cairo, Egypt Fanelwa R. Ajayi SensorLab, Department of Chemistry, University of Western Cape, Cape Town, South Africa Mousa Alghuthaymi Department of Biology, Science and Humanities College, Shaqra University, Alquwayiyah, Saudi Arabia Hassan Almoammar €rich, Department of Biology, Institute of Microbiology, Zu €rich, Switzerland; ETH Zu National Centre for Biotechnology, King Abdulaziz City for Science and Technology (KACST), Riyadh, Saudi Arabia Mohammad Ashfaq Multidisciplinary Research Institute for Science and Technology, IIMCT, University of La Serena, La Serena, Chile; School of Life Science, BS Abdur Rahaman Institute of Science and Technology, Chennai, India Asim-Mansha Department of Chemistry, Government College University Faisalabad, Faisalabad, Pakistan Anindita Behera School of Pharmaceutical Sciences, Siksha ‘O’ Anusandhan Deemed to be University, Bhubaneswar, Odisha, India Divya Chauhan Department of Chemical and Biomedical Engineering, University of South Florida, Tampa, FL, United States Xuan Chen College of Horticulture, Nanjing Agricultural University, Nanjing, China

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Contributors

Joa˜o Vinı´cios Wirbitzki da Silveira Laboratory of Green Materials, Food Engineering, Institute of Science and Technology, University of Jequitinhonha and Mucuri, Diamantina, Minas Gerais, Brazil Khemchand Dewangan Department of Chemistry, Indira Gandhi National Tribal University, Amarkantak, Madhya Pradesh, India Sayan Deb Dutta Department of Biosystems Engineering, College of Agriculture and Life Sciences, Kangwon National University, Chuncheon, Republic of Korea Ahmed M. El Hamaky Department of Mycology and Mycotoxins, Animal Health Research Institute, Agriculture Research Center, Cairo, Egypt Farid-Un-Nisa Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, Pakistan Danielle Cristine Mota Ferreira Laboratory of Food Materials Studies, Department of Food Technology, University of Vic¸osa, Vic¸osa, Minas Gerais, Brazil Mohamed Amine Gacem Laboratory of Ecosystems Protection in Arid and Semi-Arid Area, University of Kasdi Merbah, Ouargla; Department of Biology, Faculty of Science, University of Amar Tlidji, Laghouat, Algeria Mohamed A. Gad Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt; Institute of Agricultural Environment and Resources, Yunnan Academy of Agricultural Sciences, Kunming, China Keya Ganguly Department of Biosystems Engineering, College of Agriculture and Life Sciences, Kangwon; National University, Chuncheon, Republic of Korea Gina Alejandra G. Giraldo Department of Biochemistry and Biotechnology, Center of Exact Sciences, State University of Londrina, Londrina, Parana´, Brazil Ayat F. Hashim Fats and Oils Department, National Research Centre, Cairo, Egypt Atef A. Hassan Department of Mycology and Mycotoxins, Animal Health Research Institute, Agriculture Research Center, Cairo, Egypt Tajamal Hussain Institute of Chemistry, University of the Punjab, Lahore, Pakistan

Contributors

Siavash Iravani Faculty of Pharmacy and Pharmaceutical Sciences, Isfahan University of Medical Sciences, Isfahan, Iran Josef Jampı´lek Department of Analytical Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia S. Emmanuel Joshua Jebasingh Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Anu Kalia Electron Microscopy and Nanoscience Laboratory, Department of Soil Science, College of Agriculture, Punjab Agricultural University, Ludhiana, Punjab, India Kattesh V. Katti Institute of Green Nanotechnology, Department of Radiology, School of Medicine; Institute of Green Nanotechnology, University of Missouri Cancer Nanotechnology Platform, University of Missouri-Columbia, Columbia, MO, United States Harleen Kaur Department of Microbiology, College of Basic Sciences and Humanities, Punjab Agricultural University, Ludhiana, Punjab, India Harsimran Kaur Department of Microbiology, College of Basic Sciences and Humanities, Punjab Agricultural University, Ludhiana, Punjab, India Katarı´na Kra´lˇova´ Institute of Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia Ramsingh Kurrey School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur, Chhattisgarh, India Huan Li Institute of Leisure Agriculture, Jiangsu Academy of Agricultural Science, Nanjing, China Ming-ju Li Institute of Agricultural Environment and Resources, Yunnan Academy of Agricultural Sciences, Kunming, China Xinghui Li College of Horticulture, Nanjing Agricultural University, Nanjing, China Ki-Taek Lim Department of Biosystems Engineering, College of Agriculture and Life Sciences, Kangwon National University, Chuncheon, Republic of Korea

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Contributors

Muhammad Irfan Majeed Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, Pakistan Suzana Mali Department of Biochemistry and Biotechnology, Center of Exact Sciences, State University of Londrina, Londrina, Parana´, Brazil S. Mangalanagasundari Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Mogda K. Mansour Department of Biochemistry, Animal Health Research Institute, Agriculture Research Center, Cairo, Egypt Janaı´na Mantovan Department of Biochemistry and Biotechnology, Center of Exact Sciences, State University of Londrina, Londrina, Parana´, Brazil Beatriz M. Marim Department of Biochemistry and Biotechnology, Center of Exact Sciences, State University of Londrina, Londrina, Parana´, Brazil Bharti Mittu National Institute of Pharmaceutical Education and Research, Mohali, Chandigarh, India K. Murugan Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India K. Muthu Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Nimra Nadeem Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, Pakistan Syed Ali Raza Naqvi Department of Chemistry, Government College University Faisalabad, Faisalabad, Pakistan Patrick B. Njobeh Department of Biotechnology and Food Technology, Faculty of Science, University of Johannesburg, Johannesburg, South Africa Noha H. Oraby Department of Mycology and Mycotoxins, Animal Health Research Institute, Agriculture Research Center, Cairo, Egypt

Contributors

Santwana Padhi KIIT Technology Business Incubator, KIIT Deemed to be University, Bhubaneswar, Odisha, India Priti Paraliker Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra, India Fahmida Parvin Department of Environmental Sciences, Jahangirnagar University, Savar, Dhaka, Bangladesh Dinesh K. Patel The Institute of Forest Science, Kangwon National University, Chuncheon, Republic of Korea Tarun Kumar Patle School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur, Chhattisgarh, India Nabanita Patra School of Pharmaceutical Sciences, Siksha ‘O’ Anusandhan Deemed to be University, Bhubaneswar, Odisha, India K. Paulkumar Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Franciele Maria Pelissari Laboratory of Green Materials, Food Engineering, Institute of Science and Technology, University of Jequitinhonha and Mucuri, Diamantina, Minas Gerais, Brazil Mahendra Rai Department of Biotechnology, SGB Amravati University, Amravati, Maharashtra, India P. Rajiv College of Horticulture, Nanjing Agricultural University, Nanjing, China; Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India T. Jesi Reeta Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Sumayya Rehaman Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India Sharmin Yousuf Rikta Department of Environmental Sciences, Jahangirnagar University, Savar, Dhaka, Bangladesh

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Sergio Ruffo Roberto Agricultural Research Center, Department of Agronomy, Londrina State University, Londrina, Brazil Rasha M. Sayed El Ahl Department of Mycology and Mycotoxins, Animal Health Research Institute, Agriculture Research Center, Cairo, Egypt Sat Pal Sharma Department of Vegetable Science, College of Agriculture, Punjab Agricultural University, Ludhiana, Punjab, India Woo-Chul Shin Department of Biosystems Engineering, College of Agriculture and Life Sciences, Kangwon National University, Chuncheon, Republic of Korea Kamlesh Shrivas School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur, Chhattisgarh, India Jagvir Singh Faculty of Engineering, University of Alberta, Edmonton, AB, Canada Amanda L elis de Souza Laboratory of Green Materials, Food Engineering, Institute of Science and Technology, University of Jequitinhonha and Mucuri, Diamantina, Minas Gerais, Brazil Noor Tahir Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, Pakistan Neetu Talreja Multidisciplinary Research Institute for Science and Technology, IIMCT, University of La Serena, La Serena, Chile Shafi Mohammad Tareq Department of Environmental Sciences, Jahangirnagar University, Savar, Dhaka, Bangladesh Maxwell Thatyana Department of Oral Biological Sciences, School of Oral Health Sciences, University of Witwatersrand, Johannesburg, South Africa Velaphi C. Thipe Institute of Green Nanotechnology, Department of Radiology, School of Medicine, University of Missouri-Columbia, Columbia, MO, United States P. Vanathi Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India

Contributors

Khamis Youssef Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt Muhammad Zahid Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, Pakistan

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Preface Nanoagribusiness is an emerging field to broaden crop yield, rejuvenate soil health, present smart agriculture, and activate plant improvement. It’s a way that nanotechnology might propel agribusiness to nearly $3.4 trillion by 2020. This volume, Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems, collects the know-how, discoveries, and fruitful findings regarding hybrid nanomaterials (HNMs) and their applications in agriculture, food, and the environment. This book contains 25 chapters prepared by outstanding authors from Algeria, Bangladesh, Brazil, Canada, China, Czech Republic, Egypt, Germany, India, Korea, Pakistan, Slovakia, Swaziland, Turkey, and the United States. The primary three chapters from the proposed book offer the synthesis and physicochemical characterization of HNMs, including organic-inorganic HNMs, nanocomposites, core@shell structured hybrid nanoparticles, chitosan or silica-based nanosystems, and bimetallic nanoparticles. The other 22 chapters are focused on agri-foods and environmental applications. Current status applications of novel HNMs for the recognition and separation of heavy metal ions, the degradation and sensing of diverse pesticides, the controlled release of fertilizer and pesticide products, plant disease and pest management, and plant promotion as well as the purification, detection, and control of mycotoxins was investigated. Some new subject matter will probably be integrated covering the application of hybrid nanotechnology in antimicrobial agents, food packaging, environmental bioremediation, gene delivery, sensors, antimicrobial effects, pesticide delivery, veterinary medicine, and biodeterioration herbicides. Also, current volume focused on chitosan-based nanosystems in food packaging, silica-based total nanosystems, carbon nanotubes-primarily based, nanocellulose-based polymer nanohybrids for agricultural and biological applications. Other topics include using cellulose-based hydrogels for three-dimensional bioprinting for tissue engineering; humic acid and its function in enhancing soil health and plant growth promotion; multiple extra functions for mixed nanomaterials reminiscent of veterinary medication; and electrochemical detectors for environmental sensing of pollutants. This book include a few excellent summaries to examine the present discoveries, which can include reviewed articles and/or books. This is an applicable book for graduate students, researchers, and those in industrial sectors that include more than a few fields of science and technology who are also interested in studying HNMs. The current book discussed the effects of a huge type of combined, matched, conjugated, and exceptional nanocomposites in the agri-food and environment sectors applictions, as well as dealing with the most vital potential challanges, risks and opportunities. More and more people, both in academia and industrial sectors, are rediscovering the opportunities that nanotechnology can provide. Thus, the agri-food and environmental sectors are consistently on the lookout for scientific knowledge to facilitate creativity and innovation. A recent book might achieve new investigation perspectives, which is important for many researchers. Identical research could possibly be

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supportive, which requires a database to formalize nanotechnology. There are a few universities that have specialized courses in nanotechnology. Nanoscience researchers need a specific book that brings this significant body of data collected in an organized and usable way in a single place. I am truly thankful to all the authors who contributed chapters and provided their beneficial suggestions and expertise to this edited book. Without their commitment and assistance, the compilation of this book may possibly never have been feasible. Elsevier’s publisher, who also provided an extremely great level of professionalism, reliability, and tolerance during the entire procedure, is likewise significantly commended. I wish to thank Elsevier officials, in particular, Simon Holt, Senior Acquisitions Editor, Micro and Nano Technologies; Nirmala Arumugam; Mariana C. Henriques; and Narmatha Mohan, for their generous support and efforts in accomplishing this volume. Furthermore, I thank all the reviewers who dedicated their useful time to make significant comments on every chapter. I would like to express my honest appreciation to my family members for their ongoing support and assistance. Kamel A. Abd-Elsalam Agricultural Research Center, Giza, Egypt

CHAPTER

Multifunctional hybrid nanomaterials for sustainable agri-food and ecosystems: A note from the editor

1

Kamel A. Abd-Elsalam* Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt

1.1 Introduction The combination of nano-sized inorganic or organic fillers such as clay, metal ions, metal oxides, nitrides, chlorides, cellulose-based materials, silica, and biopolymers that include chitosan, pectin, alginate, chitin, etc., as well as bioantimicrobial agents such as nisin and thymol have been redesigned, in addition to enzymes. Because of the superb mechanical, physical, and tribological characteristics of hybrid nanomaterials over broad length scales, studies on hybrid nanomaterials provide an amazing outcome in the area of food packaging, plant protection, electrochemistry, and various additional applications in the environmental and agri-food sectors (Balasubramanian and Jawahar, 2019). Produced hybrid nanocomposites such as core-shell NPs are employed in ecosystem bioremediation for wastewater pollution as well as the protection of plant, animal, and human health from dangerous and unsafe resources, which include pharmaceuticals, dyes, oils, and heavy metals (Song et al., 2019). Hybrid nanomaterials and unique nanoforms were produced to enhance their application in the biotechnological and agricultural sectors. Because of their great inbuilt characteristics, they work as excellent carriers/vectors and encapsulators for multiple short-lived, fickle, and risky substances such as pesticides, fertilizers, enhancers, and hormones. Therefore, this enhances their stability and reactivity while boosting their mechanisms (Manna and Bandyopadhyay, 2018). Distinct types of organoclays and other types of hybrid systems are completely showing high efficiency in water treatment and remediation of polluted areas as well as the development of less harmful products of agrochemicals (Aranda et al., 2018; Mukhopadhyay et al., 2020). Hybrid metallic nanoparticles such as carbon and polymer-metal hybrids provide specific prospects for developing practical electrochemical bioassays and biosensors and create an innovative aspect to such assays *Corresponding author Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems. https://doi.org/10.1016/B978-0-12-821354-4.00001-7 # 2020 Elsevier Inc. All rights reserved.

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CHAPTER 1 Nanohybrids for sustainable agri-food and ecosystems

and techniques. Polymer nanocomposite-based chemical sensors have emerged as a comprehensive research procedure for sensing applications in essential aspects such as agriculture, medicine, and the detection of environmental contaminants present in the air, soil, and water. In the food sector, current sensors can be applied to diagnose different elements such as food freshness, spoilage, toxicity, and quality (Pavase et al., 2018). The combinations between nanofiller/matrix and bioactive materials provides extensive options for mechanical, thermal, optical, electrical, barrier character, and multifunctionality to develop good food packaging materials (Vasile, 2018). Lipid-based nanoparticles, including liposomes, nanoemulsions, solid lipid nanoparticles (SLN), and nanostructured lipid carriers (NLC), have appeared as promising nanoparticulate systems and are generally identified among the most appealing encapsulants in the nanobiotechnology field (Tamjidi et al., 2013). Lipid-polymer hybrid nanoparticles (LPHNPs) are next-generation core-shell nanostructures, conceptually derived from both liposome and polymeric nanoparticles (NPs) where a polymer core is surrounded by a lipid layer. Lipid polymer hybrid nanomaterials could possibly be utilized to insert DNA or RNA materials as well as a diagnostic imaging agent (Zhao et al., 2018). However, the design and preparation of multifunctional hybrid nanomaterials remain difficult and their introduction into functional applications is not yet adequate. Consequently, it is extremely desirable to discover modern nanomanufacturing and scale-up nanotechnology to design and produce complex multifunctional hybrid nanomaterials with superior functionality (Zhou et al., 2019). The objective of this book is to discover synthesis and characterization methods and the applicability of unique hybrid materials formulated with organic-inorganic such as bi/multimetallic, hybrid metallic nanoparticles, and carbon or polymer-metal hybrids in the environmental, food, and agriculture sectors. This book will offer the target audience a general view of the most up-to-date applications and prospects of multifunctional hybrid nanomaterials for sustainable agri-food and ecosystems.

1.2 What are hybrid nanomaterials? The term hybrid in an easy design involves fusion, joining, or mixing the features into one monolithic identity to change the positive aspects of conjugated product features and to reverse the disadvantages of the single components (Sailor and Park, 2012). In chemistry, this term will signify the fusion of characteristics at the molecular level, which will generate a hybrid material owning the effective functionality of each main part while not inheriting the disadvantageous features of the party component. Basically, the designing of hybrid materials triggers a combination of the expected properties with the elimination of undesirable tendencies, offering an interesting property detail for such products. This is due to hybrid materials that may locate applications in varied areas, although their first elements may well not have been regarded for those applications. These hybrid materials incorporate the exclusive properties of organic and inorganic elements in a specific part and are used as a

1.3 Hybrid nanomaterial applications in agri-food and ecosystems

sensors and in photocatalytic, antimicrobial, electronic, agricultural, environmental, and biomedical applications. Inorganic nanoparticles have a solid propensity to form aggregates. So, to improve the stableness of dispersions and the compatibility conditions of inorganic nanofillers with organic solvents or polymer matrices, the surfaces of inorganic nanofillers must be modified, by grafting polymers onto them. Surface amendment enhances the interfacial relationships among the inorganic nanofiller and polymer matrix, which leads to specific properties such as physical characteristics at low loadings of inorganic reinforcement, and additional optical and electronic properties. This book covers major hybrid nanomaterials, including core@shell structured hybrid nanoparticles, bio-based hybrid polymer nanocomposites, organic-inorganic hybrid nanoparticles, bimetallic nanoparticles, conjugated nanomaterials, hybrid upconversion nanoparticles, silica/chitosan-based nanosystems, carbon nanotube-based nanohybrids, cellulose-based hydrogels, and cellulose-based nanocrystals. This volume delivers complete details regarding the production of hybrid nanomaterials, the surface functionalization of inorganic nanoparticles, and applications of organic-inorganic nanocomposite and other nanohybrids in the agri-food and environmental fields (Fig. 1.1).

1.3 Hybrid nanomaterial applications in agri-food and ecosystems Hybrid nanomaterials have innovative potential functions in the environment and agri-food sectors. Their applications include agrochemicals applied for plant promotion, postharvest disease management and plant protection, nanosensor/nanobiosensor application in pollutant and pesticide sensing, plant pathogen diagnosis and food safety, and nanodelivery devices for gene or DNA transfer plants. Their applications in the food sector involve feed and food ingredients as well as intelligent packaging and quick-detection systems for food-borne pathogens. Hybrid materials are growing systems for veterinary applications such as animal health, food additives, drug and vaccine delivery, mycotoxin detection and degradation, and poultry production. Finally, they have applications in the treatment, preservation, and purification of wastewater. Promising applications of hybrid nanomaterials in the agri-food and ecosystem sectors are illustrated in Fig. 1.2. These new hybrid nanosystems offer benefits for sustainable environmental and agricultural development strategies.

1.3.1 Plant growth promotion More than 50% of the employed fertilizer and pesticide is usually lost inside the soil ecosystem due to leaching and decomposition, therefore contaminating the environment. To defeat these difficulties, researchers have formulated multiple hybrid nanocomposites, which usually contribute significantly to plant growth promotion and protection. Most recently, applied hybrid nanomaterials (NMs) have been generally confirmed to be more effective selections of standard fertilizers and pesticides.

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This book can be divided into six broad categories of nanohybrids: (1) the hybrids NMs generated by the fusion of organic components, (2) nanohybrids generated by conjugated of inorganic components, (3) nanohybrids generated by combined of bimetallic, (4) nanohybrids generated by the fusion of multimetallic, (5) hybrids arising due to the fusion of metallic and polymer composites, and (6) lipid-polymer hybrid nanoparticle (HNPs).

CHAPTER 1 Nanohybrids for sustainable agri-food and ecosystems

FIG. 1.1

1.3 Hybrid nanomaterial applications in agri-food and ecosystems

Eco-agri-food applications

A

B

Plant promotion and protection

Food and feed

D

E

Veterinary

Antimicrobials

Water treatment

Nanofertilizers

Food packaging

Pathogen detection

Antibacterial

Nanopesticides

Edible coatings

Disease treatment

Antifungal

Disinfection

Conservation

Pesticides sensing and degradations

Postharvest diseases

Drugs and vaccine delivery

Antiviral

Pest diagnosis

Food-borne pathogens

Reproduction, nutrition

Nematicidal

Pest control

Food additives

Mycotoxins detection

Controlled-released

Food and feed safety

Mycotoxins degradation

Purification

FIG. 1.2 The potential applications of hybrid nanomaterials (HNMs) in the agri-food sector and environmental remediation are manifold: the development of antimicrobials and agrochemicals for crop promotion and protection (e.g., nanopesticides or nanofertilizers); food and feed biosecurity (e.g., sensors for detecting pathogens); monitoring the environment, the treatment of wastewater; and veterinary applications. HNMs can be applied for the detection and separation of heavy metal ions, the destroying and sensing of insecticides, managed release fertilizer and pesticide formulations, plant protection, and plant promotion as well as the purification, detection, and control of mycotoxins. Other applications include sensor improvement, gene shipping, applications of silica/nanocellulose or chitosan-based nanosystems in edible coatings, food packaging, and plant protection. One of the most important environmental applications of HNMs has been in the treatment of water, whether in the purification, reservation, and remediation of wastewater and groundwater or through the nanocomposite separation and/or sensing of contaminants present in various aqueous systems. Nanoscopic materials such as hybrid nanoparticles, carbon nanotubes, and graphene nanosheets modified with nano-filter may be used for water desalination and nanofiltration.

HNMs, specifically the composite form and metal oxides of NMs, have the potential to boost seed germination, growth, and plant protection while enhancing photosynthesis and thus maximizing plant growth (Kataria et al., 2019; Polischuk et al., 2019). Furthermore, nanocomposite-layered fertilizers work as slow-release fertilizers by avoiding the decline of macronutrients in soil and water while employing them as fertilizers in the plant soil (Giroto et al., 2017) and also displaying water retention tendencies in the soil (Olad et al., 2018). The enhancement of the performance of slow-release fertilizers (nanocomposite-coated) may also reduce the burden of

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fertilizers and mitigate the undesirable impact of fertilizers on the environment (AlShamaileh et al., 2018). The literature on the role of nanobiofertilizers in plant and soil devices revealed that they acts proficiently for the improvement of agricultural productivity. They may perform synergistically, providing more significant preservation of soil moisture and essential plant nutrients due to the nanomaterial coating as well as the microbial inhibition triggered by the bioorganic ingredient that contains plant growth promoters by using direct and indirect interactions such as biofertilization, rhizoremediation, disease resistance, etc. Nanobiofertilizer can boost a number of positive factors in plants, that is, slow-release characteristics, raised stability of practical ingredients, use of tiny dosages, minimal nutrients harmed by degradation and leaching, masking soil nutrient destruction, and increasing crop yield quantity and quality (Kumari and Singh, 2019).

1.3.2 Plant protection The use of hybrid nanomaterials in food packaging can help to boost food safety, decrease food spoilage through suppressing the growth of pathogenic microbes, and considerably enhance the quality of fruits and their shelf life through the harvest and postharvest stage. A number of nanostructured chemicals, designated from inorganic metallic, metallic oxides, and their nanocomposites with bioactive materials, have been put on the food market. Nanocomposites symbolize a growing type of hybrid component that is created by a combined mix of organic polymers and inorganic solids and displays structural improvement and practical characteristics of great curiosity for diverse applications. Curcumin-loaded electrospun zein nanofibers (CLZN) were used to coat apples contaminated with Penicillium expansum and Botrytis cinerea. CLZN mats start a new direction for innovative applications of edible and biodegradable antifungal protective material, having the ability to reduce the fungal development of covered apples during the storage period (Yilmaz et al., 2016). Most current plant disease diagnostic techniques can offer rapid, correct, and reliable detection of plant diseases in the first stages for preventing economic yield losses as well as beneficial elements for crop production. Nanodiagnostic methods using conjugated functionalized hybrid nanomaterials may soon identify the probable severity of plant pathogens, helping experts to greatly support growers in preventing high incidence diseases in a variety of crops (Khiyami et al., 2014; Shoala, 2019). Various types of biosensors, including optical, electrical, fluorescence, piezoelectric, surface area plasmon resonance (SPR), and total inner reflection ellipsometry (TIRE), are constructed of hybrid nanomaterials constituted by a biorecognition component (antibody, DNA, enzyme, etc.) that is definitely immobilized onto nanomaterials (dendrimers, carbon nanotubes, magnetic, gold nanoparticles, graphene oxide, and quantum dots) for the detection of mycotoxins and a transducer for converting the biochemical response into a power or optical transmission (Santos et al., 2019). Ji and Xie (2020) applied MGO adsorbents to detoxify AFB1-contaminated oils; the current absorbents are comprised of MGO and magnetic decreased graphene oxides (MrGO) all combined with Fe3O4 nanoparticles.

1.3 Hybrid nanomaterial applications in agri-food and ecosystems

The outcomes showed that MGO experienced an adsorption effectiveness (AE) of 86.33% from 16.1 μg/L to 2.2 μg/L and MrGO had an AE of 88.82% from 16.1 μg/L to 1.8 μg/L, both at 37°C for 40 min with adsorbent dosage of 10 mg/ mL. MrGO and MGO were recyclable even after seven cycles without a critical lessening of the adsorbent process. Hybrid nanomaterials may perform an essential role for a synergistic strategy in tackling the concerns in mycotoxicology in the 21st century (Abd-Elsalam and Rai, 2020). Carbon nanotube was applied as an electrochemical sensors due to their substantial sensitivity and selectivity characteristics offering effective recognition of pesticide traces in environmental samples. Lately, nanomaterial/nanocomposites comprising three-dimensional (3D) graphene can be a distinctive, reputable process for onsite analysis and bioremediation of pesticides or herbicides with great features (Ali et al., 2019; Zhang et al., 2019a, b).

1.3.3 Bio/hybrid nanosensors Hybrid nanostructured materials consisting of thin films of conjugated polymers, nanofibers, bi- or metallic nanoparticles, carbon nanotubes, and enzymes possess attractive features such as a high surface area/volume ratio and size-dependent optical and electronic properties, which are highly desired for designing chemical substance sensors with optimized properties (Fig. 1.3). Reliable, inexpensive, and sensitive portable chemical sensors have been pursued highly for applications in food analysis and food security, permitting monitoring of the chemical substance composition, smell, and taste as well as contamination by microorganisms, including bacteria and fungi, among additional applications (Andre et al., 2018; Correa et al., 2017). The use of hybrid nanomaterials in sensor construction allows singlemolecule detection, an appealing characteristic for multiplex mycotoxin detection in the same sample matrix cocontaminated with several mycotoxins (Anfossi et al., 2019). The use of hybrid nanomaterials in mycotoxicology is in initial stage, however, and many multifunctional nanomaterials maybe applied for improvement sensors efficiency in the identification of several mycotoxins (Almoammar et al., 2019).

1.3.4 Hybrid nanomaterials for water purification The analysis of photocatalytic possibilities of these hybrid nanomaterials in water treatment and purification has been outlined in detail. The effectiveness of various supports such as biomass, graphene oxide, reduced graphene oxide, fly ash, polymer, etc., has been examined for their particular utility in wastewater remedies. Bionanocomposites (BNCs) were applied in the adsorptive and/or catalytic reduction of pollutants from wastewater. Likewise, bionanocomposites are generally efficiently employed to eradicate numerous organic, inorganic, radioactive, pharmaceutical, and heavy metal contaminants from sewage water. BNCs could be employed for the adsorptive and/or catalytic removal of pollutants under different pH degrees. Hybrid-magnetic nanoparticles (HMNPs) were produced as iron oxide combined

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FIG. 1.3 The improved combinations of electrical, mechanical, and thermal properties of hybrid inorganic-organic nanomaterials have resulted in major interest in various electronic applications with unique properties. Nanostructured materials and the molecular architectures are employed as active layers for chemical sensors, including thin films of conductive polymer nanofibers, metallic nanoparticles, carbon nanotubes, and enzymes. The multiple synergistic effects, properties, and interactions of nanocomposites are highlighted for the improved performance in bioanalytical, environmental, and agri-food applications. Electrochemical sensors can be employed for the detection of cations, anions, and organic compounds in food while various aptamers are used for the detection of pesticides, antibiotics, heavy metals, microbial cells, and mycotoxins.

with multiwalled carbon nanotubes (MWCNTs-Fe3O4) obtained from MWCNTs oxidized with HNO3. The obtained HMNPs were used in a particular examination to eliminate arsenic from toxified groundwater (Bavio and Lista, 2013). In contrast, the magnetic action of these nanoparticles makes possible their separation from the sample solution after the treatment.

1.3.5 Gene delivery Pollen magnetofection combined with nanomaterials is an innovative tool for enhancing and targeting gene delivery in plants to produce genetically modified crops. The engineered crops may be used in some important applications like

1.3 Hybrid nanomaterial applications in agri-food and ecosystems

the production of new antimicrobials and recombinant protein in plant cells, for enhancement yield production, cleaner biofuels, and biofertilizers. Nevertheless, all these innovations are improving our approach to design desired plants for the future (Zhang et al., 2019a, b). Hybrid exosomes that can be employed as drug delivery agents are mainly linked to small nucleic acids such as miRNAs and siRNAs, or low molecular medicines that are usually much lower than the Cas9 expressing plasmids with a minimal size of 5–6 kb. Lin et al. (2018) inserted the CRISPR-Cas9 system into exosomes and identified that the proposed hybrid exosome via incubating with liposomes could be a new strategy for drug encapsulating and delivering the CRISPR-Cas9 system in vivo or in transfection-resistant cells in vitro. The practical and intensive applications of novel hybrid nanomaterials in molecular genetic nanotechnology depend significantly on robust nanoparticle synthesis and engineering strategies. The use of natural vesicles innately produced in plant and animal cells such as hybrid exosomes as transport agents would possibly eliminate most challenges linked to the current nanodelivery system (Akuma et al., 2019).

1.3.6 Bimetallic NPs Bimetallic and metal oxide nanoparticles have had intensive usage in biomedical applications. Recently, some biological applications for bimetallic nanoparticles that are targeted have revealed their optical or magnetic characteristics. Bimetallic nanomaterials have a large number of functions such as catalysts, staining pigments, antimicrobials, insecticides, groundwater remediation, sensors, biosensors, bioimaging, and DNA detection (Srinoi et al., 2018). In addition, the applications of bimetallic nanoparticles to groundwater, soil remediation, and organophosphorus pesticide detection are essential examples of the most recent developments in environmental nanotechnology (Han and Yan, 2014; Wu et al., 2019). The development of green techniques for producing bimetallic NPs using safe biomaterials as a substrate provides a great capability for fast-developing, innovative, and ecofriendly electrocatalysts and biosensors for agrosystem applications.

1.3.7 Chitosan-based nanosystems Chitosan provides tremendous features such as an edible packaging material, owing to its good film-forming characteristics and low level of toxicity. Also, it may be applied as an excellent vehicle for combining a large range of ingredients. Moreover, chitosan has antibacterial activity against several food-borne pathogens and is often supplied to product packaging to boost the postharvest life of fresh foods. The great potential of chitosan films is recognized with AgNPs (Kadam et al., 2019), nano-ZnO (Indumathi et al., 2019), nano-MgO (De Silva et al., 2017), nano-TiO2 (Zhang et al., 2019a, b), and nano-SiO2 (Tian et al., 2018) as efficient antimicrobial agents. Novel chitosan blends with specific properties can be produced, particularly for plant growth promotion and disease management, that

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is, improved encapsulation, effective release of target substances, and increased induction properties. Karimirad et al. (2018) discovered the remarkable functionality of Rutaceae aromatic and medicinal plants such as Citrus aurantium L. essential oil herbal antioxidant-loaded chitosan nanoparticles to increase the shelf life of a white button mushroom. A layer-by-layer Lactobacillus pentosus encapsulation approach that employed chitosan and sodium phytate was identified to have great capability for the protection and transport of the probiotic L. pentosus in food and nutraceutical products (Wang et al., 2019). Several applications of nanochitosan such as a fertilizer when nanosizing micronutrients hybrid with chitosan, chitosan-functionalized nanofibers and nancomposites were employed to food technology, including nanoencapsulation of bioactive food components and their delivery, food packaging, in addition to food pathogen biosensing. Certainly, chitosan performs a significant role in nanofoods and may possibly offer a new era in health and environmental benefits connected to food sustainability. Multiple possible applications of nanochitosans in plant nutrition, abiotic stress control, pesticide biodegradation, gene delivery, and postharvest application are also presented (Al-Dhabaan et al., 2018). Several applications for chitosan nanosystems in the food industry, for example, antioxidant application, probiotics, preservative edible coatings, smart packing, barriers and shelf life extension, carriers and nutraceutical enrichment, and chitosan nanofibers, are applied for food preservation, food color, and food-borne pathogen detection. In addition, nanohybrids were employed in some plant protection applications such as pest and management, plant promotion, slow-release pesticides, and fertilizers.

1.3.8 Multifunctional nanocellulose Cellulose nanosystems are considered preferred biomaterials for several applications because of their excellent physicochemical characteristics. They are usually extracted from diverse resources consisting of woods, agri-waste, and industrial wastes. Agricultural wastes, which include rice husk, wheat straw, sugarcane bagasse, etc., are essential sources for the production of smart nanocrystals for different applications. This volume highlights modern information on the synthesis, properties, and promising applications of multifunctional nanocellulose-based hybrid materials with metal or metal oxides. Cellulose-based smart nanocrystals have important advantages such as good biocompatibility, low density, large surface area, optical transparency, and advanced physical properties. They may be applied in unique fields such as biomedical, cosmetic, fertilizer delivery, biopharmaceutical, antimicrobial agent carrier, environmental remediation, and food packaging. For instance, α-Fe2O3/CNC has been commonly utilized as a nanocatalyst to reduce phosphate from aquatic media and therefore has effective applications in wastewater treatment and the strong reduction of eutrophication (Liang et al., 2017). Bionanofungicide materials such as hexadecyl trimethyl ammonium bromide (CNC/CTAB) have been revealed to have antifungal activity against Phytophthora capsici, both in vivo and in vitro (Xiang et al., 2019). Nanocellulose-based polymers have

1.4 Environmental risks

significant organic farming applications for the controlled release of various agrochemicals such as insecticides, herbicides, and fungicides. Despite all these types of specific features, there are still a few important issues that usually commonly minimize nanocellulose-based materials for industrial applications. We hope that the acceptable charge of formulation, high yield, and decrease of environmental toxicity will void the above problems associated with the nanocellulose-based materials for professional applications.

1.4 Environmental risks There are problems with nanomaterials, including potentially hazardous outcomes in agri-food, ecosystems, and human health. Until now, these kinds of engineered nanomaterials have generally been investigated for many functions in various sectors, including catalysis, sensing, photovoltaic, food, environment, and agriculture (Kabir et al., 2018). Furthermore, nanomaterials may possibly provide effective or smart properties to food packaging to ensure that they can protect the food from exterior factors and enhance food security by using antimicrobial properties and/or responding to environmental variations. Regardless of the different positive aspects of combined nanomaterials, their particular use in food packaging may well trigger safety concerns for animal or human health, merely because they show diverse physicochemical properties from their macroscale chemical counterparts (Honarvar et al., 2016). The potential effect for individual basic safety is the migration of nanoparticles. They may enter the body using intake, breathing, or dermal contact, resulting in the health effects of exposure to some insoluble, persistent nanoparticles. Many of these health issues are presently not known. Nanoparticles also migrate to food products with feasible negative effects on food quality. Another challenge is the degradability of biopolymers and the formation of degradation products with possible undesirable effects. Likewise, there may possibly be potential ecological effects of nanopolymer composites and a few problems with end-of-life treatments such as recycling, reuse, and disposal. There is no doubt that the particular characteristics of nanoscale objects, when conjugated with biomolecules, can radically improve their cellular reactivity. Consequently, there is a superb need to understand the difficulties and concerns of the modern toxicology of developed bionanocomposites and a need for continued harmonization for risk assessment. There are extremely minor or no details regarding the nanotoxic effects of HNMs on food products, agricultural commodities, and ecosystems. There are also no international methodologies or criteria regarding nanomaterial characterization or examining their ramifications on human health and agroecosystems (Farhoodi, 2016). Therefore, it is very essential to carry out proper life cycle analysis and risk assessment studies for HNMs prior to extensive application in the most vital sectors. Additional research is required in this field as benign bulk components could become toxic, reactive substances at hybrid nanomaterial levels.

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1.5 Future perspectives Forthcoming research on the production of hybrid nanomaterials must be concentrated on innovations in nanohybrids such as new nanohybrid resources, exact control over particle size biocompatibility, mechanical properties, biostability, and morphology for potential relevance. Upcoming research from the biological aspect requires focusing on the complex interactions among such materials. To predict the biological result, each nanocomposite mixture ought to be measured separately. Novel forms of nanohybrids might lead to the commercialization of HNMs for high-efficiency applications in numerous industry sectors (Fig. 1.4). Eventually, optimizing test methods to ensure the secure manufacturing and use of HNMs is urgently needed. Hybrid nanoparticles are usually constructed from at least two different nanoparticles to conquer the limits of single-component nanoparticles, to improve properties, to accomplish new properties not possible for single nanoparticles, and/or to attain multiple functionalities for single nanoparticles. Lately, various types of hybrid nanostructures such as core-shell, yolk-shell, heterodimer, Janus, dot in nanotube, dot on nanorod, nanobranches, etc., have already been described (Ma, 2019). Photoactive hybrid nanoparticles could be used in different agri-food and environmental applications such as antimicrobial, food packaging, biocides, fertilizers, etc. Bioinspired materials are a wide term and may include

FIG. 1.4 Novel types of hybrid nanomaterials that may be applicable in agri-food and ecosystem sectors in the near future, which includes hybrid nanoparticles, bioinspired approaches, three-dimensional or four-dimensional bioprinting, peptide-oligonucleotide conjugates, metal or metal oxide nanozymes, multilayered nanomaterials, nucleic acid-templated organic or inorganic nanomaterial, etc.

1.5 Future perspectives

any type of material attained using biomaterials or influenced by biological systems in nature. These involve biopolymers, natural gums, proteins, peptides, enzymes, plant extracts, natural oils, biodots, and biochar-based nanomaterials (Kumar et al., 2019). Bioinspired methods may be applied for a vast range of applications including plant growth promotion and protection, pollutant detection and remediation, wastewater treatment, etc. Plant-derived biomaterials show impressive promise in harnessing both the natural durability of plant microarchitecture merged with their natural biological functions as supporters of cell growth. The goal of this review article is to summarize the most broadly used biomaterials extracted from land plants and marine algae: nanocellulose, pectin, starch, alginate, agarose, fucoidan, and carrageenan, with in-depth concentration on nanocellulose and alginate. The properties that render these materials as encouraging bioinks for 3D bioprinting are herein discussed, along with their potential in 3D bioprinting for tissue engineering, drug delivery, wound healing, and implantable medical devices ( Jovic et al., 2019). The complicated structure of cellulose crystals at the nanoscale impacts the properties of cellulose materials at the macroscale level. Consequently, a fundamental understanding of nanoscale mechanisms throughout multiscale modeling presents recommendations for the bottom-up layout of cellulose-based nanomaterials, based on structure-property relationships and upcoming adjustment and shaping of cellulose (Martin-Martinez, 2018) (Fig. 1.5). Plant bioprinting might strengthen researchers’

Bottom-up design Cellulose-based nanomaterials

Structure-property relationships

Fiber

Macrofibril Microfibril

Multiscale modeling

Hemicellulose Lignin

s

lose

u Cell

nan

o

tal cr ys

Cellulose

FIG. 1.5 (Right) Schematic representation of the hierarchical structure of lignocellulose biomass down to the cellulose nanocrystals. (Left) The diagram shows how the atomistic model of cellulose nanocrystals is the starting point for the bottom-up design of cellulose-based nanomaterials. Reprinted from reference Martin-Martinez, F.J., 2018. Designing nanocellulose materials from the molecular scale. PNAS 115 (28), 7174–7175 with permission from PNAS, under Open Access Journal License.

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knowledge of plant shapes and morphogenesis, and may benefit from the large-scale production of preferred tissues or plants. Three- or four-dimensional printed hydrogel nanocomposites are bringing in much interest in the detection and reduction of agricultural and environmental contaminants. The current review focuses on the most significant and rising concerns in modern research into hydrogel nanocomposites for the detection and removal of pollutants, such as visual detection, enzyme-based biosensors, visible-light photocatalysis, design of 3D network structures, 4D printing, and multistimuli-responsive hydrogels (Hou et al., 2018). The field of peptide-DNA nanobiotechnology is still in its relative infancy; nevertheless, it has great potential for future materials. Peptide-oligonucleotide conjugates can be used for the production of bioactive nanomaterials. Peptides offer bioactivity that can mimic that of proteins while oligonucleotides such as DNA could be used as scaffolds to immobilize other molecules with nanoscale accuracy (MacCulloch et al., 2019). Related studies are required to see how to universalize any probable applications of peptide-oligonucleotide hybrid molecules in multidisciplinary research such as genomics and proteomics that provide ecosystem solutions crucial to agriculture and the surrounding environment. Nevertheless, knowledge on the development and applications of artificial metal and metal-oxide nanozymes in aquatic ecosystems is even now at the principal stage. Artificial metal and metal-oxide nanomaterials with intrinsic enzymemimicking activity may easily catalyze the removal and transformation of R-OH in aquatic media. These improvements will offer key research directions beneficial to the multifunctional applications of artificial nanozymes in ecosystem applications (Chen et al., 2019). Multifunctional multilayered nanomaterials, including graphite and graphenes, layered double hydroxides (LDHs), and synthetic clays such as laponite are generally subjected to extreme research not only because of their ecofriendly, naturally degradable, and biocompatible aspects, but also due to the role that these materials play in the advancement of controlledrelease pesticides or herbicides as well as drug delivery carriers in agrochemical and pharmaceutical formulations (Bernardo et al., 2019). Nanobiotechnologists have utilized new methods for plant genome editing to improve agricultural crops. A hybrid between specific nucleic acid amplicon and organic or inorganic nanoparticles and molecular genetic techniques is fairly costeffective for production in the food industry, agriculture, industrial biotechnology, and various other sectors linked with the bioeconomy. For example, exosomes may be investigated as a secure and natural nanodelivery model to raise the bioavailability of these compounds. Moreover, it is likely that these vesicles already function as nanocarriers within the plant and animal tissues (Akuma et al., 2019). Researchers used distinct methods to encapsulate the CRISPR-Cas9 system into exosomes and discovered that the offered hybrid exosome via incubating with liposomes could be an innovative approach for pharmaceutically encapsulating and delivering the CRISPR-Cas9 system in vivo (Lin et al., 2018). Additional studies are required on the biogenesis of plant-derived exosome-like vesicles and how they interact with

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1.6 Conclusion Currently, nanotechnology offers vital revolutionary improvement in biotechnology and biomedicine related to human, animal, and plant science such as increasing health protection and production and consequently increasing worldwide income. The use of nanotechnology through hybrid nanomaterials that occupy an exclusive corner among standard nanoparticles and nanocomposites makes them higher-order efficient materials that provide possibilities for multiplexing, effective degradation, and controlling pollutants in a practical sustainable approach. In summary, this volume, Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems, gathers 25 chapters offering unique information on the production of several designs of hybrid nanomaterials and their particular applications in the agri-food and environmental sectors. To be able to expand the application of biological nanoparticles, the integration of biomolecules with various types of nanoparticles that include inorganic and polymeric throughout many biofunctionalization approaches has been demonstrated. In the near future, we have the possibility to generate hybrid nanostructures such as bioinspired nanostructured polymer nanocomposites, 3D- or 4D-printed hydrogel nanocomposites, peptide-oligonucleotide hybrid molecules, metal oxide nanozymes, and LDH-based modified bioactive molecule delivery systems. Definitely, this innovative generation of hybrid materials, generally created from a worldwide study effort of numerous researchers in the last few years, will certainly open a significant number of possible applications in multiple aspects such as the environment, food packaging, agriculture devices, biomedical fields, gas sensors for environmental monitoring, crop protection, and the controlled release of pesticides or micronutrients in the agriculture field. Therefore, the future of the multifunctional hybrid bio-nanomaterials in enhancing agricultural food production and environmental protection is extremely excellent. This may be established not only as an ecofriendly strategy, but also as a cost-effective approach for sustainable agriculture development.

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Core-shell hybrid nanoparticles: Production and application in agriculture and the environment

2 Siavash Iravani*

Faculty of Pharmacy and Pharmaceutical Sciences, Isfahan University of Medical Sciences, Isfahan, Iran

2.1 Introduction Nanotechnology and nanobiotechnology demonstrate substantial roles in different fields, including pharmaceutics, biomedicine, agriculture, the environment, biomaterials, advanced materials, biophysics, drug targeting/delivery, biodiagnostics, diagnosis/bioimaging, genetic manipulation, and bioelectronics. The smaller size and high surface-to-volume ratio of nanoparticles (NPs) are the key characteristics that make them beneficial in the agricultural, environmental, and biomedical fields due to the improvement of numerous novel characteristics, the ease of functionalization, and the conjugation of biomolecules (Iravani, 2011; Mohammadinejad et al., 2016, 2019; Varma, 2012, 2014a, b, 2016, 2019). Core-shell NPs show substantial advantages and properties over simple NPs, causing the improvement of characteristics, including dispersibility enhancement, less cytotoxicity, bio/cytocompatibility, enhanced thermal and chemical stability, and improved conjugation with other bioactive molecules (Fig. 2.1). For instance, when the preferred NPs are toxic and may initiate trouble to the host tissues and organs, the coating of a benign material on top of the core can make the NPs much less toxic and more biocompatible. Occasionally, the shell layer not only performs as a nontoxic layer, but also improves the core material property. In the case of semiconductor coreshell NPs, the shell of other materials can improve the optical property and photostability. The hydrophilicity of NPs is crucial for dispersing them in biosystems (aqueous). The acceleration in biodispersivity and bio/cytocompatibility makes it an appropriate alternative to conventional drug-delivery vehicles. Coating the hydrophilic material onto the core surface in the form of core/shell NPs can overcome the problems of dispersibility and bio/cytocompatibility when the core material is hydrophobic *Corresponding author Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems. https://doi.org/10.1016/B978-0-12-821354-4.00002-9 # 2020 Elsevier Inc. All rights reserved.

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Synthesis methods

CHAPTER 2 Core-shell hybrid nanoparticles

Applications

22

Microwave-assisted synthesis Hydrothermal coprecipitation Solvothermal method Chemical vapor deposition (CVD) Combustion waves Stober method Pyrolysis of polymers method Hybrids methods Greener synthesis/ biosynthesis methods

Remove heavy metals Chemical and biomolecular sensor Detection drugs Sensors Biosensor development of new diagnostic platforms Cathode catalysts Vectors Nanocatalysts Parasitology/antileishmanial activities Removal of pharmaceuticals & pollutants

FIG. 2.1 Core-shell NPs: synthesis methods and important applications.

(Law et al., 2008; Sounderya and Zhang, 2008). The conjugation of biomolecules onto the particle surface is crucial for different bioapplications. In many cases, the material of interest may be difficult to conjugate with a particular type of biomolecule; a coating of appropriate biocompatible materials can assist in solving this problem. Typically, a coating of inert materials can enhance the stability of core particles, when the core materials are vulnerable to chemical/thermal alterations during exposure to the surrounding environments. In this case, core/shell NPs are promising for bioapplications. The core/shell NPs are mostly generated for biomedical applications based on the surface chemistry, which enhances its affinity to bind with drugs, receptors, and ligands (Gilmore et al., 2008; Sahoo and Labhasetwar, 2003). The bio/cytocompatibility can enhance the therapeutic value of core-shell NPs, and encourage researchers to synthesize innovative drug carriers with enhanced features, such as increased residence time, increased bioavailability, increased specificity, and the reduction of dosing quantity and frequency (Mahmud et al., 2007; Panda et al., 2008; Van Tomme et al., 2008). Core-shell NPs are extensively applied for bioimaging, as they have good biocompatibility compared to simple NPs (Chen et al., 2010). Generally, the contrasting potentials of core-shell NPs originate from the core materials; the shell materials are responsible for the surface characteristics, including biocompatibility and the conjugation of bioactive materials, because of the existence of reactive moieties on the surface. The shell thickness can be tuned to offer enough contrasting characteristics as a contrast agent as well as binding of biomolecules for targeted drug delivery, specific binding, and biosensing applications (Pinho et al., 2010). In this chapter, some important examples of core-shell nanoparticle production as well as their important applications are highlighted.

2.2 Core-shell NP synthesis

2.2 Core-shell NP synthesis Various bottom-up and top-down approaches have been reported, optimized, and principally applied through physical, chemical, or biosynthetic means or a combination thereof (Iravani, 2011; Jamdagni et al., 2016, 2018; Mohammadinejad et al., 2016, 2019). Some important examples of core-shell NP synthesis are summarized in Table 2.1. For instance, the one-pot production of thermally stable core-shell gold NPs was reported through the surface-initiated atom transfer radical polymerization of n-butyl acrylate and a dimethacrylate-based cross-linker. The higher reactivity of the cross-linker enabled the generation of a thin cross-linked polymer shell around the surface of the gold NP before the growth of linear polymer chains from the shell. The cross-linked polymer shell acted as a robust protective layer, preventing the dissociation of linear polymer brushes from the surfaces of gold NPs and offering the NPs significant thermal stability at high temperature. This synthetic method might be

Table 2.1 Some examples of core-shell NPs and their synthesis methods. Core-shell hybrid NPs Pd@Pt and Cu@Ag Core-shell ironcarbon NPs Fe3O4@carbon

Silica@silver Ni/Fe3O4 Au/Ag Au-Pd Fe3O4@SiO2 Au@Pd Au-Ag Au@Pt Fe3O4/Au Silver-protein

Synthesis methods

References

Microwave-assisted synthesis Hydrothermal coprecipitation Combination of hydrothermal and chemical coprecipitation Electroless reduction Greener method using Moringa Oleifera Greener method using Dioscorea bulbifera Greener method using Cacumen platycladi Greener method using green tea extract Greener method using tryptophan Greener method using gelatin Greener method using gallic acid Greener method using ascorbic acid Greener method using Piper betle L.

Miyakawa et al. (2014) Lima et al. (2019) Rafiee and Khodayari (2016)

Devi et al. (2014) Prasad et al. (2017) Ghosh et al. (2015) Zhan et al. (2011) Sharma and Tapadia (2016) Srivastava et al. (2013) Alarfaj and El-Tohamy (2016) Zhang et al. (2015) Makarov et al. (2014) Usha Rani and Rajasekharreddy (2011)

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simply expanded for the fabrication of other kinds of inorganic/polymer nanocomposites with considerably improved stability (Dong et al., 2008). The production of Fe3O4@C core-shell NPs has been reported in a single step by hydrothermal coprecipitation (Xuan et al., 2007). The generation of Fe3O4@C occurred in this manner: Fe3O4 NPs were produced by the reduction of Fe3+ by glucose in alkaline conditions from the decomposition of urea. The magnetic particles generated in the solution possessed a reactive surface that, after the carbonation of glucose, bonded with carbon, producing the shell of the Fe3O4 particle (Xuan et al., 2007). Additionally, Fe3O4@C with a core-shell tubular structure was prepared using chemical vapor deposition (CVD). The α-Fe2O3 nanotubes were heated in a tubular furnace under an N2:C2H2 flow at 450°C for 30 min (Zhu et al., 2010). In another study, superparamagnetic Fe3O4@C core-shell NPs were fabricated for organic dye removal from aqueous solutions, and the effects of adsorption time and pH on adsorption ability (Zhang et al., 2011). It was demonstrated that both these factors have an influence on the adsorption procedure, wherein the NP exhibited the highest adsorption capacity of 90% of MB in basic pH (7–8) and 210 min under stirring. After the adsorption was completed, the NPs could simply be removed from the water by applying a magnetic field (Zhang et al., 2011). Nowadays, natural sources and bio-inspired materials can be applied for engineering nanomaterials instead of using complicated methods; bio-based synthesized NPs have significant applications in pharmaceutics, biomedicines, and in finding innovative therapeutic and clinical approaches. The greener biosynthesis of coreshell NPs has several advantages compared to conventional methods (Iravani, 2011; Jamdagni et al., 2016, 2018; Mohammadinejad et al., 2016, 2019). For example, plant-derived materials show substantial advantages for fabricating NPs and nanostructures while containing particular functional groups on their surfaces as well as biocompounds (as the capping and reducing agents); these include enzymes (e.g., nitrate reductase) amino acids, starch, glucose, terpenothe ids, polyphenols, alkaloids, phenolic acids, flower pollen, and proteins. Greener approaches can be applied to reduce environmental pollutions and enhance economic development through green chemistry (Iravani, 2011; Mohammadinejad et al., 2016, 2019; Wu et al., 2008). Additionally, bio-inspired strategies are inexpensive and more environmentally friendly than the conventional physical and chemical methods (Iravani, 2011; Mohammadinejad et al., 2016, 2019). Chemically produced NPs may be coated with materials that are applied in the synthesis procedure that restrict their applications in pharmaceutical and medical studies due to the possible related trace amounts of impurities. (Allafchian et al., 2017; Zandpour et al., 2018). Prasad et al. (2017) demonstrated biologically synthesized magnetic nickel/iron-oxide core-shell NPs using Moringa oleifera extract (about 20 g). Moreover, Venkateswarlu et al. (2015) reported two-step bio-based generated Fe3O4-Ag core/shell NPs (approximately 50 nm) using Vitis vinifera stem extract. The plant extracts contained chemical materials with various functional groups responsible for reducing metal ions and capping the produced NPs. Therefore these are preferable for biological evaluations and analyses.

2.3 Applications of core-shell NPs

2.3 Applications of core-shell NPs Core-shell NPs show improved characteristics when compared to single NPs because of their increased performance and durability as well as the breadth of their applications with special economic value (Moghaddam et al., 2017). Core-shell multifunctional NPs show exclusive physiochemical characteristics and can be applied for catalysis, giant magnetoresistance (GMR) sensing, electromagnetic interface shielding or microwave absorption, biomedical applications, drug-delivery systems, and environmental remediation (Table 2.2). Generally, in these nanostructures, the core includes the inexpensive and simply oxidized metals, and the noble shells include the relatively noble metals, carbon, silica, polymers, etc. (Wei et al., 2011). Because of some earlier-mentioned unique properties of core-shell NPs, they can be applied in numerous fields of science and technology such as medicine, engineering, industry, material science, etc. These structures have several optimized features, namely their ability to function over a wide range of temperatures and pH, antimicrobial properties, and magnetic conductivity (Singh et al., 2017). Core-shell nanostructures are especially attractive due to their optimal morphology and adjustable pore size (NPs with porous shell) as well as the free space between the core and shell (which imparts more stability under harsh environments). Finally, the enhanced biocompatibility and economic validation for the large-scale production of powerful absorbents to eliminate contaminants from polluted waters are some other valued attributes. Some of the core-shell nanostructures are multifunctional and thus can be used for several applications with magnetic and luminescent parts. Their magnetic component can help improve the penetration of NPs into

Table 2.2 Some applications of core-shell nanostructures. Core-shell nanostructures

Applications

References

Ag-ZnO Ag-Cu2O Ag-TiO2

Disinfect Vibrio cholera 569B Photocatalysis Degradation of azo dyes

Pt-SnO2 Ag-CeO2 Au-CdS Au-TiO2 Au-Ag

Degradation of formaldehyde Methylene blue degradation and water splitting Degradation of rhodamine B Photocatalysis Detection of drugs

Das et al. (2015) Li et al. (2013) Khanna and Shetty (2014) Chang et al. (2014) Wu et al. (2015)

Au-Ag Au-Pd CoFe2O4@SiO2-NH2

Antileishmanial activities Cathode catalysts Remove heavy metals

Xiao-Li et al. (2014) Gao et al. (2014) Alarfaj and El-Tohamy (2016) Ghosh et al. (2015) Yang et al. (2016) Ren et al. (2017)

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cells and also enhance the resolution of traditional magnetic resonance images (MRI) while the luminescent part can assist in luminescent-based detection (Zaimy et al., 2016). Additionally, multifunctional NPs can be applied for the delivery of biomolecules, such as antibodies, proteins, and genes for treatment (Yang et al., 2008). Biodegradable cationic amphiphilic core-shell polymeric NPs show the capability of loading hydrophobic drugs through their core, and the capability of binding to DNA through their cationic shells. The manufacture of core-shell NPs with desired structures and various interesting pharmaceutical, biomedical, environmental, and agricultural applications will stimulate researchers to work in this field (Kemin et al., 2006). Spherical Fe3O4@C NPs (about 7 nm) have been produced using citrus pectin (as the carbon source) (Zhang et al., 2016). The generated NPs showed the dramatic capability of removing methylene blue for a maximum adsorption capacity of 141.3 mg g 1 as well as superior recyclability (more than 20 cycles). Additional experimental results demonstrated that the adsorption kinetics and isotherm fitted well with the pseudo-second-order kinetic and Freundlich isotherm models, respectively (Zhang et al., 2016). In another study, mesoporous magnetic Fe3O4@C nanospheres were produced by hydrothermal coprecipitation at 200°C for 24 h (Zhang et al., 2013). The effect of core-shell nanospheres was studied and compared with Fe3O4 nanospheres for Cr(IV) removal from water. Cr(IV) removal analyses were accomplished by adsorbing Cr(IV) from aqueous solutions at 28°C and pH 7.6; the nanospheres were dispersed in the Cr(IV) solution. Then, after 150 min, the magnetic materials were attracted and separated by an external magnet. It was reported that Fe3O4@C nanospheres (about 6.2 nm) removed more Cr(IV) when compared with magnetic Fe3O4 nanospheres, reaching 92.4% (Zhang et al., 2013). Nanoprobes comprised of iron oxide/titania (Fe3O4@TiO2) core/shell magnetic NPs were reported. As dopamine molecules can self-assemble onto the surface of the titania substrate, dopamine was applied as the linker to immobilize succinic anhydride onto the surfaces of the iron oxide/titania NPs. IgG can be immobilized via amide bonding. These NPs showed the potential of targeting various pathogenic bacteria, and can efficiently inhibit the cell growth of the bacteria targeted by the NPs under irradiation of a low-power UV lamp within a short period (Chen et al., 2008). Additionally, a nanoparticle catalyst comprising an Ru core covered with an approximately 1–2 monolayer thick shell of Pt atoms was produced. For H2 streams containing 1000 ppm CO, H2 light-off was completed by 30°C, which was meaningfully improved than for traditional Pt-Ru nanoalloys (85°C), monometallic mixtures of NPs (93°C), and pure Pt particles (170°C) (Alayoglu et al., 2008). In another study, 12-tungstophosphoric acid (PW) immobilized on carbon-coated magnetic NPs was produced via a combination of hydrothermal and chemical coprecipitation (Rafiee and Khodayari, 2016). The intermediate carbon layer produced from starch can be applied for protection of the magnetic core and improvement of the dispersion and catalytic activities of the NPs. The high-resolution transmission electron microscopy (HRTEM) image demonstrated that the catalyst had a well-defined core-shell structure (about 50 nm). The produced NPs were applied as nanocatalysts for

2.3 Applications of core-shell NPs

the generation of different bis(indolyl)methanes and β-functionalized indoles in water. The catalyst can be recovered easily by applying an external magnetic field and reused several times without an appreciable loss of its catalytic activity (Rafiee and Khodayari, 2016). Silver-SiO2 core-shell NPs (about 118.2  4.6 nm) have been synthesized. The produced NPs showed significant antifungal influences at a low concentration of 0.5 ppm. It was reported that the stimulated reactive oxygen species (ROS) by these NPs were responsible for the influences of growth inhibitions on the pathogenic fungi (Zheng et al., 2012). In another study, conjugated polymer and core-shell magnetic NPs containing biosensors were manufactured for pesticide evaluations and analyses. The monomer 4,7-di(furan-2-yl)benzo[c][1,2,5]thiadiazole and core-shell magnetic NPs have been generated for producing the biosensing device; it can be applied as an immobilization platform for the detection of pesticides (paraoxon and trichlorfon as the model toxicants). It was observed that under optimized conditions, a low detection limit, high sensitivity, and rapid response could be obtained (Dzudzevic Cancar et al., 2016). Silver-ZnO core-shell nanocomposites were prepared. Zinc oxide was coated on biogenic silver NPs produced by Andrographis paniculata and Aloe vera leaf extract. The prepared nanocomposites showed antimicrobial activities against Candida krusei. The antifungal mechanistic aspects of core-shell nanocomposites could be due to the formation of ROS that may degrade cellular compounds (Das et al., 2016). Additionally, hybrid nanosystems based on new 2-((4-chlorophenoxy)methyl)-N(substituted phenylcarbamo-thioyl)benzamides and Fe3O4@C18 core-shell NPs were reported. After the production and analysis of the benzamides, they were loaded on Fe3O4@C18 nanostructures. The produced hybrid nanosystems showed an accelerated efficiency in inhibiting the growth of C. albicans biofilms. The prepared nanosystems showed suitable biocompatibility, and can be applied as nanocarriers for antifungal substances (Limban et al., 2018). It was reported that magnetic core-shell nanocomposites can be applied for removing different toxic and hazardous materials from waters, including heavy metals, pesticides, dyes, toxic organic chemicals, and different biocontaminants. Core-shell magnetic nanostructures show some unique advantages, including low cost, high efficiency, better stability, outstanding magnetic and separation properties, and improved biocompatibility (Deshpande, 2017; Lima et al., 2017; Shah et al., 2016). In one study, magnetite silica core-shell NPs (with high stability and reusability) were prepared and analyzed as a suitable nanoadsorbent for eliminating Zn(II) from aqueous solutions (with a maximum capacity of 119 mg g 1 at room temperature). These NPs were synthesized by combining coprecipitation and sol-gel approaches; they could be simply separated from aqueous solutions by a magnet (Emadi et al., 2012). Moreover, core-shell Fe3O4@C hybrid NPs that were ecofriendly were prepared. Consequently, significant heavy metal ion removal was obtained for Pb(II), Cd(II), Cu(II), and Cr(VI) up to 100%, 99.2%, 96.6%, and 94.8%, respectively. Additionally, the produced NPs could be simply separated from the aqueous solutions after adsorption because of the relative large submicrometer

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size and the improved external magnetic fields presented by the iron-based cores ( Ji et al., 2018). Additionally, core-shell particles containing a core of Fe3O4 coated with trimethyl chitosan/siloxane hybrid shells have been generated by the coating method. Experiments investigated the potential of the produced particles for the magnetically assisted removal of the antibiotic sulfamethoxazole from aqueous solutions. It was reported that sulfamethoxazole-based particles offer more developed adsorption capacity than their counterparts produced by pristine chitosan (Soares et al., 2019).

2.4 Conclusions and future perspectives Core-shell hybrid nanostructures can be fabricated for the purposes of better solubility, improved thermal/chemical stabilities, lower toxicity, and better permeability/ specificity. There are valuable developments in the field of greener synthesis of NPs (especially for core-shell NPs). Core-shell NPs can be applied in environmental remediation for water pollution and the protection of human health from exposure to toxic and hazardous materials, including pharmaceuticals, dyes, oils, and heavy metals. Indeed, extrascientific investigations and industrial implementation of applications in this area may assist in increasing the quality of life. Nanoscientists may feel stimulated to investigate the applications of core-shell hybrid NPs instead of single NPs. Methods for industrial production and structural/physical property compatibility analysis between the core and shell structural materials are infrequently investigated and are crucial for evaluating the stability of core-shell hybrid NPs. For the quality improvement of these NPs, it appears that more elaborate studies are needed in the future. Core-shell nano/microfunctional materials can be applied in various fields, including environmental remediation, agriculture, catalysts, and energy. These structures can be prepared on a large scale by applying the optimized conditions.

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Wu, L., Fang, S., Ge, L., Han, C., Qiu, P., Xin, Y., 2015. Facile synthesis of Ag@CeO2 coreshell plasmonic photocatalysts with enhanced visible-light photocatalytic performance. J. Hazard. Mater. 300, 93–103. Xiao-Li, L., Shan, L., Min, L., Xue-Feng, Y., Li, Z., Qu-Qua, W., 2014. Facile synthesis of Au nanocube-CdS core-shell nanocomposites with enhanced photocatalytic activity. Chin. Phys. Lett. 31, 064203. Xuan, S., Hao, L., Jiang, W., Gong, X., Hu, Y., Chen, Z., 2007. A facile method to fabricate carbon-encapsulated Fe3O4 core/shell composites. Nanotechnology. 18, 035602. Yang, Y., Shi, J., Kawamura, G., Nogami, M., 2008. Preparation of Au-Ag, Ag-Au core-shell bimetallic nanoparticles for surface-enhanced raman scattering. Scr. Mater. 58, 862–865. Yang, G., Chen, D., Lv, P., Kong, X., Sun, Y., Wang, Z., Yuan, Z., Liu, H., Yang, J., 2016. Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications. Sci. Rep. 6, 35252. Zaimy, M.A., Jebali, A., Bazrafshan, B., Mehrtashfar, S., Shabani, S., Tavakoli, A., Hekmatimoghaddam, S.H., Sarli, A., Azizi, H., Izadi, P., Kazemi, B., Shojaei, A., Abdalaian, A., Tavakkoly-Bazzaz, J., 2016. Coinhibition of overexpressed genes in acute myeloid leukemia subtype M2 by gold nanoparticles functionalized with five antisense oligonucleotides and one anti-CD33(+)/CD34(+) aptamer. Cancer Gene Ther. 23, 315–320. Zandpour, F., Allafchian, A., Vahabi, M.R., Jalali, S.A.H., 2018. The green synthesize of silver nanoparticles by arial part of Dorema ammoniacum D. extract with antimicrobial analysis. IET Nanobiotechnol. 12. Zhan, G., Huang, J., Du, M., Abdul-Rauf, I., Ma, Y., Li, Q., 2011. Green synthesis of Au-Pd bimetallic nanoparticles: single-step bioreduction method with plant extract. Mater. Lett. 65, 2989–2991. Zhang, Z., Kong, J., Novel, J., 2011. Magnetic Fe3O4@C nanoparticles as adsorbents for removal of organic dyes from aqueous solution. J. Hazard. Mater. 193, 325–329. Zhang, H., Liu, D.L., Zeng, L.L., Li, M., 2013. ß-Cyclo dextrin assisted one-pot synthesis of mesoporous magnetic Fe3O4@C and their excellent performance for the removal of Cr (VI) from aqueous aolutions. Chin. Chem. Lett. 24, 341–343. Zhang, G., Zheng, H., Shen, M., Wang, L., Wang, X., 2015. Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid. J. Phys. Chem. Solids 81, 79–87. Zhang, W., Zhang, L.Y., Zhao, X.Y., Zhou, Z., 2016. Citrus pectin derived ultrasmall Fe3O4@C nanoparticles as a high-performance adsorbent toward removal of methylene blue. J. Mol. Liq. 222, 995–1002. Zheng, L.P., Zhang, Z., Zhang, B., Wang, J.W., 2012. Antifungal properties of Ag-SiO2 core-shell nanoparticles against phytopathogenic fungi. In: Advanced Materials Research. vol. 476. Trans Tech Publications, pp. 814–818. Zhu, Q., Tao, F., Pan, Q., 2010. Fast and selective removal of oils from water surface via highly hydrophobic core-shell Fe2O3@C nanoparticles under magnetic field. Appl. Mater. Interfaces 2, 3141–3146.

CHAPTER

Hybrid inorganic-polymer nanocomposites: Synthesis, characterization, and plant-protection applications

3

Ayat F. Hashima, Khamis Youssefb,*, Sergio Ruffo Robertoc, Kamel A. Abd-Elsalamb a

Fats and Oils Department, National Research Centre, Cairo, Egypt bPlant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt cAgricultural Research Center, Department of Agronomy, Londrina State University, Londrina, Brazil

3.1 Introduction Polymer nanocomposites have received great attention from nanoscience academics and industry due to their great mechanical, physical, and tribological characters. The addition of nano-sized inorganic fillers such as clay, Al2O3, CaCO3, TiO2, ZnO, and SiO2 has reformed the mechanical and physical properties of the polymers extensively, and in standard the nanocomposites are advanced to virgin polymers in lots of features (Balasubramanian and Jawahar, 2015). The combination of nanoparticles in the polymer has amended the properties of the polymer significantly. This paves the way to use nanocomposites in several agricultural applications such as water treatment, disease detection, drug-delivery systems, food processing, food health screening, pest detection and management, and improvement of sustainable agriculture (Hashim et al., 2016). Some investigations show that using nanocomposites as fertilizers may increase nutrient efficiency, reduce soil toxicity, minimize potential negative consequences related to overdoses, and decrease the frequency of the utility. For this reason, nanotechnology has a high capability for reaching sustainable agriculture, mainly in developing nations (Qureshi et al., 2018). Nanocarrier-enabled managed slow release additionally has been utilized for plenty of other programs and functions, including insecticides, food, and active ingredients transferred to targeted sites (Hayles et al., 2017; He and Hwang, 2016). The nanocomposite packaging complements the shelf life of many types of meals, mainly through antimicrobial dispositions and electrical sensors (Idumah et al., 2019). The nanoclay incorporation reduces the water absorption and therefore improves the performance of the polymer. In this chapter, the synthesis, characterization methods, and applicability of inorganic-polymer hybrid nanocomposites in plant protection are discussed. *Corresponding author Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems. https://doi.org/10.1016/B978-0-12-821354-4.00003-0 # 2020 Elsevier Inc. All rights reserved.

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3.2 Categorization of functional hybrid materials Hybrid materials are nanocomposites at the molecular scale, having at a minimum one element, organic or inorganic, with a distinguishing length at the nano size (Judeinstein and Sanchez, 1996). The properties of the hybrid materials are not just the result of the individual contributions of their components, but also from the strong synergy produced by a hybrid interface (Sanchez et al., 2003). The nature of the inorganic interface, including the surface energy, the types of interactions present, and the existence of labile bonds, shows a strong role in controlling a wide range of properties (electrical, mechanical, optical, catalysis, sensing capability, separation capacity, and chemical and thermal stability). Due to their great importance, different functional hybrid materials can be divided into two main classes (Class I, II) depending on the nature of the interface combining the organic components and inorganic materials ( Judeinstein and Sanchez, 1996). Class I deals with hybrid systems where the organic and inorganic parts act together with weak bonds, including van der Waals, electrostatic, and hydrogen bonds. In addition, class II indicates hybrid materials in which these components are linked by covalent or ionic-covalent chemical bonds.

3.3 Synthesis approaches toward polymer nanocomposites Nanocomposites can be synthesized by the in situ method of inorganic particles or by the dispersion of fillers in a polymeric matrix (Kickelbick, 2007). Polymer nanocomposite synthesis usually applies bottom-up or top-down approaches. In the bottom-up approach, precursors are used to build and grow, from the nanometric level, wellorganized structures. Additionally, a building block approach can be used, where already formed units or nanoobjects are hierarchically combined to originate the desirable material. This approach has an advantage compared to in situ nanoparticle formation because at least one structural element is well defined and regularly does not have significant structural changes during the matrix formation. Chemical processes such as sol-gel, chemical vapor deposition (CVD), template preparation, or spray pyrolysis are employed as bottom-up methodologies (Ruiz-Hitzky et al., 2011). On the contrary, top-down approach, bulk material breaks down into smaller pieces or patterning, using in most cases physical methods such as the dispersionlayered silicates in polymer matrices. Several methods have been employed for the preparation of polymer-based inorganic nanoparticle composites (Fig. 3.1). The important ones are: (i) intercalation of nanoparticles with the polymer or prepolymer from solution (Yano et al., 1998; Rong et al., 2001); (ii) in situ intercalative polymerization (Ariga and Nalwa, 2009; Xu et al., 2008); (iii) melt intercalation (Sarkar et al., 2012); (iv) a direct mixture of particulates and polymer (Wright and Sommerdijk, 2001; Maneeratana, 2007); (v) template synthesis (Ebelman, 1846); (vi) in situ polymerization (Brinker and Scherer, 1990); and (vii) the sol-gel process (Yamane et al., 1978).

3.4 Polymer-based inorganic nanocomposites

FIG. 3.1 Preparation scheme of hybrid inorganic-polymer nanocomposites.

3.4 Selected examples on the development of polymer-based inorganic nanocomposites Epoxy and polydimethylsiloxane (PDMS) nanocomposites are prepared using the sol-gel processes. These reactions have been used widely in the synthesis of inorganic materials, and are one of the most common ways for preparing amorphous hybrid networks in situ at low temperatures (Bounor-Legar
e and Cassagnau, 2014; Pomogailo, 2005; Zou et al., 2008). The sol-gel process is well described and consists of two steps: the hydrolysis of a molecular precursor and a polycondensation reaction to form the inorganic complex. Both reactions can also happen simultaneously once hydrolysis has begun. Epoxy-SiO2 and epoxy-TiO2 nanocomposites were synthesized using tetraethyl orthosilicate (TEOS) and tetraethylorthosilicate (TEOT), respectively, as the

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precursors for the inorganic oxides (Wu and Hsu, 2010). Glycidyloxypropyl trimethoxysilane (GPTMS) was used as a coupling agent. For the epoxy-SiO2 nanocomposites, they followed a one-step procedure by mixing all the reactants and adding HCl dropwise while stirring. A similar method was used for the epoxy-TiO2 nanocomposites, but a mixture of tetraethylorthosilicate and acetylacetone was added dropwise. Maleic anhydride (MA)-grafted polyethylene/clay nanocomposites were synthesized using simple melt compounding (Wang et al., 2001). The behavior of intercalation and exfoliation relied on the hydrophilicity of the polyethylene grafted with the chain length of the organic modifier in the clay and maleic anhydride. While polyethylene has a higher grafting level of MA than the critical grafting level of maleic anhydride and the number of methylene groups in the alkylamine chain is more than 16, polyethylene/clay nanocomposites are totally exfoliated. Nylon 6/MMT nanocomposites with low molecular weight had districts of intercalated and exfoliated clay platelets while the medium and high molecular weight nylon 6/MMT nanocomposites showed well-exfoliated structures. As the MW (molecular weight) increased, so did the extent of clay platelet exfoliation for the nanocomposites (Schubert et al., 1995; Turova et al., 2002). Nano-SiO2 particle/linear low-density polyethylene (LLDPE) was prepared via in situ polymerization (Hench and West, 1990). A slight increase in MW with the larger particles was apparent. It was detected that higher amounts of SiO2 resulted in lower molecular weight. It was found that the larger particles displayed higher activity due to fewer interactions between SiO2 and methylaluminoxane. Poly (methyl methacrylate/clay nanocomposites (PMMA) were prepared by a novel pseudodispersion polymerization in scCO2 (supercritical carbon dioxide) (Kickelbick, 2008). Indeed, using an effective stabilizer [fluorinated surfactantmodified clay (10F-clay)] for PMMA polymerization in CO2 can enhance polymer yields as compared with traditional hydrocarbon surfactant-modified clay. Methyl methacrylate/clay nanocomposite/layered silicate intercalated nanocomposites were prepared using scCO2 (Rehahn, 1998). The morphology of silicate is homogeneous, as clay concentrations relative to 40 wt%, the intercalated silicate structure is thermodynamically restricted regarding clay separation.

3.5 Characterization of hybrid inorganic-polymer nanocomposites Dynamic light scattering (DLS) measurements are considered to be the most known way for determining polymer sizes in a solution. Infrared spectroscopy is one of the majorly potent analytical techniques, which offers the possibility of chemical identification. IR, when coupled with intensity measurements, may be a good choice for quantitative analysis. X-ray diffraction has assumed a focal role in recognizing and describing solids since the early stage of this century. The nature of bonding and the

3.6 Hybrid inorganic-polymer nanocomposites and plant-protection field

working criteria for distinguishing between the short-range and long-range order of crystalline arrangements from the amorphous substances are largely derived from X-ray diffraction. Therefore, it remains a helpful apparatus to get structural information. Scanning electron microscopy (SEM) shows the distribution of morphological structures such as fillers and their agglomerates in polymer nanocomposites, Thermal analysis may be defined as the measurement of the chemical and physical properties of materials as a function of temperature. The two main thermal analysis methods are thermogravimetric analysis (TGA), which automatically records the change in weight of a sample as a function of either temperature or time, and differential thermal analysis (DTA), which determine the difference in temperature between a sample and an inert reference material as a function of temperature. DTA therefore detects changes in heat content. Differential scanning calorimetry (DSC) is an analytical method that assists in recognizing the thermal behavior of polymer nanocomposites. It aids in finding the glass transition temperature (Tg) of polymers and polymer composites.

3.6 Hybrid inorganic-polymer nanocomposites and plant-protection field The preparation of inorganic oxide nanoparticles in situ legitimately in the polymer medium is an elective way to deal with the synthesis of polymer nanocomposites, in spite of nanocomposites that are handled utilizing conventional ex situ blending systems. The upgrades in the properties detected for these hybrid materials settle on them alluring decisions for application in many fields, including coatings, wrapping materials, nanodielectrics, and photovoltaics (Adnan et al., 2018). Generally, polymer/clay nanocomposites contain an organic/inorganic hybrid polymer matrix containing platelet-shaped clay particles that have sizes in the order of a few nanometers thick and several hundred nanometers long. Because of their high aspect ratio and high surface area, the clay particles, if properly dispersed in the polymer matrix at a loading level of 1–5 wt%, instruct unique combinations of physical and chemical properties to make them attractive for films and coatings in a wide range of industries (Han et al., 2010). In the field of plant protection, polymer nanocomposites are biodegradable and ecofriendly. Toward this path, the improvement of mulch films can be helpful for farmers to control weeds (Ray, 2013). The greatest benefit of nanopesticides is that they are powerful at ensuring crops. The improvement and commercialization of these items requires profoundly specialized item advancement, advertising advancement, and market instruction (Shivani, 2015). This could come essentially from huge players for quick development. All these together are explanations behind the fast improvement. Several species of fungi and bacteria have been controlled using inorganic-polymer nanocomposites (Fig. 3.2).

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FIG. 3.2 Selected examples of fungi and bacteria controlled by hybrid inorganic-polymer nanocomposites.

3.6.1 Hybrid inorganic-polymer nanocomposites against plant pathogenic fungi One of the potential uses of silver (Ag) is in plant disorders. Ag shows different methods of inhibitory activity against plant pathogenic fungi. Consequently, it might be utilized with relative well-being for the control of different plant pathogens, in contrast to chemical fungicides (Min et al., 2009). Some metal oxide nanoparticles including zinc (Zn), copper (Cu), and Ag have antimicrobial impact. The antibacterial and antifungal efficacy of ZnO microparticles has been accounted for by Sawai and Yoshikawa (2004). Panacek et al. (2009) revealed that Ag nanoparticles would have a good antifungal impact against Candida by lesser does. Likewise, ZnO nanoparticles have noteworthy antifungal properties against Botrytis cinerea and Penicillium expansum and incremental inhibitory impacts by various fixations (He et al., 2011). ZnO and CuO nanoparticles can be compelling against Candida albicans (Najafzadeh et al., 2015). The antifungal impact of Cu nanoparticles against plant pathogenic growth was accounted by Cioffi et al. (2004). Nanofungicides can be integrated in a simple, financially savvy way and are appropriate for planning new kinds of biohybridnanocide materials that would be utilized as another inviting antimicrobial agent against various fungal pathogenic microbes (Abd-Elsalam and Alghuthaymi, 2015). The effect of chemically produced Cu nanoparticles against Penicillium digitatum and Fusarium solani on citrus was studied (Youssef et al., 2017). Various studies on the antifungal efficacy of chitosan (CS) against plant pathogens have been

3.6 Hybrid inorganic-polymer nanocomposites and plant-protection field

extensively reported (Baba et al., 1996; Rabea et al., 2003; Reddy et al., 1998; Sautista-Banos et al., 2006). The fungicidal activity of the clay-chitosan nanocomposite was tested in vitro and in vivo against the green mold of citrus fruit caused by P. digitatum (personal communication). One of the most important attributes of chitosan is associated with its fungistatic or fungicidal properties against postharvest fungi (Alternaria alternata, Colletotrichum gloeosporioides, Fusarium oxysporum, Rhizopus stolonifer, Penicillium spp., Botrytis cinerea, Neurospora crassa) with various concentrations of chitosan (Bautista-Banos et al., 2006; Benhamao and Theriault, 1992; Bhaskara-Reddy et al., 2000; Palma-Guerrero et al., 2009; Reglinski et al., 2010). Nanochitosan is compelling against various kinds of microorganisms (Ahn et al., 2009; Alt et al., 2004; Yang et al., 2012). A biosynthesized Ag nanoparticle-chitosan composite was connected to build up successful antibacterial activity (Di et al., 2012). The new CS-Ag-nanoparticle composite was incorporated and was revealed to have a significantly higher antimicrobial action than its parts in the pertinent fixations (Sanpui et al., 2008). The Ag/CS nanoformulation has significant antifungal action against screened organisms, for example, Aspergillus flavus, Alternaria alternata, and Rhizoctonia solani. The synergistic antimicrobial efficacy of a CS-Ag nanoparticle composite within the sight of subatomic iodine was expanded (Banerjee et al., 2010). A CS-silica hybrid aerogel was synthesized by sol-gel by integrating an inorganic network in the occurrence of an organic polymer (Ebisike et al., 2018). A CS modified with CuNPs was assessed to be compelling against two microorganisms influencing food quality and, in this manner, could be utilized to improve sustenance quality and broaden the timeframe of realistic usability of sustenances (Ca´rdenaz et al., 2009). The antifungal properties of some inorganic nanoparticles such as S (sulfur), Ag, CuO, MgO, and ZnO were found alone or joined with biopolymers in all respects as of recently distributed articles (Brunel et al., 2013; Mohan et al., 2011). Through in vitro examination, the synthetic mix of CS nanoparticles was discovered to be most efficient at 0.1% focus and demonstrated 89.5%, 63.0%, and 60.1% development decreases of A. alternata (Saharan et al., 2013). The high synergistic impact between chitosan and Cu on the diminishing parasitic development of Fusarium graminarum was inspected. The consolidated copper (II) chitosan colloids are another age of Cu-based biopesticides (Brunel et al., 2013). Smaller-scale CS and CS-based microparticles joined with Cu particles were screened for fungicidal intensity against the toxicogenic growth of F. solani (Vokhidova et al., 2014). A CS biopolymer has been utilized to coat diverse sorts of leafy green vegetables in view of its antimicrobial exercises and to deliver an assortment of plasticized CS films for the security of sustenance items due to the created mediated modified atmosphere (Miranda et al., 2007). Recently, CS-Cu nanocomposites were synthesized and characterized while their fungicidal effectiveness was confirmed against Sclerotium rolfsii and R. solani (Rubina et al., 2017). Also, regarding the plant host itself, the impact of Cu-CS nanoparticles on the physiological and biochemical modifications during maize seedling

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growth was investigated by Saharan et al. (2016). This study recommended that Cu-CS nanoparticles improved the seedling growth of maize by activating the reserved food, principally starch, through the higher action of α-amylase. The results of the last few years on the application of chitin- and CS-based molecules in plant yields were reviewed by Malerba and Cerana (2019). The biodegradable hybrid nanocomposites of CS/gelatin and Ag nanoparticles were tested as effective alternatives to plastic packaging materials for the packaging of red grapes (Kumar et al., 2018). CS-based polymers and nanoparticle complexes with different molecules were used on different plant species. Harpin was used against R. solani on tomatoes (Nadendla et al., 2018); tripolyphosphate was used to stimulate plant growth and the biomass accumulation of pepper (Asgari-Targhi et al., 2018); thiamine was used for the stimulation of chickpea growth and resistance against Fusarium oxysporum (Sathiyabama et al., 2019); salicylic acid was used for the stimulation of lettuce and maize growth and improved disease resistance (Kumaraswamy et al., 2019; Martin-Saldan˜a et al., 2018). A CS/nanosilica/sodium alginate extended the shelf life of fruit and inhibited pathogen growth on the Chinese winter jujube (Zizyphus jujube Mill. cvDongzao) (Kou et al., 2019). Ag-CS nanocomposites were planned as capable fungicidal agents for the prevention of strawberry grey mold (Moussa et al., 2013). Silica-alginate microcapsules were used to prepare the prochloraz microcapsules to protect prochloraz against degradation under UV irradiation and alkaline conditions (Zhang et al., 2014). Cellulose filaments offer an incredible surface for microbial development. In light of their atomic structure and huge dynamic surface territory, cellulose fibers might be a perfect medium for bioactive, biocompatible, and brilliant materials (Belyaev, 2000; Stashak et al., 2004). The cellulose/Cu composites were created by physical techniques and demonstrated a high antifungal impact. The microbial development of Saccharomyces cerevisiae decreased in contact with the cellulose/ Cu composites. However, the viability relied upon the systems connected to an amalgamation of the composite material and on the realistic convergence of Cu particles. The practicality of the cellulose/Cu composites to repress the development of pathogens in contact with trickled organic product juices was tried under controlled conditions (Llorens et al., 2012a, 2012b). The affectability of certain strains of Fusarium, Penicillium, and Aspergillus was applied to a Cu surface, and found versatile spores of Aspergillus niger. The negligible inhibitory centralizations of Cu sulfate was about 4.7 mmol/kg for P. expansum, and around 8 mmol/kg for B. cinerea (Judet-Correia et al., 2011). Ag particles from cellulose/Ag nanocomposites are powerful enough to lessen microbial development in contact with meat or natural product exudates. Then again, proteins neutralize the inhibitory activity of Ag particles against waste-related pathogens, becoming the organic product that dribbles a mostly good substrate to understand the ideal antimicrobial exercise of Ag in sustenance safeguarding applications (Llorens et al., 2012b; Lloret et al., 2012). Silica-Ag nanoformulation comprising nano-Ag joined with nano-SiO2 successfully controlled fine molds of pumpkin on a concentration as low as 0.3 ppm. It also demonstrated antifungal action against the plant-tainting organisms Rhizoctonia solani, Botrytis cinerea, Magnaporthe

3.6 Hybrid inorganic-polymer nanocomposites and plant-protection field

grisea, Pythium ultimum, and Colletotrichum gloeosporioides at 3.0 ppm with different degrees (Hae-Jun et al., 2006). The starch balanced out Ag NPs demonstrated a decent antifungal action against Candida albicans (Raji et al., 2012). The fungicidal effectiveness of some antifungals, for example, amphotericin B, posaconazole, itraconazole, and voriconazole, was not as great as starch-settled Ag NPs (Panacek et al., 2009). A polylactic corrosive (PLA) nanobiocomposite was joined with Ag nanoparticles and cellulose nanocrystals to get an antimicrobial film with improved boundary properties (Fortunati et al., 2013). Cu-containing nanomaterials have been assessed as antimicrobial specialists for food-packaging applications. This nanoantimicrobial was made of Cu nanoparticles embedded in poly-lactic corrosives, which has been tried as a biodegradable polymer framework (Longano et al., 2013). PLA/ZnO nanocomposites are a potential contender for applications in food-packaging applications (Murariu et al., 2011).

3.6.2 Hybrid inorganic-polymer nanocomposites against plant pathogenic bacteria Cu is an intriguing possibility to be actualized with regard to novel sanitation techniques. Cu is a basic cofactor for metalloproteins and proteins and, at high focus, is a wide-ranging antimicrobial that is compelling against principal nourishment-borne pathogenic microbes such as Salmonella enteric and Campylobacter jejuni (Faundez et al., 2004). As of late, hybrid materials dependent on chitosan have been incorporated, including leading polymers, metal nanoparticles, and oxide operators, because of their incredible antimicrobial properties (Li et al., 2010). The bactericidal effects of chitosan TPP nanoparticles stacked with different metal particles were tried, and the outcomes demonstrated that antibacterial efficacy was improved by the stacked metal particles (Du et al., 2008). The monocomponent CS is an antimicrobial operator that is not, as of now, fulfilling the prerequisites of certain conditions. For example, the mix of chitosan with other inorganic operators Ag, Zn, SiO2, and TiO2 and among them chitosan-Ag nanoparticles composite had significantly had high antibacterial action with just a little nearness of Ag-nanoparticles which display potential antifungal properties (Li et al., 2010). Chitosan has a high chelating capacity with various metal particles, for example, Ag, Cu, Zn, Mn, and Fe in acidic conditions. This chitosan metal complex is more grounded in its antimicrobial action (Kong et al., 2010). Chitosan nanoparticles and Cu-stacked nanoparticles could notably decrease the development of various pathogens and display higher antibacterial action than chitosan itself or doxycycline (Qi et al., 2004). The antimicrobial actions of metallic Cu nanoparticles orchestrated in the chitosan polymer were assessed (Usman et al., 2013). A cellulose nanocrystal can offer a high antimicrobial impact for ZnO nanoparticles (Azizi et al., 2008). The cellulose agents were observed to be exceptionally dynamic against Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus than the parent Cloxacillin antibiotic medication and cellulose. The created cellulose rod-like nanocrystal/polyrhodanine center sheath nanoparticles showed

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promising antimicrobial properties against Escherichia coli and Bacillus subtilis (Tang et al., 2015). Clay/clay nanocomposites showed a synergistic effect against Escherichia coli and Staphylococcus aureus (Han et al., 2010). Polymer-clay nanocomposites are a class of hybrid materials composed of organic polymer matrices and nanoscale organophilic clay fillers (Kim et al., 2003). When nanoclay is mixed with a polymer, three types of composites (tactoids, intercalation, and exfoliation) can be obtained (Xu et al., 2006). The biological control antagonists are adsorbed on a chitosan-immobilized silica nanocomposite on Ralstonia solanacearum. The growth of tomato seedlings was also investigated, leading to improved microbial effectiveness against the Ralstonia solanacearum and amplified tomato yield (Dennis et al., 2016). The mode of action of Cu-polymer nanocomposites was related to more than one toxicity: (i) Cu ions produce reactive oxygen species, lipid peroxidation, protein oxidation, and DNA degradation, (ii) Cu ions break and subsequently disintegrate the bacterial cell wall and membrane, and (iii) Cu ions released in the bacteria bind to DNA and trigger genotoxicity, endocytosis, and direct diffusion (Tamayo et al., 2016) (Fig. 3.3). The toxic mechanisms of various polymer/NP and Cu composites

FIG. 3.3 The antibacterial effects observed in Cu-polymer nanocomposites are based on three phenomena: (i) Release of Cu ions, (ii) release of Cu nanoparticles from nanocomposites, and (iii) biofilm inhibition. Reprinted from with Tamayo, L., Azo´car, M., Kogan, M., Riveros, A., Pa´ez, M., 2016. Copper-polymer nanocomposites: an excellent and cost-effective biocide for use on antibacterial surfaces. Mater. Sci. Eng. C 69, 1391–1409 with permission from Elsevier.

References

depend on their ion release capacity as a direct relationship among these assets and the antimicrobial performance was determined. A comparable propensity was discovered in polymer/Ag composites (Radheshkumar and M€unstedt, 2006). The polymer matrix is consequently an essential issue in the bactericide conduct of the composites as independent of the metal filler (Ag or Cu); the ion release rate further relies upon the matrix properties (Cioffi et al., 2005; Radheshkumar and M€ unstedt, 2006).

3.7 Conclusion and future perspectives In the field of plant protection, polymer nanocomposites are recyclable, green, and environmentally ecofriendly. Toward this path, the improvement of mulch films can be helpful for farmers to protect their crops. As a summary, regardless of the open difficulties, particles dependent on hybrid inorganic polymers have demonstrated value in different parts of plant science generally, and in particular the plant protection field. The enormous number of papers currently published demonstrate the fervor of scientists for the utilization of these particles in agriculture. This should prompt important innovation in a concise period and expansion of their utilization to a different field of plant science.

Acknowledgment Sincere thanks to Conselho Nacional de Desenvolvimento Cientı´fico e Tecnolo´gico (CNPq) Grant #315844/2018-3 to Dr. Youssef Khamis.

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Preparation of nanocomposites from agricultural waste and their versatile applications

4

Josef Jampı´leka,*, Katarı´na Kra´lˇova´b a

Department of Analytical Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia bInstitute of Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia

4.1 Introduction From time immemorial, humankind has generated and accumulated waste of various origins; thus, it should manage waste disposal as well. During past centuries, there was mainly biological waste that decomposed with time; unfortunately, currently, plastic waste and electronic scrap are accumulated around inhabited zones. Thus, biodegradable wastes or, in an acceptable time scale, degradable wastes were replaced by waste, with which not only natural processes but also people cannot cope. In addition, these types of waste can endanger human health and can be considered as biological and/or chemical hazards, making them an ecological burden (Al-Salem et al., 2009; Barles, 2014; Ben and Jerry, 2019; EPA, 2019; Evans et al., 2012; Heller et al., 2019; Kaya, 2016; Lebreton and Andrady, 2019; Mwanza and Mbohwa, 2017; Ragaert et al., 2017; V€ais€anen et al., 2016; Yu et al., 2016). One way to reduce waste accumulation is by recycling or using biodegradable plastics. Waste from agriculture and food production falls into the category of biodegradable waste. However, these wastes need not only be converted into livestock feeds, manure, and compost or incinerated to produce heat but can also be used to obtain "building" materials, especially cellulose ( Jawaid et al., 2017; Rajinipriya et al., 2018; Sangeetha et al., 2017). In higher plants, cellulose is organized in a hierarchical structure consisting of β-(1!4)-linked D-glucopyranose chains that are laterally bound by hydrogen bonds to form microfibrils with a diameter in the nanoscale range, which are further organized into microfibril bundles (Klemm et al., 1998). Bioagricultural waste, or biocracy, can also be used to fabricate charcoal, highly porous biochar possessing a broad range of nanoscale pore sizes, or nanoscale silica. *Corresponding author Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems. https://doi.org/10.1016/B978-0-12-821354-4.00004-2 # 2020 Elsevier Inc. All rights reserved.

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These "building" materials can be used to produce nanomaterials (NMs) for a wide variety of applications. Nanocellulose, nanoscale carbon-based materials, and nanosilica are used nowadays to fabricate constituents of nanocomposites (NCs) utilized for miscellaneous purposes in industry, agriculture, and medicine or the decontamination of polluted environments. Agricultural waste such as banana or orange peels, wheat whiskers, straw, cotton or corn stalks, coconut or almond shells, corn silk, rice husks, oil palm empty fruit bunches, bagasse, peanut hulls, or ginger rhizome (see Fig. 4.1) could also be successfully applied for these purposes ( Jampı´lek et al., 2019; Jampı´lek and Kra´ˇlova´, 2015, 2017a,b,c, 2018a,b,c, 2019a,b; Jawaid et al., 2017; Sangeetha et al., 2017; Zamani et al., 2019). Nanocellulose is represented by cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs), and cellulose nanowhiskers can be fabricated from any cellulose source material, including agricultural waste (see Figs. 4.2–4.3). The mechanical disintegration of cellulose fibers with approximately 20–40 nm in width and several micrometers in length containing both crystalline and amorphous regions results in CNFs showing high length-to-diameter aspect ratios that, when used as reinforcement fillers in composites, could pronouncedly improve their mechanical properties (e.g., Khalil et al., 2017; Perumal et al., 2018b; Ukkund et al., 2019; Xu et al., 2018). CNFs were isolated from much of the agricultural waste, such as banana peels (BP) (Tibolla et al., 2018, 2019), Agave fourcroydes Lem. (Fazeli et al., 2018) or wheat straw (WS) fibers (Fan et al., 2018), coconut palm petiole residues (Xu et al., 2015), rice straw (RS) pulp (Hassan et al., 2018), sugarcane bagasse (SCB) (Patil et al., 2018a; Rani et al., 2018), energy cane bagasse (Yue et al., 2016), or pineapple leaf (Balakrishnan et al., 2017). CNFs characterized by highly ordered architecture consisting of the self-assembly of repetitive building blocks into higher-order structures, which are stabilized by noncovalent interactions, were reported to be fabricated, for example, from steam exploding RS fibers, RS cellulose microfibrils

FIG. 4.1 Agricultural waste types applied to fabricate nanocomposites.

4.1 Introduction

FIG. 4.2 Electron microscope images of nanofiber cellulose extracted from trees (Nippon, 2019).

FIG. 4.3 Electron microscope image of nanofiber cellulose extracted from stalks. Published with the kind permission of JEOL(EUROPE)SAS.

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(Wang et al., 2018a), or coir fibers (Yue and Qian, 2018). Using a surface modification of CNFs such as by grafting the designed polymer onto the CNF surface, the CNF properties could be further improved (e.g., Zhang et al., 2017a). CNCs could be fabricated from various agricultural wastes using the preferential hydrolysis of some lessorganized regions in cellulose that are more susceptible to the catalytic hydrolysis of the glycosidic bonds (Pereira and Arantes, 2018; Perumal et al., 2018a). CNCs were prepared from RS (Perumal et al., 2018a,b), rice husks (RH) (Kargarzadeh et al., 2017), oil palm trunks (Lamaming et al., 2017), mango seed shells (Silva et al., 2019), SCB (El Achaby et al., 2017; Kassab et al., 2019; Lam et al., 2017), and bleached SCB (Ferreira et al., 2018, 2019). In addition, Dai et al. (2018) isolated carboxymethyl cellulose (CMC) from pineapple peels. On the other hand, microfibrillated cellulose was isolated from the bleached materials of RS, bagasse, and cotton stalk biomass waste (Adel et al., 2016). Cellulose nanowhiskers were prepared from jute (Kasyapi et al., 2018) or from oil palm mesocarp fibers (de Campos et al., 2017). Advances in the CNC manufacturing methodologies focusing on principal cellulose resources and the main processes used for their isolation were summarized by Trache et al. (2017). Nanocellulose applications as a filler material for NC production to be used for food packaging were overviewed by Bharimalla et al. (2017). The findings related to the application of the antimicrobial bio-NC of polylactic acid (PLA) and nanocellulose produced from agricultural waste in food packaging were summarized by Gan and Chow (2018). A critical review on agrowaste cellulose applications for biopolymers with an emphasis on CNC and CNF composites derived from waste biomass cellulose as well as bacterial nanocellulose and biodegradable polymer matrices (polylactide, polycaprolactone, and polyhydroxybutyrate) that could show biocompatibility and good thermomechanical properties and represent the best polymeric substitutes for various (petro)polymers was presented by Motaung and Linganiso (2018). A comparative review of the preparation methods of nanocrystalline cellulose from biomass and waste materials was presented by Mishra et al. (2019). Agricultural wastes such as RH (Arumugam et al., 2018; Salama et al., 2018; Sohrabnezhad and Mooshangaie, 2019; Wang et al., 2019; Ziksari and Pourahmad, 2016), RH ash (Afzaal and Farrukh, 2017; Vasamsetti et al., 2018), RS (Bhattacharya and Mandal, 2018), corn stalks (Kaya et al., 2018), and cottonseed hulls (Boonmahitthisud et al., 2017) are frequently used as raw materials to prepare SiO2 nanoparticles (NPs, see Fig. 4.4; ACS Material, 2019) that will be subsequently applied in NCs. By carbonization of the RH SiO2/carbon NC (Chu et al., 2018), microscale porous carbon (PC)/SiO2 composites (Cui et al., 2017) or SiO2/carbon hybrid NPs (Biswas et al., 2017) could be prepared. The application of RH as a pore-forming agent was described by Dele-Afolabi et al. (2018a,b). In metal NPs fabricated using plant extracts, the secondary material capping assigned to bioorganic compounds (e.g., phenolic compounds, terpenoids, or proteins) is bound to the surface of NPs. Also, compounds from plant extracts having the aldehyde and hydroxyl group as a functional group in the structure cause the reduction of metal ions and stabilization (Masarovicova´ et al., 2014; Sangeetha

4.1 Introduction

FIG. 4.4 Electron microscope image of silicon nanoparticles. Provided by ACS Material, 2019. Silicon Nanoparticles. Advanced Chemical Supplier Material, LLC, Pasadena, CA, USA. https://www.acsmaterial.com/silicon-nanoparticles.html.

et al., 2011). Aqueous peel extracts of grapefruit (Najafinejad et al., 2018), bottle gourds (Prasad et al., 2017), Citrus paradisi (Ayinde et al., 2018), Coccinia grandis (Devi and Ahmaruzzaman, 2017), Punica granatum (Adyani and Soleimani, 2019), lemon, black grapes, cucumbers (Stan et al., 2017), or bananas (Newase and Bankar, 2017) applied as reducing and stabilizing agents to fabricate metal NPs applied in various NCs were reported as well. Activated carbon (AC, see Fig. 4.5) used in composite adsorbents was prepared from RH biomass (Thennarasu et al., 2018), SCB (Sharma et al., 2019), the biomass of pomelo peels (Wu et al., 2016), cucumber peels (Mahmoodi et al., 2019), and Palmyra tuber peels (Natarajan et al., 2016) while biochar (see Fig. 4.6; BiocharProject, 2011) was fabricated from the BP (Kaushal et al., 2019), pomelo peel (Wang et al., 2018b), bamboo biomass (Huang et al., 2019), RS (Wang et al., 2018a; Zhou et al., 2019), corn straw (Yang et al., 2019), SCB, RS, peanut shells (Yi et al., 2019), and RH (Richard et al., 2017). PCs for NC were prepared from BP (Yang and Park, 2018), pomelo peel (Yuan et al., 2016a), WS (Fang et al., 2018a) discarded bagasse (Yuan et al., 2016b), and SCB (Madhu et al., 2016). Fang et al. (2019) and Liu et al. (2019a) reported the preparation of carbon fibers derived from cotton stalks and bagasse waste, respectively. It should be also noted that Paul et al. (2019) published a comprehensive review focused on the engineering properties of produced concrete using ash from agricultural wastes, for example, RH, bamboo leaf, SCB, etc. This chapter is focused on the application of various agricultural waste materials, such as wheat and rice straws, corn and cotton stalks, bamboo biomass, sugarcane bagasse, bananas, shaddock and various other peels, rice husks, and coirs, for the production of nanocellulose, starch, biochar, and activated coal, as well as nanoscale silicon/silica that are subsequently used for the fabrication of NMs and nanocomposites for technical and biomedical applications. The most frequently used methods for the preparation of NMs are briefly characterized as well.

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FIG. 4.5 Electron microscope image of activated carbon.

FIG. 4.6 Electron microscope image of biochar. Freely provided by BiocharProject, 2011. Spreading the Word About Biochar. http://biocharproject.org/ charmasters-log/biochar-electron-microscope-images.

4.2 Preparation methods of nanocomposites

4.2 Preparation methods of nanocomposites and their constituents from agricultural wastes The frequently used methods to fabricate NCs using agricultural waste such as hydrothermal carbonization, the sol-gel method, coprecipitation, polymer solution casting, the phase inversion technique, ball milling, and direct compounding (see Fig. 4.7) are briefly characterized below. NCs could also be prepared using in situ synthesis (Ucankus et al., 2018). Hydrothermal carbonization (Fang et al., 2018b; Heidenreich et al., 2016; Lucian and Fiori, 2017; Wang et al., 2018c) is a green route to fabricate carbonaceous aerogels that frequently uses waste biomass, which is an ideal carbon source utilizing also the inherent porous tissue structure of applied biomass. This method usually utilizes biomass heating in the presence of water in a pressure vessel at pressure ca. 1 MPa for approximately 12 h. After this time, the carbon of the reactants is completely reacted, and the majority of the carbon (90%–99%) occurs in the form of an aqueous sludge consisting of solid porous brown coal spheres with pore sizes ranging from 8 to 20 nm. The sol-gel process represents a change of inorganic colloidal suspension from a liquid state to a gel state through polycondensation reactions. While the sol is a stable dispersion of colloidal particles in a solvent, the gel consists of a three-dimensional (3D) continuous network of sol particles that encloses the liquid phase. This method enables fabricating multicomponent compounds with a controlled stoichiometry, and the particle size of synthesized NPs could be controlled by the concentration of reactants, temperature, mixing mode, the rate of hydrolysis, and the condensation reaction (Rao et al., 2017; Sajjadi, 2005; Soytas¸ et al., 2019). NPs could also be fabricated by coprecipitation, that is, simultaneous precipitation of more than one component. However, this method requires vigorous stirring,

Hydrothermal carbonization Phase inversion

Polymer solution casting

Ball milling

Solvent casting

Methods

Direct compounding

Sol-gel method Coprecipitation

FIG. 4.7 Applied methods of nanocomposite production using agricultural waste.

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and by the addition of a precipitating agent (e.g., NaOH) to the precursor solution, controlled particle size could be obtained. The three main mechanisms of coprecipitation are inclusion, occlusion, and adsorption (Kandpal et al., 2014; Vaculı´kova´ et al., 2012a,b, 2017). In the case of inclusion, an impurity with the ion radius and a charge similar to that of the carrier occupies a lattice site in the crystal structure of the carrier, causing a crystallographic defect. Adsorption occurs when the adsorbate (impurity) is weakly bound to the surface of the precipitate while an occlusion occurs when the adsorbed impurity gets physically trapped inside the crystal as it grows. In polymer solution casting, the polymer is dissolved or dispersed in solution, coated onto a carrier substrate, and, after removing the solvent by drying, a solid layer on the carrier is formed. A standalone film fabricated by stripping the cast layer from the carrier substrate could be laminated with other webs or coated with other materials, resulting in multilayer products. Using this method, high-quality films with superior optical, mechanical, and physical film properties could be prepared (M€ uller et al., 2017; Tavares et al., 2017; Yan et al., 2019). Phase inversion techniques (Gao and McClements, 2016; Guillen et al., 2011) are frequently applied for the synthesis of polymer membranes. In this method, the polymer is transformed from the liquid phase of the cast polymer solution to the solid phase, a swollen 3D macromolecular complex, or gel. Ball milling is a traditional powder processing technique that allows reducing  ´kova´ particle sizes and could also be used for mixing different materials (Cernı et al., 2015; Petrovic et al., 2018). In the indirect compounding method, NMs and polymers (Hussain and Mishra, 2018) are synthesized before blending; however, the aggregation of NPs is not desirable. It could have been avoided (i) by surface modification of NPs or the polymer; (ii) by optimization of synthesis parameters (e.g., temperature, shear force, mixing speed); or (iii) by the addition of dispersants or compatibilizers. There are several direct compounding techniques such as solvent casting, melt blending, template synthesis, electrospinning, and self-assembly. Solvent casting (Schruben and Gonzalez, 2000; Siemann, 2005) is based on a solution system in which the solvent can solve the polymer and disperse the NM. The improved mobility of the polymer chains mediated by the solvent results in the intercalation of the polymer in NM layers or sheets. The method can be used for water-soluble polymers; however, the need for large amounts of organic solvents is considered to be a disadvantage of this method. In the melt blending method ( Jong, 2011, 2012; Schut, 2009), no solvent is required and polymers and NMs are mixed in the melt under shear (extrusion or injection molding) and intensive mixing. This results in the thermal motion of polymer chains and the formation of the molten mass into NM layers, whereby either intercalated or delaminated/exfoliated polymer NCs are created. This method could be used to prepare NMs from thermoplastic polymers and polymers that are not suitable for in situ polymerization or solvent casting. Although the absence of a toxic solvent belongs to the advantages of this method, high temperatures could damage NMs.

4.3 Individual agricultural wastes

In template synthesis (Huczko, 2000; Liu et al., 2013; Wade and Wegrowe, 2005), the pores of a host material are used as a template to direct the growth of new materials. The polymer is a nucleating agent that provides the growth of crystals of inorganic filler. After the growth of crystals, the polymer intercalates between the NM, and a polymer composite is formed. Electrospinning (Bhardwaj and Kundu, 2010; Haider et al., 2018; Leach et al., 2011) is a method suitable for the production of nanofibers. In this method, the electrically charged jet of a composite solution in the needle is obtained using high voltage, and the charged jet is then ejected from the tip of the needle. After ejection, the solvent is evaporated, which results in nanofiber formation on the collector. Self-assembly is a process in which components organize themselves into desired shapes and functions (Boal et al., 2000; Genixa and Oberdisse, 2018; Grzelczak et al., 2010). In in situ synthesis, precursors of polymer NCs (metal ions for NMs or monomers for polymer) are combined, and the formation of NMs or the polymerization of monomers occurs (Adnan et al., 2018; Guo et al., 2014; Mittal, 2011).

4.3 Individual agricultural wastes used for fabrication of a wide variety of nanocomposites 4.3.1 Straws Straw obtained by harvesting cereals is an agricultural byproduct composed of the dry stalks of cereal plants after the grain and chaff have been removed. It acts as both fodder for animals and a building material. Moreover, it is a valuable source to fabricate various NCs. Composites of PLA and dopamine-treated or 12-aminododecanoic acid-modified montmorillonite (MMT) WS fibers used as fillers showed improved thermal stability and mechanical properties resulting in a 367% increase of the tensile strength compared to the unmodified precursors. Moreover, the interlayer spacing of the two-step modified MMT was 123% higher than that of the unmodified MMT (Fan et al., 2018). Composites of PLA with microcrystalline cellulose prepared by acidic (H2SO4) hydrolysis of WS and used to reinforce the polymer matrix were fabricated by melt blending to improve the brittleness of PLA. These showed increased tensile modulus and strength up to 262 and 73.01 MPa, respectively (Xian et al., 2018). BioNCs based on thermoplastic benzylated WS and nanoclay prepared via solvent casting were prepared by Jafari et al. (2018). Nanoclay improved all mechanical properties except the elongation at the break. A bioNC containing 5% nanoclay resulted in an increase in crystallization, retardation of the thermal decomposition process, minimum water absorption, and the highest hydrophobicity compared to other tested samples. According to researchers, this bioNC can be considered an alternative to oil-based plastics in biomembranes and bioseparation processes. Using in situ hydrothermal synthesis water stable NPs of metal-organic framework UiO-66 made up of [Zr6O4(OH)4] clusters with 1,4-benzodicarboxylic acid struts immobilized within

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positively charged WS were prepared. They expressed high selectivity and preference to phosphate and could be used as adsorbent for effective phosphate removal from water to prevent eutrophication and water bloom (Qiu et al., 2019). Nanofibrillated cellulose/polyvinylpyrrolidone/AgNP films showing good flexibility and tensile strength properties as well as electrical conductivity properties were reported as antistatic and electrostatic dissipative materials that can be applied for sensitive electronic component packing (Khalil et al., 2017). WS cellulose-based hydrogels were fabricated by polymerization from solution and then used as a template for the in situ preparation of Ni and CuNPs, which were tested as catalysts in H2 formation from the hydrolysis of NaBH4. This showed that these composite hydrogels could be used up to fivefold with 100% conversion and 77.5% and 70% activity, respectively. After 30-day storage, the hydrogel-Ni and hydrogel-Cu composites preserved 70% and 65% activity, respectively (Ding et al., 2018). WS-derived PC, which was subsequently decorated with an Fe2O3 ultrathin film, exhibited high performances for supercapacitors, reflected in specific capacitance up to 987.9 F/g (219.5 mAh/g) at a current density of 1 A/g, a capability rate of 423.8 F/g at 30 A/g, and superior cyclability (82.6% capacitance retention after 3000 cycles). An aqueous asymmetric supercapacitor having this NC as the anode material delivered a high specific energy of 96.7 Wh/kg and a high specific power of 20.65 kW/kg (Fang et al., 2018a). A 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized straw cellulose-doped yttrium oxide NC obtained via a hydrothermal method showed good antibacterial effectivity against Escherichia coli and Staphylococcus aureus. This activity could be improved by visible light, suggesting that this NC could be successfully used for cleaning microbial contamination (Zhang et al., 2017b). By immobilizing the "rod-like" nano-sized La(III) (hydr) oxides within a quaternary-aminated WS, an NC was fabricated that was characterized with superb sequestration of phosphate in the pH range from 3.0 to 7.0 without significant La(III) leaching. It showed excellent stability without considerable capacity loss in 10 cycles of adsorption-desorption experiments. The specific adsorption of phosphate by nano-La(III) (hydr)oxides was connected predominantly with the formation of "needle-like" lanthanum phosphate NPs (Qiu et al., 2017). An amphoteric adsorbent derived from WS pretreated with alkali and acid hydrolysis (to remove lignin and hemicellulose) and modified with monochloroacetic acid and a graft polymerization cationic monomer of 2-(dimethylamino)ethyl methacrylate showed maximum adsorption capacities of anionic dye orange II up to 506 mg/g at pH 2. In the cationic/anionic dyes, binary systems exhibited significantly enhanced adsorption properties toward anionic dyes at the acid condition while the opposite behavior was observed at the alkaline condition (Lin et al., 2017). Hybrid CNFs/chitin nanowhiskers (CNW) were fabricated via casting and evaporation from CNFs and CNWs prepared from chitin and WS subjected to TEMPO-oxidation and acid hydrolysis prior to high-pressure homogenization. They showed improved mechanical properties due to multivalent physical interactions between CNFs and CNWs as well as high transparency and excellent flexibility (Feng et al., 2018a). The melt mixing method was used to fabricate

4.3 Individual agricultural wastes

bioNCs of D,L-lactide-D-valerolactone-D,L-lactide and nanowhiskers with a width in the range of 80–300 nm prepared from jute by the controlled acid hydrolysis method; they were uniformly dispersed in the triblock matrix. Reinforcing with 8 wt% nanowhiskers caused an increase in the tensile strength and modulus by 130% and 50%, respectively (Kasyapi et al., 2018). A composite corn distarch phosphate-based film with incorporated modified microcrystalline corn straw cellulose (MMCSC) prepared by ultrasonic/microwave-assisted treatment showed improved properties. Composite films containing 20% MMCSC exhibited water vapor permeability of 2.917  107 g/m h Pa, suggesting their potential use in food packaging (Shao et al., 2018). The addition of 15% superfine corn straw particles prepared by 0.5–1.5 h ball milling incorporated into the starch-based films pronouncedly improved the mechanical properties of the films (Wu et al., 2018). Iron oxide/carbon NC from maize straw administered to different groups of poultry birds along with aflatoxin B1 at a dose of 0.3%/kg feed was found to be very effective in detoxifying aflatoxin B1 in the gastrointestinal tract of poultry birds with no harmful effects (Zafar et al., 2017). Yang et al. (2019) prepared thornlike iron-based biochar composites by the combination of an electrochemical modification with one-step pyrolysis of FeCl3-pretreated corn straw-derived biochar, in which the rod-like crystalline Fe3O4 NPs were uniformly dispersed in the inner and outer structure of the biochar. The composite adsorbent showed a Pb adsorption capacity of 113 mg/g and could be used for high-performance wastewater treatment. Using silica xerogel fabricated from corn stalk ash in ambient pressure drying by the sol-gel method, which was dispersed in epoxy resin, silica xerogel/epoxy NCs were fabricated that exhibited enhanced thermal and acoustic insulation performance and slightly higher water sorption than the neat epoxy resin (Kaya et al., 2018). A cornstalk fiber grafted poly(dimethylaminoethyl methacrylate) (PDMAEMA) adsorbent was prepared by atom transfer radical polymerization using poly(vinyl alcohol) (PVA) to enrich the OH groups of the fibers, resulting in increasing PDMAEMA grafting density. It reached an adsorption capacity for Cr(VI) of 145 mg/g and achieved adsorption equilibrium in approximately 10 min (Wen et al., 2018). By the incorporation of urea into a polymer matrix composed of a corncob-g-poly (acrylic acid)/bentonite network and linear polyvinylpyrrolidone, Wen et al. (2017) fabricated a slow-release NC via microwave irradiation at 320 W for 4.5 min. This showed the high performance of controlling water and nitrogen losses and its ability to reduce the nitrogen release rate contributed to the improved growth of cotton plants. Films of hydroxypropyl cellulose/RS oxidized CNC (OXCNC) NCs prepared via casting and evaporation, which contained 10% OXCNC and were used for coating paper sheets, increased the tensile strength properties and water vapor permeability while decreasing the porosity of the paper sheets (El-Wakil et al., 2016). Films fabricated by solution casting from hydroxypropyl methylcellulose, nisin, and TEMPOoxidized nanofibrillated cellulose (NFC; 5%–75%) isolated from RS pulp showed not only improved thermomechanical, mechanical, and moisture barrier properties than films without NFC, but also exhibited considerable antimicrobial activities

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against S. aureus with the controlled release of nisin (Hassan et al., 2018). Comparisons of PVA composite films reinforced by CNFs prepared from steam-exploded RS fibers or RS cellulose microfibers (CMFs) showed that composite films containing CNFs had better mechanical properties and transparency and comparable thermal stability. However, they had weaker water resistance than composites containing CMFs, which can cause more polar groups in CNFs (Wang et al., 2018a). Biocomposites of chitosan (CS) and RS-derived nanocrystalline cellulose (width in the range of 10–15 nm and length of several hundred nm) fabricated by an acid hydrolysisultrasonic treatment and blending casting showed superb interfacial compatibility and tensile strength at a nanocrystalline cellulose concentration of 5%, securing its superlative optimal dispersion as well as strong H-bonds and electrostatic interactions between CS and nanocrystalline cellulose (Xu et al., 2018). Films based on PVA/CS NC, reinforced with rod-like shaped CNC isolated from RS by acid hydrolysis with a particle size of about 15 nm in diameter, improved the tensile strength (98.15 MPa) and thermal stability of the films. The films showed good antifungal and antibacterial activity, suggesting their use in food-packaging applications (Perumal et al., 2018b). NC films, in which CNCs isolated by acidic (H2SO4) hydrolysis from RSs pretreated with NaOH, NaClO2, and CH3COOH were used as fillers in an MMT clay-PVA matrix, showed pronounced improvement of thermal stability and tensile properties by increasing the CNC concentration up to 6 wt%. They were also found to extend the shelf life of freshly harvested mangoes by 19 2 days (Perumal et al., 2018a). SiO2 NPs extracted from RS as fillers were used to fabricate NC polymeric membranes containing a polyether-polyamide block copolymer to improve the efficiency of CO2 separation from its streams, whereby the composite membranes were prepared by solution casting. At an SiO2 concentration of 5 wt% in the membrane, the permeability of CO2 reached 270.0 Barr and the permeability trend for pure gases for both pressure (3–7 kg/cm2) and temperature (30–50°C) variation decreased as follows: CO2 > air > CH4 (Bhattacharya and Mandal, 2018). The coprecipitation method was used to fabricate NCs of charcoal prepared by the thermal decomposition of RS with MgO; these showed a high adsorption efficiency for the removal of reactive Dye Blue 221 from synthetic textile wastewater (Moazzam et al., 2017). RS biochars were produced at 300°C, 500°C, and 700°C, and were treated with 0.5 M HCl. They exhibited superb Cr sorption capacity with >90% of the total Cr removed at pH 2, whereby Cr(VI) adsorption mechanisms involved Cr (VI) reduction (Cr(III) being the dominant species adsorbed to the biochars) and anionic adsorption (Zhou et al., 2019). The adsorption of Pb(II), Cu(II), and Zn (II) by hydroxyapatite-biochar NC fabricated from RS by slow pyrolysis and subsequently treated with CaCl2 and (NH4)2HPO4 solutions, which was investigated in single and ternary metal systems, was affected by pH in both the single and ternary metal ion systems. The adsorption isotherm of Pb(II) fitted with the Langmuir model while those of Cu(II) and Zn(II) fitted with the Freundlich model. The maximum adsorption capacity of the NC exceeded that of pristine RS biochar (especially for Pb(II)) (Wang et al., 2018d). Fathy et al. (2019) reported the fabrication of graphene

4.3 Individual agricultural wastes

oxide (GO) sheets using simple hydrazine-free methods based on RS, using the catalytic acid spray method in the presence of CoSiO3 NPs as a catalyst. This showed to some extent higher interlayer spacing compared to GO produced by other processes. By adjusting the fabrication parameters such as acid strength or catalytic doses, the weak interbond between the GO sheets could be overcome without cracking them. The space-confined and self-absorptive synthetic strategies were applied to fabricate composites of amorphous SnO2 NPs anchored in the WS carbon substrate, which could be used as an anode to lithium-ion batteries. These composites showed an initial capacity of 517.6 mAh/g and a capacity ratio of 53% in the potential range 0–1.0 V to that of 0–3.0 V at 0.05 C (80 mA/g) after 100 cycles. The improved electrochemical performance and stability of this anode material compared with pure SnO2 and graphene (GR)-coated SnO2 prepared by a spray drying and calcining process could be caused by the space-confined structure of WS providing a robust connection between the amorphous SnO2 and the carbon substrate (Kong et al., 2018). In a polyvinyl chloride (PVC)/RS/GO sustainable NC prepared using the direct compounding method, the noncovalent and physical interactions between the cellulose/hemicellulose portions of the RS fibers and GO functional groups resulted in the increase of mechanical characteristics. The presence of 1 wt% GO nanosheets in the NC was able to enhance the mechanical strength of PVC up to 9%, suggesting that they act as compatibilizers suppressing the incompatibility between PVC and RS fibers (Bagherinia et al., 2017). A critical analysis and comparison of biomass-derived nanostructured carbons and their composites as anode materials for lithium-ion batteries were presented by Long et al. (2017). The soy protein isolate films containing mercerized soybean straw and nanocellulose produced by acid (10 nm thick and 300 nm long NPs with a crystallinity index of 57%) or enzymatic hydrolysis (10 nm thick and >1 mm long with a crystallinity index of 50%) as reinforcing fillers showed improved film tensile strength by 38% and 48%, respectively, and decreased prolongation at the break compared with control films when a nanocellulose content of 5 wt% was applied (Martelli-Tosi et al., 2018). Biochar prepared using bamboo biomass modified with an Mg/Al-layered double hydroxide (LDH) intercalated with ethylenediaminetetraacetic acid (EDTA) by calcination showed a maximum adsorption capacity of Cr(VI) at 38 mg/g; it could be used for removing heavy metals in wastewater (Huang et al., 2019). Carbon fibers (CFs) derived from cotton stalks introduced into Ni-Al LDH nanosheets as the conducive matrix prevented their aggregation and enhanced the electrical conductivity of the NC, resulting in a specific capacitance of 1214.9 F/g at 1 A/g, a rate capability of 917.0 F/g at 10 A/g, and good cyclability of 528 F/g after 1000 cycles at 20 A/g. An aqueous asymmetric supercapacitor having this NC as the cathode material could deliver specific energy of 20.1 Wh/kg at 932 W/kg (Fang et al., 2019). The carbon nanotube (CNT)/TiO2 NC, in which cotton stalk waste was used as a carbonaceous precursor for CNT preparation, was prepared by the sol-gel method of titanium isopropoxide in the presence of CNTs and subsequently by calcination at 500°C for 180 min under flowing N2 gas. This TiO2@CNT NC was

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then wrapped by AgNPs in the presence of 4-[(4-aminobenzoyl)amino]-1decylpyridinium bromide. The resulting TiO2@CNTs/AgNPs/C10 NC exhibited good dispersion of AgNPs by the surfactant and excellent degradation of methylene blue (MB) dye under visible light irradiation as well as high stability connected with a large surface area of 146 m2/g (Azzam et al., 2019).

4.3.2 Peels and shells A peel is the outer protective layer of a fruit or vegetable that can be peeled off. A shell, the outer covering of fruits with hard walls such as hazelnuts, chestnuts, or coconuts, is inedible and may be removed before eating the nut meat inside. Magnetite (Fe3O4) NPs prepared using agro-waste extracts such as peel extracts of lemon, black grapes, and cucumbers as reducing and stabilizing agents were investigated for the removal of a mixture of seven antibiotics from aqueous media. They showed >90% removal of the studied antibiotics, except sulfamethoxazole and trimethoprim, and were more effective than Fe3O4 NPs fabricated by conventional methods (Stan et al., 2017). The green synthesis of metal NPs using banana peel extracts (Bankar et al., 2010), Citrus sinensis (Kaviya et al., 2011), Momordica charantia (Pandey et al., 2012), or Annona squamosa (Kumar et al., 2012) was previously reported. NCs of a Cr-based metal-organic framework (MIL-101(Cr)) with different amounts of cucumber peel-derived AC (2, 5 and 10 wt%), in which the composite materials demonstrated the same morphology as MIL-101(Cr) octahedral crystals on an AC bed, were fabricated by Mahmoodi et al. (2019). A composite of 5% of MIL-101(Cr) reached more than twofold BET surface area compared to AC (2412.1 versus 1096.83 m2/g, respectively). Its investigation for removing Acid Green 25 and Reactive Yellow 186 dyes from the binary systems showed that the adsorption capacity changed less than 9% after five cycles. Biosynthesized Pd-supported Fe3O4 magnetic NPs prepared using the aqueous peel extract of bottle gourds (calabash) acting as the reducing and capping agents showed a face-centered cubic structure with a uniform size of 50 nm and a high surface area (27.6 m2/g). They exhibited increased magnetic properties of saturation magnetization and were found to effectively catalyze the reduction of MB dye (Prasad et al., 2017). A composite fabricated of AgNPs green synthesized using C. grandis (ivy gourd) peel extract and AC prepared from sawdust showed better catalytic activity in the degradation of Naphthol Green B dye (97% degradation within 1 h) than pure AgNPs; the photodegradation process was more effective for the removal of this dye than adsorption (Devi and Ahmaruzzaman, 2017). Nanocellulose-prepared green gram husk cellulose that was reinforced in unsaturated polyester with 5 wt% showed a peak tensile strength of 39 MPa. Nanocellulose reinforced in banana fiber hybrid composites were characterized by enhanced tensile strength, flexural strength, and impact strength (Movva and Kommineni, 2019). Khawas and Deka (2016) described the isolation and characterization of CNFs from culinary BP using high-intensity ultrasonication combined with chemical

4.3 Individual agricultural wastes

treatment. By increasing the output power of ultrasonication ranging from 0 to 1000 W, a reduced-size CNF with a thinner and needle-like structure was generated. It showed enhanced thermal properties, suggesting that CNFs could be applied as useful reinforcing material in bioNCs. The casting method was used to prepare banana starch-based NC films with cellulose nanofibers, which were isolated from BP (Musa paradisiaca) by enzymatic hydrolysis. The film structure was modified by the incorporation of CNFs. Strong interactions between the starch matrix and CNFs caused considerable improvement of the water barrier, the mechanical properties, the UV light barrier, and the opacity in comparison with the control film, suggesting the potential of such films to be used in food packaging (Tibolla et al., 2019). Cellulose nanofibers isolated from BP by chemical (alkaline treatment and bleaching followed by acid hydrolysis with 0.1%, 1%, or 10% (v/v) H2SO4) and mechanical (high-pressure homogenizer) treatments showed a main diameter of 3.72 nm and zeta potential values in the range from 37.60 to 67.37 mV, which were characterized by high crystallinity values (63.1%–66.4%). They were reported as suitable reinforcing agents of polymeric matrices used in food packaging (Tibolla et al., 2018). Optimized NCs were fabricated from a mixture of banana starch and CNFs isolated from BP combining chemical and mechanical treatments with five passages through the high-pressure homogenizer. The nanofibers prepared using the casting method, pronouncedly enhanced the properties of the starch-based material such as tensile strength, Young’s modulus, water-resistance, opacity, and crystallinity. Such NCs could be applicable as reinforcing elements (Pelissari et al., 2017). CS/BP powder NCs for wound-dressing applications were prepared by the incorporation of dried peels ground to powder and applied as nanofillers within the CS matrix with the subsequent addition of glycerol as the plasticizer and cross-linker to the membranes. They were characterized with a decreased swelling degree of the CS matrix and the membranes containing 10 wt% BP powder showed the highest synergistic activity against Gram-positive and Gram-negative bacteria as well as yeast (Kamel et al., 2017). Ag-Au NCs biosynthesized using BP extract powder showed the highest inhibition of Pseudomonas aeruginosa biofilm when compared with individual AuNPs and AgNPs. This synergistic activity against antibacterial biofilm formation could be used in the development of novel therapeutics against multidrug-resistant bacterial biofilms (Newase and Bankar, 2017). The modification of an electrode with a multifunction composite of AgNPs prepared using Azadirachta indica leaf extract embedded in biochar fabricated from the BP via pyrolysis resulted in superb cyclic stability of 79% after 5000 charge/discharge cycles. It also showed high energy and power density of 40 Wh/kg and 490 W/kg, respectively, at 1 A/g. Moreover, with ultrasonic-assisted adsorption of Congo Red dye, this composite exhibited approximately 98% adsorption within 5 min of contact time (Kaushal et al., 2019). In composites of MnO2/BP-derived porous carbon (BPC) prepared by a hydrothermal method, the BP maintained after freeze-drying its hierarchical natural porous structure, providing sufficient growth space for MnO2 and reducing the agglomeration of MnO2 particles. The MnO2/BPC composites with considerable amounts of hierarchical pores and large pore volume applied in supercapacitors showed a specific

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capacitance of 139.6 F/g at 300 mA/g as well as a good cycling stability with a capacitance retention ratio of 92% after 1000 cycles (at 1 A/g) (Yang and Park, 2018) By annealing the Ni(NO3)2 solution-treated activated BP with orderly arranged nanopores, Ni/GR core/shell NPs were formed and mild hydrothermal treatment resulted in the uniform anchoring of urchin-like NiCo2O4 nanowires on the surface of hierarchically porous AC scaffolds fabricated from activated BP. Assembling activated BP (as the negative electrode) and NiCo2O4/activated BP (as the positive electrode) resulted in a high-performance asymmetric supercapacitor with excellent specific capacitance, high power density, and competitive cycling robustness; the NiCo2O4/activated BP hybrid electrode showed a threefold higher specific capacitance than the activated BP electrode (Zhang et al., 2016). Shaddock peels used as biotemplates for Pd-functionalized one-dimensional (1D) SnO2 nanostructures prepared using a hydrothermal method resulted in a 1D fiberlike morphology exhibiting superb gas-sensing performances toward butane. This was attributed to the 1D morphology while the large internal surface area of sensing materials provided more active sites for the reaction between butane molecules and adsorbed oxygen ions. NCs of SnO2 functionalized with 5 mol% Pd showed detection limits of 10 ppm with responses of 1.38 0.26. The sensor exhibited rapid response/recovery times (3.20/6.28 s) at 3000 ppm butane, good repeatability, and long-term stability (Zhao et al., 2019). Zr and La hydroxide/cellulose-based biocomposites, in which shaddock peels (SP) were used as biohosts to support the bimetallic oxides while zirconium and lanthanum hydroxides were used for selective phosphate removal, showed more available interface interactions toward the adsorbed ions due to some rod-like or amorphous NPs (20–150 nm) anchored inside the SP. These SP-Zr-La NCs were pH-sensitive and their adsorption capacity for phosphate increased with increasing temperature and showed improved stability due to the "shielding effect" in a low humic acid surrounding exhibited by the biocarrier. The increase in the molar ratio of the accompanying ions/phosphate from 0- to 10-fold resulted in only 27.2%–36.7% adsorption loss of the SP-Zr-La NC compared to an 86.2%–91.6% loss observed with cationic SP (grafted with quarterly ammonium groups) (Du et al., 2019). From the immersion of dried SPs into a mixture of Co(NO3)2/GO for approximately 12 h and the following heating at 800°C for 2 h under an N2 atmosphere, a GR-Co/CoO SP-derived carbon foam (SPDCF) hybrid was fabricated. The carbonized shaddock peel was characterized by a hierarchical porous nanoflake structure, GR was uniformly dispersed into the carbon foam, and Co/CoO NPs were formed on the GR-SPDCF. This hybrid prepared as the anode material for lithium-ion batteries could maintain a capacity of 600 mAh/g at 0.2 A/g after 80 cycles, considerably exceeding that of graphite (372 mAh/g). The improved performance of the nanohybrid could be connected with the existence of lots of uniform Co/CoO NPs and the hierarchical structure of GR-SPDCF contributing to alleviating the mechanical stress during lithiation/delithiation (Zhou et al., 2018). Papaya peel powder microparticles (MPs) produced by spray drying with gelatin originating from nutraceutical capsule waste biodegradable films with antioxidant properties and increased tensile strength and Young’s modulus were prepared with

4.3 Individual agricultural wastes

the potential to be applied as packaging for food products with high-fat content susceptible to oxidation. The films containing 7.5% MPs were found to exhibit the most efficient active barriers reflected in higher antioxidant activity (Crizel et al., 2018). Fish gelatin films with incorporated mango peel extract (1%–5%) showed a decrease in water vapor permeability and lower film solubility, whereby films with higher peel concentrations showed improved free radical scavenging activity but higher rigidity and lower flexibility (Adilah et al., 2018). In addition, starch-based NC films consisting of starch nanocrystals (SNC) from mango seed kernels, and CNC from mango seed shells used at an optimal ratio of 5 wt% CNC and 8.5 wt% SNC on a starch basis exhibited enhanced strength, modulus, and barrier to water vapor compared to the unfilled film, although the elongation has been impaired. The needle-like CNC showed a higher water vapor barrier effect and improvement of elastic modulus than SNC exhibiting round-like rather than platelet-like morphology, which impaired more elongation (Silva et al., 2019). Using pectin derived from jackfruit (Artocarpus heterophyllus) peels, pectin/apatite bioNCs showing good biocompatibility were prepared, and could be applied as bone graft materials (Govindaraj et al., 2018). Using the impure MMT and extract of pomegranate fruit waste, a new green fungicide was synthesized via a low-cost intercalation technique in which the plant extracts were intercalated between interlayers of MMT NPs. The NC showed higher loading yields of up to 70% and exhibited by 102% higher antifungal activity against Botrytis cinerea than single MMT NPs (Balooch et al., 2018). Composites of nanoscale zero-valent iron supported by carbonized pomegranate peel fabricated by liquid-phase chemical reduction and investigated as adsorbents of malachite green (MG) achieved a 99.7% dye adsorption for the adsorbent dose of 0.15 g in 30 min of equilibration time with a maximum adsorption capacity of 32.47 mg/g. This suggests that it could be used instead of AC for dye removal in industrial wastes (Gunduz and Bayrak, 2018). The pulsed plasma in the liquid technique was applied to synthesize zero-valent iron nanostructures using a commercial DC power source to produce such plasma on water and methanol resulting in 80% and 97% particles, respectively, composed of metallic iron. The orange skin impregnated with these nanostructures effectively removed Cr(VI) from the water solution, with the nanostructures formed in water being slightly more effective (Olea-Mejia et al., 2017). Composites of TiO2-CeO2 NPs (approximately 57 nm) supported on carbon, purchased using the pyrolysis of orange peel, that showed a specific surface area of 296 m2/g were able to degrade 40% of phenol after 240 min of UV irradiation (Lara-Lopez et al., 2017). As an excellent catalyst for Suzuki-Miyaura and Sonogashira cross-coupling reactions, Pd NP-decorated magnetic pomegranate peel-derived PC (Fe3O4@PC) NC was reported. According to the coprecipitation method of iron ions, Fe3O4 NPs decorated on PC were fabricated and magnetically separable Fe3O4@PC was then decorated with PdNPs by reducing H2PdCl4 in the presence of sodium dodecylsulfate used as both the surfactant and reducing agent (Pourjavadi and Habibi, 2018).

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Ultrasonically modified bilayered Ag-MgO NCs with a diameter of approximately 20–100 nm (comprising AgNP embedded within MgO NPs) prepared via aqueous peel extract of C. paradisi (grapefruit red) under an accelerated uniform heating technique exhibited stronger antibacterial activity against E. coli than MgO NPs and could be used in water purification (Ayinde et al., 2018). An Fe3O4@polythiophen-Ag magnetic nanocatalyst was fabricated by coating the magnetic particles with the branched polythiophene and using grapefruit peel extract to reduce AgNO3, whereby the Ag nanocatalyst was precipitated on the polymer surface. The degradation of azo dyes such as methyl orange (MO) and MB by this nanocatalyst was performed in 1 min and the nanocatalyst can be restored by a magnet after each experiment and reused eightfold without substantial loss of activity (Najafinejad et al., 2018). A 3D porous AC prepared with pyrolysis, precarbonization, and alkali activation of the biomass of pomelo peels characterized with numerous micro/meso/macropores and large specific surface area (1665 m2/g) enabled the incorporation of CNTs and reduced graphene oxide (rGO). The hybrid carbon film containing 80 wt% of AC/rGO/CNT exhibited a capacitance of 214 F/g at 1 A/g, a good rate capability, and superb mechanical properties (Wu et al., 2016). Polypyrrole-modified biochar derived from the slow pyrolysis of pomelo peel exhibited mainly anion-exchange behavior reflected in notably increased fluoride adsorption with a maximum adsorption capacity 18.52 mg/g at 25°C. The adsorption equilibrium was reached at 24 h, whereby as the main adsorption mechanism, ion exchange was estimated (Wang et al., 2018b). Prussian blue/natural porous framework NCs were prepared in aqueous solution under in situ gamma radiation using apple, corn stalk, and pomelo peel and having a layered porous structure with 70–100 nm irregular Prussian blue, a regular polygonous porous structure with 50–70 nm cubic Prussian blue, and a hierarchical porous structure with 10–20 nm spherical Prussian blue, respectively. These exhibited maximal radioactive Cs+ adsorption capacities of 67.3, 62.1, and 83.8 mg/g, suggesting their potential to be used in the treatment of radioactive wastewater (Chang et al., 2018). Carbon-based Fe3O4 NCs prepared by a one-step hydrothermal method using waste pomelo peels as the carbon precursors were reported as superb and recyclable adsorbents for magnetic solid phase extraction of 11 triazole fungicides in fruit samples, showing the limits of detection and quantification in the range of 1–100, 0.12–0.55, and 0.39–1.85 μg/kg (Ren et al., 2018). Using a one-step carbon thermal-reduction method, Ma et al. (2016) fabricated iron carbide/tungsten carbide/graphitic carbon (Fe3C/WC/GC) NCs, a porous structure that consisted of Fe3C NP-encased graphitic carbon layers with highly dispersed nanoscale WC. In these NCs, waste biomass such as pomelo peel was utilized as a carbon source, the Fe3C served as the active site for oxygen reduction reaction, and the graphitic layers and WC NPs stabilized the Fe3C surface, preventing it from dissociation in the electrolyte. The Fe3C/WC/GC NCs could be considered efficient electrocatalysts for oxygen reduction (Ma et al., 2016). By a simple immersing method, large numbers of Ni2+ ions were loaded on supporting material consisting of pomelo peel while

4.3 Individual agricultural wastes

GR foam-like 3D PC/NiNPs NCs were prepared by carbonization of the formed pomelo peel/Ni2+. These NCs with superb catalytic activity and good electrical conductivity showed excellent electrochemical performance toward the oxidation of glucose and could be used as glucose electrochemical sensors exhibiting a wide linear range (15.84–6.48 mM) and a low detection limit (4.8 mM) (Wang et al., 2017). An effective metal-free electrocatalyst for the oxygen reduction reaction as well as a nitrogen-doped nano-PC derived from waste pomelo peel were reported (Yuan et al., 2016a). Through in situ loading of the CoNiAl-layered double hydroxide on the surface of a 3D sponge-like carbonaceous aerogel (CA) with hierarchical pores and superb mechanical flexibility fabricated from pomelo peels using the hydrothermal method, NCs with a core-shell structure (CoNiAl-LDH@CA) were prepared after applying a second hydrothermal treatment. These NCs can be applied as electrode materials for supercapacitors (specific capacitances of 1134 F/g at 1 A/g and 902 F/g at 10 A/g, respectively, without a capacitance decrease after 4000 cycles) (Zhang et al., 2017c). In biocomposites of carboxymethyl chitosan (CMCS) and CMC from pineapple produced using ferulic acid plant extract as the cross-linker showing particle sizes of approximately 626 nm, the cross-linking occurs at the amine group of CMCS and carboxyl group of ferulic acid and the hydrogen bonding between the hydroxyl group of CMC and carboxyl group of ferulic acid. This system could be used as a matrix delivery system for hydrophilic sunscreen agents such as TiO2 and phenylbenzimidazole sulfonic acid (Wongkom and Jimtaisong, 2017). By the introduction of carclazyte (felspar retaining some alkali) in a pineapple peel CMC-g-poly(acrylic acid-co-acrylamide) hydrogel, an NC showing a superabsorbent property with improved the swelling capacity in various solutions and salt- and pH-sensitivity as well as remarkable sensitivities to various surfactant solutions; simulated physiological fluids were prepared (Dai and Huang, 2017). Using CMC isolated from pineapple peel, PVA/CMC hydrogels reinforced with GO and bentonite were fabricated as excellent adsorbents of MB with the maximum adsorption capacity calculated from the Langmuir isotherm model of 172.14 mg/g at 30°C, exceeding that of hydrogels without GO and bentonite additives (83.33 mg/g). GO and bentonite addition to hydrogels also resulted in the enhanced thermal stability and swelling ability of hydrogels (Dai et al., 2018). Using the peel extract of P. granatum as a reducing and stabilizing agent, magnetically separable Ag/Fe3O4/rGO NCs of a crystalline nature were prepared, showing efficient and high catalytic activity for 4-nitrophenol, MB, MO, and methyl green (MG) within a few seconds (Adyani and Soleimani, 2019). A bimetallic NC of facecentered cubic NiO/MgO pseudocapacitors prepared via the polyphenols of P. granatum peel extracts was reported as an efficient photocatalyst for the degradation of organic dyes under artificial light irradiation, causing 87% and 73% degradation of MB and MO, respectively, within 10 min of exposure (Fuku et al., 2018). AC/anatase TiO2 nanotube (AC/ATNT) composites consisting of Palmyra tuber (Palmyra sprout) peel-derived AC-loaded anatase TiO2 nanotubes prepared by the alkali

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hydrothermal method using anatase TiO2 NPs showed tubular morphology and enhanced surface area and exhibited enhanced adsorption and photocatalytic rhodamine 6G degradation exceeding that of pristine ATNT. This was connected with the decrease in the photo-produced charge carrier recombination (Natarajan et al., 2016). The rGO@AuNCs were prepared by mixing the solution of GO fabricated by the oxidation of natural graphite powder according to an optimized Hummers method with HAuCl4. The mixture was then moved to a heating bath of 80°C, peanut peel extract was added, the solution was centrifuged, and the formed NC was lyophilized. In the presence of rGO@AuNCs showing crystalline behavior, the catalytic degradation of MB and MG in dark conditions (no sun or UV radiation) reached approximately 93% and rGO@AuNCs also showed good catalytic performance at reducing the 4-nitrophenol to 4-aminophenol in the presence of NaBH4 (Patil et al., 2018b). Magnetic biochar fabricated from wastes such as SCB, RS, peanut shells, herb residue, and steel pickling waste liquor serving as iron salt was investigated for the removal of Cr(VI). In these magnetic composites, the Cr(VI) was electrostatically attracted to the surface of the materials, whereby most of the adsorbed Cr(VI) was reduced (the dominant role in the reduction of Cr(VI) played Fe(II) contained in biochar), and the rest of the Cr(VI) was complexed with carbonyl groups in magnetic biochar. The maximum adsorption capacity of Cr(VI) estimated with magnetic sugarcane biochar (43.122 mg/g) was approximately 1.298-, 3.175-, and 3.677-fold higher than that observed with RS, peanut shells, and herb residue-derived biochars, respectively (Yi et al., 2019). Nanocellulose prepared from pistachio shell powder reinforced in a polyester matrix at 5 wt% showed good thermal stability and a pronounced rise in the tensile and flexural strengths of 43 and 127 MPa, respectively (Movva and Kommineni, 2017). The fabrication of GR-tin oxide NCs from coconut shells consisted of three steps: (i) coconut shell carbonization, (ii) oxidative treatment using a modified Hummers’ method, and (iii) one-pot hydrothermal treatment. This resulted in rod-like structures that did not aggregate, even after storage of 30 months. These NCs inhibited the bacterial growth of P. aeruginosa on nutrient agar plates showing a zone of inhibition 38  0.7 mm after 24 h incubation (conc. 1 mg/mL) and an MIC of 250 μg/mL, suggesting that they could be used for biomedical applications (Mohan et al., 2019). Composite sheets prepared using recycled low density polyethylene and sorghum bran (5–20 wt%) by melt compounding and compression molding showed increased moduli and tensile strength with increasing fiber loading with lower hardness, suggesting that sorghum bran particles can be applied as good reinforcements for polymer matrix composites (Ogah, 2017). Hydrogel NC films prepared from SiO2 NPs and cotton seed hull pretreated with NaOH and NaOCl for delignification and bleaching, respectively (used as a source of cellulose), via the phase inversion method without a chemical cross-linking agent of cellulose showed improvement of the tensile strength and modulus as well as the elastic modulus at SiO2 NP content of 2–6 wt% and up to 10 wt%, respectively, whereby the incorporation of SiO2 NPs caused a decrease of the elongation at the break (Boonmahitthisud et al., 2017).

4.3 Individual agricultural wastes

4.3.3 Rice husk RHs (or rice hulls) are hard at protecting the coverings of grains of rice. A biodegradable NC made from cassava starch and CNCs isolated via acid hydrolysis of cellulose extracted from the RH via chemical treatment that were prepared using the solutioncasting method showed increased storage modulus, tensile properties, and thermal stability as well as lower water uptake. This is suitable to produce NC films that could be utilized as food packaging films and shopping bags (Kargarzadeh et al., 2017). By coating cotton fabric with functionalized AC prepared from RH biomass and functionalized with a suitable silane coupling agent, an ultraviolet protection factor of 63.9 was achieved, being approximately 20-fold higher than that of pristine cotton (3.2). Enhanced tensile strength behavior was observed as well (Thennarasu et al., 2018). In RH biochar/high-density polyethylene composites prepared via melt mixing followed by extrusion, the biochar improved the creep resistance, dynamic viscoelasticity, and stress relaxation properties of the composites, whereby the creep resistance and stress relaxation decreased with increasing temperature (Zhang et al., 2017d). Pulverized biochar was fabricated by RH pyrolysis and pulverized using the ball-mill method to obtain NPs with a size of 45 nm to be used as particulate reinforcement in an unsaturated polyester matrix at 2.5 wt% concentration in NC. This caused a 56.3% and 6.4% decrease in the specific wear rate of the specimen and the coefficient of friction, respectively, with corresponding parameters of cured pure resin (Richard et al., 2017). In the composite of MCM-41 (a mesoporous material with a hierarchical structure from a family of silicate and alumosilicate solids) with RH prepared under hydrothermal conditions, in which the Ag/AgBr NPs were incorporated by the in situ method, the RH served as the SiO2 source as well as a substrate for the deposition of MCM-41. At 1.5% AgBr loading, the composite reached 99.0% removal of Eriochrome Black-T dye from aqueous solution under visible light, the maximum adsorption showing at pH 2 while at pH 7 its decomposition occurred (Sohrabnezhad and Mooshangaie, 2019). RH combusted at 600°C was used to produce amorphous SiO2 applied for the fabrication of CuO/RH ash-MCM-41 NCs containing 5 and 10 wt% Cu and calcined at 300°C and 500°C. These NCs exhibited remarkable antibacterial activity against S. aureus and E. coli (Ziksari and Pourahmad, 2016). Fe3O4/RH-based macro/mesoPC bone NCs prepared by the high-temperature hydrothermal treatment of RHs hydrothermally pretreated by HCl aqueous solution and subsequently impregnated with ferric nitrate and urea aqueous solution (the precursor of Fe3O4 NPs) at 600°C and then treated with NaOH aqueous solution to dissolve SiO2 and produce mesopores were reported as a superior high-rate anode material for lithium-ion batteries (Fan et al., 2017). Su et al. (2016) reported that at the fabrication of b-phase silicon carbide (SiC) NPs (20–30 nm) from RHs by a magnesiothermic reduction at a relatively low temperature of 600°C, the SiO2 was at first reduced to Mg2Si in the rapid exothermic process. The Mg2Si then reacted with residual SiO2 and C to produce SiC showing

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notable electromagnetic wave absorption with a minimum reflection loss of 5.88 dB and a reflection loss band width MC1 > parent coir fibers. A further increase of thermal stability could be achieved with

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the increase of Ag concentration during coating. Coating of lignocellulosic coirs with AgNPs resulted in an increase in the dielectric constant of these NCs connected with the stacking of charges at their extended interface, whereby the dielectric properties were affected by the size and coating level of the AgNPs in the NC and the hydrophobicity of the fibers. AgNP-coated fibers showed improved thermal stability compared to the parent coir. Because sintering temperatures for AgNP-coated coir fibers could reach 600°C or more, such fibers show higher packing density and insulating properties. They could find wide applications such as materials for embedded capacitors, optoelectronic devices, metal oxide semiconductor field effect transistors, and integrated circuits (Rout et al., 2019). Coir fibers, after bromination with saturated bromine water and subsequent treatment with an SnCl2 solution, drying, and grinding to nanoscale dimensions, were mixed with epoxy resin to prepare an NC fire retardant with pronouncedly improved fire-retardant properties such as smoke density and limiting the oxygen index (Sen and Kumar, 2010). Superior mechanical properties were reported to optimize hybrid composites fabricated using coir fibers with 3-aminopropyltriethoxysilanefunctionalized clay and glass spheres using a vacuum-assisted resin transfer molding, in which the reinforcing effect of the particles resulted in the improved load transfer between the fiber and the matrix (Muthu et al., 2018). Coir CNFs showing a mean diameter of 5.6  1.5 nm were fabricated using a TEMPO-mediated oxidation system (TEMPO/NaClO/NaClO2, pH 4.8) with subsequent ultrasonic treatment. They were used to prepare composite films with PVA characterized with pronounced elongation at the break, enhanced tensile strength, and thermal stability when the number of nanofibrils represented 3% of the dry film weight (Wu et al., 2019). Corn silks are weak fibers growing in the tuft or tassel from the tip of the ear of corn. N, P, and Fe tri-doped nanoPC electrocatalysts for the oxygen reduction reaction in air electrode derived from plant biomass corn silk designed by Wan et al. (2016) could be used in high-performance zinc-air batteries. These nanocatalysts showed a tolerance of methanol poisoning effects in alkaline media, excellent stability, and pronouncedly higher photocatalytic activity as well as higher voltage and higher specific capacity than the Pt/C catalyst in a zinc-air battery. A new embedded heterogeneous photocatalyst based on a corn silk/TiO2 NP composite was able to raise the adsorption of species by increasing the active surface area. It showed good activity in the photocatalytic oxidation of Direct Blue 15 (>90% conversions within 30 s) (Nadaroglu et al., 2018). Bagasse is the dry pulpy fibrous residue that remains after sugarcane or sorghum stalks are crushed to extract their juice. The composite film was prepared using CNCs fabricated by extraction from SCB. Following alkali bleaching and acid hydrolysis treatments, it showed a needle-like structure with an average aspect ratio of 55 and a crystallinity index of 80, which were dispersed into κ-carrageenan biopolymer matrix, decreased the light transmittance values, and improved the mechanical properties in comparison with the neat κ-carrageenan film (Kassab et al., 2019). CNCs obtained by the acid hydrolysis of bleached SCB and functionalized with adipic acid showed reduced nanocrystal dimensions compared to nonfunctionalized

4.3 Individual agricultural wastes

CNCs. They could be used as a reinforcing phase in hydrophobic polymeric matrices, unlike the nonmodified ones, which are suitable for hydrophilic matrices (Ferreira et al., 2018). Thermoplastic starch/cellulose nanofiber-based NCs prepared by thermally plasticizing regular cornstarch by sorbitol and reinforcing it with CNFs (30–40 nm) were extracted from SCB using alkali steam explosion coupled with high shear homogenization. NCs showed pronouncedly improved mechanical and barrier properties, more so than the neat polymer (Rani et al., 2018). Saha et al. (2019) prepared a CS-cellulase nanohybrid and immobilized it on alginate beads for the hydrolysis of ionic liquid pretreated SCB in order to investigate cellulase recycling. They found that this immobilized nanohybrid exhibited a higher immobilization yield and stability in comparison with immobilized cellulase at the optimum condition and could be successfully recycled up to fivefold. Sharma and Bajpai (2018) prepared a cross-linked hybrid polymer network using CS and SCB, which were microfibrillated by ultrasonication of their suspension in an ionic liquid 2-hydroxy ethylammonium formate, in the presence of MMT clay. The sample prepared with optimized amounts of initiator, monomer, and cross-linker and suitable microwave irradiation exhibited slow and steady swelling up to 15,000%, resulting in a hydrogel formation in 15 days. In studying the swelling and reswelling in water, it was found that the swelling degree increased up to three cycles and then became constant. Moreover, the NC showed antimicrobial activity against S. aureus and E. coli. PLA bio-based composites with the cellulose fiber extracted from the SCB and prepared through fused deposition modeling 3D-printing technology showed less tensile strength and flexural strength, but increased flexural modulus compared with neat PLA; the best results were observed with an SCB content of 6 wt% (Liu et al., 2019b). In composite PVA films reinforced with alkali-treated bagasse fibers disposed by solution casting, the Young’s modulus and tensile yield stress of the composites containing 8% fiber filler was three- and twofold higher than that of neat PVA films, whereby with increasing filler content, the composite films showed a slight decrease in the thermal stability and increased water uptake (Guo et al., 2018). NC scaffolds with highly porous structures prepared by CNCs obtained from SCB incorporated with PVA showed considerably improved mechanical, swelling, and thermal behaviors compared to neat polymers. At 10 wt% CNCs, the biocompatibility with a human fibroblast skin cell line (CRL-2522) was observed. The powerful attachment, proliferation, and penetration of human fibroblast skin cells on the scaffold was demonstrated, suggesting that such NC scaffolds could be applied as an alternative biomaterial in tissue engineering (Lam et al., 2017). BioNC films fabricated by CNCs extracted from SCB using sulfuric acid hydrolysis and a PVA/CMC blend matrix by the solvent casting method containing 5 wt% CNC dispersed at the nanoscale exhibited an increase in the tensile modulus and strength by 141% and 83%, respectively, and a reduction of the water vapor permeability by 87%, suggesting that they could be used in food-packaging applications (El Achaby et al., 2017). Cellulose nanofibers extracted from energy cane bagasse and incorporated in a hydrogel composed of a flexible interpenetrating polymer network (IPN) core and a rigid semi-IPN shell prepared by chemical cross-linking of PVA and sodium

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alginate with Ca2+ and glutaraldehyde showed a maximum methyl blue adsorption capacity that was 10% higher than hydrogel without CNFs. This also showed enhanced mechanical strength, viscoelasticity, and density due to additional H-bonds among the polymer molecular chains generated by CNFs, whereby the compressive strength of the composite hydrogel was 3.2-fold higher than that of the neat hydrogel (Yue et al., 2016). A novel polyaniline-coated bagasse fiber composite with a coreshell heterostructure providing effective electromagnetic shielding performance was designed by Zhang et al. (2017a). The NC exhibited superior electrical conductivity (2.01  0.29 S/cm) and enhancement of electromagnetic properties due to the improved conductivity and the core-shell architecture. This NC could be used as a conductive filler to endow polymers with electromagnetic shielding ability. In bioactive packaging to preserve food, a 10 wt% SCB fiber-reinforced starch foam composite containing 8 wt% oregano essential oil showing antimicrobial activity against E. coli and S. aureus was recommended (Ketkaew et al., 2018). The pretreatment of bagasse powder with choline acetate and subsequent nanofibrillation resulted in a strong increase of the specific surface area compared to the control bagasse (32 versus 0.83 m2/g) and enhanced tensile toughness of esterified bagasse/polypropylene composites (1.29 versus 0.52 J/cm3) (Ninomiya et al., 2018). NCs of poly(butylene adipate-co-terephthalate) reinforced with CNCs isolated from bleached SCB by acid hydrolysis and functionalized by adipic acid, which were prepared by solution-casting method followed by covered with silver thin film by magnetron sputtering, showed improved thermal and mechanical properties and effectively decreased formation of the E. coli biofilm formation suggesting their potential use as food packaging (Ferreira et al., 2019). The controlled release of dimethyl phthalate from an NC granular formulation consisting of CNFs derived from waste SCB mixed with gelatinized maize starch and urea formaldehyde was observed. The reduction in the initial release rate and higher overall release of the encapsulated compound could be connected with water uptake-induced diffusion and barrier effects rendered by the nanocellulose network. The comparison with neat starch granules showed that reinforcing starch with 2–4 wt% CNFs led to a considerable reduction in porosity and 20–30% enhancement of the water uptake (Patil et al., 2018a). In the high-density polyethylene/ bagasse flour containing organomodified MMT (OMMT) NCs produced by melt blending, the OMMT strongly enhanced the flame retardancy of the NCs because the nanoclay-produced silicate char situated on the surface layer of the NC increased the flame resistance of the samples. The incorporation of 6 wt% OMMT into the composites resulted in a 22.43%–34.06% increase of the limiting oxygen index corresponding to a minimum concentration of O2, expressed as percentage volume, in a flowing mixture of O2 and N2 that will support the combustion of a material initially at room temperature (Kord et al., 2017). Nitrogen-doped nano-PC sheets showing a BET surface area of 1284 m2/g fabricated via thermal annealing of low-cost discarded bagasse under a flowing NH3 atmosphere showed superb catalytic activity for an oxygen reduction reaction in alkaline media, decent catalytic ability in acidic media, and superior stability and methanol tolerance (Yuan et al., 2016b). Babu and Ramesha (2019) used a melamine-assisted liquid exfoliation approach to fabricate nitrogen doped GR-like

4.3 Individual agricultural wastes

carbon nanosheets (NBCs) from SCB with the potential to be applied in high areal density Li-S batteries. NBCs were able to efficiently trap polysulfides, and the S@NBC composites prepared by the chemical absorption of the S onto the NBC matrix had excellent performance as a cathode for the Li-S battery. They showed a reversible capacity of 1169 mAh/g at 0.2 carbon with 77% capacity retention after 200 cycles and exhibited 85% retention of higher-order polysulfide, even after 200 cycles. This extraordinary cycling performance could be connected with the effective chemisorption of sulfur and polysulfides by the nitrogen-doped carbon. A real capacity of 12 mAh/cm2, which is threefold higher than that of a contemporary lithium-ion battery, could be achieved by stacking four cathode layers, resulting in increasing sulfur loading to 12 mg/cm2. A friction material composition containing 5 wt% of bagasse fibers/particles as functional/friction additives and 5 wt% Al2O3 NPs as an abrasive showed a specific wear coefficient of 1.18 107 and a friction coefficient of 0.369. Increasing the waste content resulted in a reduced density of composites. Through the dynamometer wear/friction test, the conventional features of the wear surface were estimated, including a first and second plateau and wearing debris (Amirjan, 2019). Liu et al. (2019a) fabricated Fe3O4/carbon fiber (Fe3O4/CF) composites derived from bagasse waste by in situ growth and a graphitization process, in which the multiple interfaces and hierarchical microstructure of NCs were constructed by the Fe3O4 nanocrystals uniformly embedded in PC fibers. The Fe3O4/CF composites investigated as lightweight microwave absorbers exhibited a maximum reflection loss value of 48.2 dB at 15.6 GHz with a thickness of only 1.9 mm, achieving an absorption bandwidth of 5.1 GHz covering the frequency range of 12.9–18.0 GHz. The hydrothermal method was used to fabricate the SCB carbon/MnO2 NC electrode material, in which SCB was used as the carbon source, KOH as the activation agent, and the obtained carbon with a rich porous structure acted as the host for MnO2. The specific capacitance of SCB carbon, MnO2, and the composite electrode were calculated as 280, 163, and 359 F/g, respectively, and after 2000 cycles of charge and discharge, the composite showed 94% capacitance retention (Xiong et al., 2018). Functional PC-ZnO NCs were fabricated using SCB as a carbon precursor and ZnCl2 as an activating agent. Glassy carbon electrodes modified by this composite showed excellent electrochemical properties and enabled the simultaneous detection of ascorbic acid, dopamine, and uric acid or environmental pollutants (e.g., H2O2, N2H4) with desirable sensitivity, selectivity, and detection limits. The stainless steel electrodes modified by these NCs exhibited superb performances for supercapacitor applications as well (Madhu et al., 2016). A ZnO-tetrapods/AC (ZnO-T/ AC) NC was designed as an adsorbent for the decontamination of Cr(VI) from an aqueous medium containing ZnO. It was synthesized by flame transport synthesis approach and AC was fabricated from SCB with NaOH impregnation following carbonization. The NC achieved 97% removal efficiency at pH 2 (Sharma et al., 2019). Motaung and Mochane (2018) presented a systematic review focused on recent findings related to the use of SCB, a byproduct of sugarcane mills after sugar extraction, consisting of abundant and available natural fibers as fillers in polymer composites.

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CHAPTER 4 Preparation of nanocomposites from agricultural waste

Cassava starch films reinforced with cellulose nanowhiskers from oil palm mesocarp fibers obtained by sulfuric acid hydrolysis followed by microfluidization fabricated by casting showed a strong reinforcing effect at 2 wt% nanowhisker loading, reflected in a 70% increase in elongation at the NC break, whereby the interaction between the filler and matrix through hydrogen bonding was estimated (de Campos et al., 2017). It should also be mentioned that the investigation of CNFs isolated from coconut palm petiole residues using chemical pretreatments and mechanical treatments by a grinder and a homogenizer showed that chemical pretreatments improved the CNF crystallinity from 38% to 70%. Also, a combination of 15-fold of grinding followed by 10-fold of homogenization resulted in increased thermal stability of the fiber samples, which could be used in nanofiber-reinforced composites (Xu et al., 2015). Lamaming et al. (2017) described a chlorine-free method for the isolation of CNCs from oil palm trunks, in which water prehydrolyzed samples were subjected to soda pulping, then acidified and ozone bleached. This resulted in improved CNC crystallinity (up to 75%), reduced lignin (150 hours

Potassium nitrate beads Urea

Chitosan and graphene oxide Hydrogel (polyacrylamide, methylcellulose, calcic montmorillonite) Young stem of Gliricidia sepium

–

7 days

N,N0 -Methylene bisacrylamide

200 hours

Bortolin et al. (2013)

–

>60 days

Kottegoda et al. (2011)

–

300 hours

Kottegoda et al. (2015)

N,N0 -Methylene bisacrylamide

>60 days

Rashidzadeh et al. (2015)

Urea-modified hydroxyapatite nanoparticles Urea

NPK

Layered double hydroxides; montmorillonite clay Clinoptilolite-hydrogel nanocomposite (hydrogel consists of sodium alginate, ammonium persulfate, acrylamide, acrylic acid)

References Golbashy et al. (2017) Li et al. (2019)

nanocomposite on maize was investigated through a pot experiment, which illustrated efficient promotion in iron uptake and the growth of the maize crop. The ASO, being hydrophobic, imparted greater stability to the fertilizer in aqueous solutions with the extended nutrient release for up to 100 days. Apart from this, the nanocomposite-based iron fertilizer also exhibited high reuse efficiency along with a decreased residual effect and farm expenditures. Another type of fertilizer formulation developed through nanointerventions involved the triggered release of nutrients in response to some reaction or product so as to synchronize the release rate of nutrients with the plant requirements. Here, pH was used as a suitable trigger to regulate the release of iron from the nanocomposite composed of microcrystalline cellulose (MC), ferrous sulfate (FeSO47H2O), and nanorods of natural nanoclay and attapulgite (ATP) (Wang et al., 2016). The carboxyl groups on the MC surface chelated with Fe2+ to form CC-Fe2+ microfibers. Their microfibers were then strongly covered or encapsulated using ATP nanorods, which resulted in the formation of the desired fertilizer. This fertilizer was highly responsive to pH as the acidic conditions facilitated the release of iron due to the reduced strength

115

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CHAPTER 5 Fertilizer and pesticide nanoformulations

of the ATP coating. Thus, the ATP nanorods served as an efficient pH-controlledrelease coating because the pH of the media greatly controlled the CC-Fe2+ chelation as well as the hydrogen bond between the ATP coating and CC-Fe2+ microfibers, which allowed the modulation of the nutrient release timed accurately with the plant nutrient demands in different growth phases. Also, the presence of ATP nanorods imparted great adhesion capabilities to the nanocomposite, which allowed efficient adsorption of the fertilizer on the surface of corn leaves, thereby reducing the loss of fertilizer by increasing its uptake efficiency (Wang et al., 2016). The formulation of a novel nanofertilizer involved the inclusion of nitrogen, phosphorus, and potassium (NPK) molecules in chitosan nanoparticles and the resultant nanocomposite was applied on a wheat crop in sandy soil through a foliar spray. The application of the nanochitosan-NPK fertilizer improved the growth as well as yield parameters of the wheat crop as compared to the control (Abdel-Aziz et al., 2016). Apart from this, nanofertilizers can also amplify the reaction rates of various synthesis processes in plant cells due to the higher surface area (increased reactivity) and greater bioavailability of nutrients, which further improves the quality of plant produce by increasing the protein, oil, and sugar content in the final product (Singh et al., 2017). Evidences suggesting a positive impact of nanomaterial applications on crop yield can be found in the published literature (Table 5.2). These indicate better delivery of essential nutrients and higher uptake efficiencies through the application of micronutrient nanoparticles such as Zn, Mn, Fe, and Cu oxide nanoparticles or through encapsulation in nanomaterial assemblies (Bandyopadhyay et al., 2014; Monreal et al., 2016).

5.4.2 Nanopesticides: Novel nanocarrier-based formulations for sustainable pest control Nanopesticides are applied to agricultural soils or crops alongside other agrochemicals with an aim to increase (i.e., additive interactions) or decrease (i.e., antagonistic interactions) the potential effects on soil organisms (Simonin et al., 2018). Information regarding some of the nanopesticides and their impact on the target organisms is compiled in Table 5.3. Although nanopesticides play a crucial role in integrated pest management by protecting the crops from pests, insects, and fungal and bacterial diseases, their application may have potential unintended consequences on nontarget organisms. These may include beneficial plant-associated microorganisms involved in plant nutrition, such as mycorrhizal communities or nitrogen-fixing bacteria. Their unregulated application may also have detrimental consequences on soil fertility and plant yields over the long term as a result of repeated exposure. Thus, in order to maintain sustainability, the side effects of nanopesticide use on soil ecosystems, including on humans, must be explored. Straw ash-based biochar and biosilica have been used for the synthesis of chlorpyrifos nanocomposites, which showed properties of reduced loss via washing, volatilization, and leaching, thereby improving the efficiency of the pesticide and reducing the risk of environmental pollution (Cai et al., 2013). A composite of copper

Table 5.2 Application of nanocomposites for fertilizer nutrient delivery and their impact on crop growth and yield attributes.

Nanocomposite

Test crop

Urea-sodium humateattapulgitepolyacrylamide (USH-ATP-PAM) nanocomposite

Maize

Nanochitosan polymethacrylic acid-NPK fertilizer (CS-PMAA-NPK)

Wheat (Triticum aestivum)

Application method and study conditions

Parameters affected

Remarks

Growth

Yield

Quality

Mechanism

Ancillary benefits

Soil application; pot and field experiments

• Significantly

–

–

• Upregulation of

–

Zhou et al. (2017)

Foliar application; pot experiment

Considerable progressive improvement in all growth variables at vegetative and reproductive stages

–

expression of severalN-uptake related genes • Increased N-ion flux in maize roots • Modification of the soil microbial community • Increased number of bacteria involved in Nmetabolism, organic matter degradation, and iron cycle –

Marked reduction in the leakage of electrolyte from nanofertilized plants

Abdel-Aziz et al. (2016)

increased plant height • Higher leaf chlorophyll content

Improved yield variables at different concentrations of nanocomposite (89.37% increase in crop yield)

References

Continued

Table 5.2 Application of nanocomposites for fertilizer nutrient delivery and their impact on crop growth and yield attributes—cont’d Parameters affected

Remarks

Growth

Yield

Quality

Mechanism

Ancillary benefits

Soil application; pot experiments

Improved seed germination and seedling growth

–

–

–

• Enhanced soil

French bean

Foliar spray (10%); pot experiment

–

Presence of CSPMAA-NPK nanoparticles in phloem tissue

French bean

Foliar spray (20 μg/L); pot experiment

Significant increase in all growth parameters (root and shoot length, fresh and dry weight, leaf area) Significant increase in all growth parameters (root and shoot length, fresh and dry weight, leaf area)

–

CNT-NPK particles observed in both xylem and phloem tissues

Nanocomposite

Test crop

Poly(acrylic acidco-acrylamide) AlZnFe2O4/ potassium humate superabsorbent hydrogel nanocomposite (PHNC) Nanochitosan NPK (CS-PMAANPK)

Wheat

Carbon nanotubes loaded NPK (CNTs-NPK composite)

Application method and study conditions

moisture retention capacity • Delayed seedling wilt (approximately by 6–9 days) Reduced electrolyte (ion) leakage throughout the experimentation period

Reduced electrolyte (ion) leakage throughout the experimentation period

References Shahid et al. (2012)

Hasaneen and Abdelaziz (2016)

Hasaneen and Abdelaziz (2016)

Ureamontmorillonitepolyacrylamide hydrogel and paraformaldehyde nanocomposite

Italian ryegrass (Lolium multiflorum Lam.)

Soil application; greenhouse pot experiment

Mesoporous TiO2/ SiO2 nanocomposite

Tomato

Exposure to nanocomposite (80Ti-20Si); postharvest shelf life study

• MUPf treated

–

plants exhibited higher N content (30%) • Increased dry matter yield (by 53%) • Higher total N uptake (by 43%) • Improved recovery efficiency (by 60%) –

–

• Delayed epicarp coloration • Less fruit softening • Negligible ethylene climacteric peak

Lowered N losses as compared to urea application

–

Pereira et al. (2017)

• Nanocomposite-

• Reduced

de Chiara et al. (2015)

enabled complete degradation of ethylene

produce losses • Prolonged shelf life

120

Table 5.3 Effect of different types of nanocomposite pesticides on target organisms. Nanocomposite Polymerizing/ cross linking agent

Acephate

Di-chloromethane

Polyethylene glycol

Diethylphenylacetamide (DEPA)

Soya lecithin nanoformulation

Polyethylene glycol and dichloromethane

Imidacloprid

Sodium alginate nanoparticles Polycitric acid nanocapsules Carboxymethyl chitosan nanocapsules Nanoemulsuion in n-butyl acetate

Poly vinyl alcohol

Leafhopper

Polyethylene glycol

Glyphodes pyloalis Armyworm larvae

Imidacloprid Methomyl

Permethrin

Pyridalyl

Alginate nanocapsule

PONNEEM (neem oil, karanj oil, azadirachtin, and karanjin)

Chitosan nanoparticles

Azidobenzaldehyde

Target organism

Biological effect

References

Spodoptera litura, Lipaphis erysimi (mustard aphid), and Bemisia tabaci (whitefly) Culex tritaeniorhynchus

Decrease in acetylcholinesterase activity; increase in pesticidal activity

Pradhan et al. (2013)

Increase in larvicidal activity; significant damage in epithelial cells and peritrophic membrane with extensive midgut content leakage Reduction in pest population

Balaji et al. (2015)

Increase in mortality rate Increase in mortality rate

Kumar et al. (2014) Memarizadeh et al. (2014) Sun et al. (2014)

Soybean lecithin with soybean phosphatidylcholine Calcium chloride

Culex quinquefasciatus

Increase in mortality rate

Anjali et al. (2010)

Helicoverpa armigera

Saini et al. (2014)

Tripolyphosphate and glutaraldehyde

Helicoverpa armigera

Increase in toxicity as compared to conventional formulation Increase in larvicidal activity; nanoformulations resulted in abnormalities in the growth and development of larvae

Gabriel Paulraj et al. (2017)

CHAPTER 5 Fertilizer and pesticide nanoformulations

Active ingredient

Organic/ inorganic compound

Neem oil

Zein nanoparticles

Essential oil (Zanthoxylum rhoifolium)

Polycaprolactone, Span 60, and acetone nanospheres Organic polymers

Polyethylene glycol

Chitosan nanoparticles

Silver nanoparticles

Neem cake

No significant effect on survival, growth, and reproduction

Pascoli et al. (2019)

Bemisia tabaci

Significant reduction in number of eggs (up to 96%) and nymphs (up to 98%) with encapsulation Increase in repellent activity with nanoformulations

Christofoli et al. (2015)

Increase in pesticidal activity with control efficacy against adult stage up to 80% as compared to 11% in case of free garlic oil preparation Increase in mortality rate; decrease in larval and pupal mass as compared to control and emulsified pesticides Increase in toxicity against larvae and pupae

Yang et al. (2009)

Blattella germanica

Tribolium castaneum

Polyethylene glycol nanocapsule

Carvacrol and linalool

Caenorhabditis elegans

Gum arabic

Helicoverpa armigera and Tetranychus urticae Aedes aegypti

Gonza´lez et al. (2016)

Campos et al. (2018)

Chandramohan et al. (2016)

5.4 Nanoformulations and crop plant responses

Essential oil nanoparticles (Geranium maculatum and Citrus bergamia) Garlic essential oil

Pluronic F-68 (block-copolymer of ethylene oxide and propylene oxide)

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CHAPTER 5 Fertilizer and pesticide nanoformulations

nanoparticles with polymers such as polyvinyl methyl ketone, polyvinyl chloride, and polyvinylidene fluoride has been shown to increase the antifungal activity against Saccharomyces cerevisiae (Cioffi et al., 2004). Nanocomposites can also be synthesized with an aim to achieve the triggered release of the AI. Coumarin-based photo-responsive polymers have been employed for the photo-responsive release of AI because of their strong fluorescence and efficient photo-release activity (Atta et al., 2015). Similarly, thermoresponsive polymers can also be used for the temperature-controlled release of pesticides. Polydopamine and poly(N-isopropyl acrylamide) are such polymers that have been used for the preparation of emamectin benzoate microcapsules. These microcapsules exhibited a temperature-dependent release of the AI (Shen et al., 2017). Novel pH-responsive biodegradable nanocapsules of poly(γ-glutamic acid) and chitosan can be used for the release of AI at acidic pH (Imoto et al., 2010) as the size of the nanocapsules gets enhanced at low pH (pH 1).

5.5 Challenges of nano-based agrochemicals In recent years, there has been a great increase in the number of patents issued for the development of nano-based agricultural products and applications, demonstrating the vast prospects of nanoagriculture (Dang et al., 2010; Kim et al., 2018). However, despite the presence of numerous research publications and patents regarding the prospects of nanoagriculture in crop fertilization and protection, the commercialization of nanoproducts is extremely limited, which may be attributed to the existence of various challenges and knowledge gaps surrounding their usage (Kim et al., 2018). Specific challenges associated with nanotechnology include low investments in research and development infrastructure, high production costs, low agricultural returns, and inefficiencies in the transfer and implementation of technology in the agricultural sector that limits progression (Huang et al., 2015; Kah, 2015; Parisi et al., 2015). Further, these products may pose risks to agriculture and food production as these are the two most susceptible areas of application, where the uptake and accretion of engineered nanomaterials in plants can contaminate the food chain, causing high risks to humans as well as the environment (Peng et al., 2017). Thus, it is of utmost importance to acquire appropriate knowledge regarding the various advantages and challenges offered by the implementation of nanotechnology in the agricultural field so as to avert the emergence of unreasonable hopes and stigmas related to their novel applications (Iavicoli et al., 2017).

5.5.1 Technical issues related to industrial production of nanoformulations of agrichemicals Various technical constraints obstruct the successful production and implementation of nanofertilizers. One of these is the higher energy demands of processes involved in the production of nanoparticles. Another major technical challenge is the inherent

5.5 Challenges of nano-based agrochemicals

tendency of the nanoparticles to aggregate, dissolve, or be coated due to the adherence of surrounding materials on their surface, which alters their surface chemistry and proposed function. Such NP aggregation cancels out the size-dependent benefits of the fertilizers by transforming them into nonnano entities before use, thereby counteracting the main purpose behind the creation of these nanofertilizers (Dimkpa and Bindraban, 2018). Additionally, the mode of nanofertilizer delivery is another major factor that influences the industrial production of nanoformulations. The delivery systems of nanosuspensions may include various mechanisms such as direct foliar sprays, soil application of nanosuspensions or their dried forms, broadcast of dried nanoformulations, or through seed coating (Dimkpa et al., 2015a,b). Such challenges necessitate the development of effective yet responsive and functionalized nanofertilizers that not only improve plant growth and yield, but also include more efficient and safe technologies for fertilizer applications (Dimkpa and Bindraban, 2018).

5.5.2 Commercial constraints—Economic profitability and market viability The high costs involved in processing/production, the shortcomings in the scalability of research and development for trial as well as for industrial production of nanoproducts, and the concerns related to the public’s perception of the product in terms of its impact on health and environmental safety are some of the challenges that are commonly encountered in the commercialization of nanotechnology-based products (Agrawal and Rathore, 2014). Practically, all the studies regarding nanofertilizers provide a general view of their agronomic benefits. However, these studies fail to address the particulars associated with the economic consequences of their use. Therefore, analyzing the expenses and returns involved in nanoagrochemical production and its application is crucial for the effective implementation of these nanoproducts (Dimkpa and Bindraban, 2018). An economic analysis of various nanomaterials as well as production methods is required to compare and identify the best-suited nanomaterials and production routes for the generation of highly effective, cost-efficient, and sustainable nano-based agricultural products (nanocomposites/nanofertilizers) facilitating higher returns as the nanomaterial manufacturing expenses can amplify the final cost involved in crop production (Dimkpa and Bindraban, 2018; Pereira et al., 2015). Such a comprehensive analysis determining the economic aspects of nano-based products in comparison to traditional agrochemicals can serve as an important information tool in guiding the flow of future investments from various industries as well as the end users or growers toward the application of nano-based agricultural products (Dimkpa and Bindraban, 2018). However, the commercialization and bulk use of the nano-based products must be regulated and strictly monitored through common, government-devised, and globally applicable standards (Agrawal and Rathore, 2014).

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5.5.3 Nanotoxicity and the environmental safety perspectives of nano-based agrochemical use The application of nanomaterials in agriculture in the form of nanopesticides and nanofertilizers acts as a major gateway that may contaminate the food chain and cause nanotoxicity (Kim et al., 2018). Various methods of regulating toxicity and preventing food chain contamination have been proposed, including the safer and effective use of nanoproducts; elucidating the interactions, fate, and toxicity of nanomaterials in the environment; and giving due consideration to risk assessment factors (Mishra et al., 2017). These methods involve nanoecotoxicology studies that deal with knowing the toxicity of nanoparticles that are able to retain their particle size, properties, and reactivity after entering the environment. That is, these studies aim at investigating the actual behavior of nanoparticles in natural conditions in relation to other particles and contaminants ( Jampı´lek and Kra´ˇlova´, 2017). The ecotoxicology studies of nanoagri-products are important due to the increasing use of nanotechnology-based products in the agriculture and food industries. Toxicity or biosafety is a major hurdle in the production of nanopesticides. A risk assessment of nanopesticides is mandatory before these can be placed in market. Detailed studies on nanopesticides need to be conducted that should include aspects such as their dosage in different environments, their physical and chemical characterization, uptake, bioaccumulation, mobility, potential residue, durability, the fate of the nanoparticles in soil, the mechanisms whereby the nanoparticles enter and traverse through cellular membranes and cell walls, the structural and chemical properties that contribute to their toxicity, and the mechanism underlying trophic transfers (Kookana et al., 2014). This will allow understanding the real effects of nanoagro-chemical applications and help in reducing environmental risks. Nanopesticides should degrade faster in soil and slower in plants while maintaining residue levels below the criteria in food products (Khot et al., 2012). Kah et al. (2016) studied the sorption and degradation behavior of a bifenthrin nanoformulation in soil and reported that the nanoformulation of the pesticide bifenthrin facilitated its mobility along with the soil profile, although its bulk form was largely immobile. The transport of nanopesticides can be predicted through a phenomenon exhibited by natural colloids (Ng et al., 2012). Nanopesticides applied to crop plants can enter the food chain through trophic transfer. Therefore, for sustainable pest control, their effect on humans and animals needs to be assessed. Wan-Jun et al. (2010) compared the effect of nanochlorfenapyr with its conventional preparation on mice. They performed micronucleus tests and comet assays with three different doses and reported similar DNA and chromosomal damage with both the preparations; however, the severity of these effects was less in the nanopreparation as compared to the conventional preparation. Various studies have demonstrated the effect of nanopesticides on soil microbiomes. Liu et al. (2014) synthesized carboxymethyl-β-cyclodextrin-magnetic nanoparticles loaded with diuron and studied their effect on soil chemical and biological properties. They reported a significant decrease in urease enzyme activity with an

5.6 Future roadmap

increase in exposure time compared to the control diuron. They also observed a decrease in the overall bacterial and actinomycete population with an increase in dose concentration. Simonin et al. (2018) carried out a mesocosm study to evaluate the effects of a Cu(OH)2 nanopesticide on the plant-soil microbiome. They observed that nanopesticides did not cause significant adverse effects when applied in conjugation with conventional farming with high fertilization rates. However, detrimental effects on soil microbial processes were observed in context of low-input organic farming. In addition to pest control, nanopesticides also alter the biochemical profile of the plants. For example, nanopesticide Cu(OH)2 nanowires showed a variety of dependent effects on high and low anthocyanin varieties (HAV and LAV) of basil (Tan et al., 2018). Nanowire application increased the n-decanoic, dodecanoic, octanoic, and nonanoic acid content in LAV, but decreased levels of n-decanoic, dodecanoic, octanoic, and tetradecanoic acids were observed in HAV. The maximum benefits of environmentally friendly nanotechnologies in agriculture can be exploited only if environmentally safe doses of nanoparticles can be validated. This can be achieved by performing long-term in situ field trials, carrying out studies on trophic chain transfer, and examining the relationship between nanoparticle-insect, nanoparticle-plant, and nanoparticle-microorganism interactions (Kookana et al., 2014). However, investigations deciphering the risks associated with the use of nanomaterials in agriculture have not been comprehensively carried out, rendering the interactions between plants and nanomaterials as a major area of concern. Various evidence indicating the potential toxic effects of the engineered nanoparticles (ENPs) can be located in the published literature. This suggests that based on specific properties of nanoparticles such as nanoparticle type, size, and concentration as well as plant species and cell tissues, ENPs may exert chemical or physical toxicity on plants and may also alter the rhizosphere microflora as these particles remain adhered to the plant roots (Aiken et al., 2011; Buzea et al., 2007; Frenk et al., 2013; Iavicoli et al., 2017; Monreal et al., 2016). However, in certain cases, concentration-based agglomeration, aggregation, and the solubility of nanoparticles in the dispersion media may also give rise to nanotoxicity, thereby restricting the practical implications of nanomaterials in agriculture as well as generating phytotoxic effects even at lower doses (Kumar et al., 2018). Therefore, gaining insight into the underlying mechanisms of these interactions can help bring rapid advancements in nanoagriculture through the development of biocompatible nanoproducts, thereby making it a sustainable agricultural practice (Kim et al., 2018).

5.6 Future roadmap Nanotechnology holds great potential in improving agricultural practices and production by utilizing the knowledge from all the cross-disciplinary fields. It may prove to be beneficial in stimulating the development of effective, sustainable, and ecofriendly agrochemicals (Kim et al., 2018). Studies involving three-way

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comparisons between nanoformulations, conventional products, and AI are highly recommended to elucidate the fertilization and plant-protection mechanisms, followed by an evaluation of the performance of novel products against existing formulations. The initial evaluations need to be performed under gnotobiotic or controlled environmental conditions to screen and validate the ecosafe formulations. Further, large-scale field trials of developed nanoagrochemicals against their conventional counterparts would provide a more realistic approach for determining the benefits of nanoagricultural applications in terms of their efficiency, cost-effectiveness, and environmental impact. Apart from this, extensive characterization of both nano as well as nonnano products under a diverse range of application conditions must be included in all the nanoagrochemical-related studies to design adequate tools for their regulation and the associated benefits. Additionally, a holistic analysis of nano-based products can be carried out to ensure responsible advancements and commercialization of technology (Kah et al., 2018). Through improvements in fertilizer production and utilization, nanotechnology can pose a significant impact on the environment, energy, and the economy (Naderi and Danesh-Shahraki, 2013). Likewise, nanoscale plant-protection agents can provide improved efficacy, besides curtailing environmental pollution and better addressing the development of resistant pests.

5.7 Conclusion Agricultural productivity has been enhanced several-fold through the application of agri-chemicals, particularly fertilizers and pesticides. However, hazardous environmental and health complications were identified during the postgreen revolution era due to run-off, volatilization, and lixiviation of the active compounds or persistent residues derived from these agri-chemicals causing eutrophication, contamination of the land and groundwater resources, and green-house gas emissions. Therefore, the idea of nanoscale material, novel materials with high surface-area-to-volume ratios, emerged as AI loading agents or delivery vehicles. The early research on these materials was inspired from the slow, controlled, and even targeted release of AI from natural nanoscale soil minerals, the aluminosilicate-clays, zeolites, and layered double hydroxides (LDHs). However, later a cognitive approach of admixture and reaction among nanoscale, polymer/clay mineral and the AI components was utilized to develop nanocomposites. As these products may effectively address the dwindling use efficiencies of the applied products, probably due to injudicious use that may exceed twice the required application rates, considerable research efforts both in academia and industry have targeted the development of composites for slow, controlled, and targeted release of fertilizers and pesticides. These are anticipated to tremendously improve use efficiencies through the reduction of nontarget losses as well as the decreased cost of crop production and environmental degradation to enhance crop productivity while being ecologically sensible. Further, research and technological interventions are desirable that aim at the optimization of

References

fabrication protocols and the search for nonpolluting or biodegradable low-cost continuous matrix materials for making nanofertilizers or nanopesticides an economically viable venture.

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Singh, A., Jaswal, A., Singh, M., 2019. Impact of neem coated urea on rice yield and nitrogen use efficiency (NUE). Agric. Rev. 40, 70–74. Solanki, P., Bhargava, A., Chhipa, H., Jain, N., Panwar, J., 2015. Nano-fertilizers and their smart delivery system. In: Nanotechnologies in Food and Agriculture, Springer, Cham, pp. 81–102. Songkhum, P., Wuttikhun, T., Chanlek, N., Khemthong, P., Laohhasurayotin, K., 2018. Controlled release studies of boron and zinc from layered double hydroxides as the micronutrient hosts for agricultural application. Appl. Clay Sci. 152, 311–322. Sun, C., Shu, K., Wang, W., Ye, Z., Liu, T., Gao, Y., Zheng, H., He, G., Yin, Y., 2014. Encapsulation and controlled release of hydrophilic pesticide in shell cross-linked nanocapsules containing aqueous core. Int. J. Pharm. 463, 108–114. Sun, Y., Ma, Y., Fang, G., Ren, S., Fu, Y., 2016. Controlled pesticide release from porous composite hydrogels based on lignin and polyacrylic acid. Bioresources 11, 2361–2371. Suppan, S., 2017. Applying Nanotechnology to Fertilizer: Rationales, Research, Risks and Regulatory Challenges. Institute of Agriculture and Trade Policy, Washington, DC, USA. https://www.iatp.org/sites/default/files/2017-10/2017_10_10_Nanofertilizer_SS_f.pdf. Tan, W., Gao, Q., Deng, C., Wang, Y., Lee, W.Y., Hernandez-Viezcas, J.A., PeraltaVidea, J.R., Gardea-Torresdey, J.L., 2018. Foliar exposure of Cu(OH)2 nanopesticide to basil (Ocimum basilicum): variety-dependent copper translocation and biochemical responses. J. Agric. Food Chem. 66, 3358–3366. Tang, X., Alavi, S., 2011. Recent advances in starch, polyvinyl alcohol based polymer blends, nanocomposites and their biodegradability. Carbohydr. Polym. 85, 7–16. Varadachari, C., Goertz, H.M., 2010. Slow-release and controlled-release nitrogen fertilizers. In: Bijay, S. (Ed.), ING Bulletins on Regional Assessment of Reactive Nitrogen, SCONING, New Delhi. Wang, S., Nguyen, A.D., 2018. Effects of Zn/B nanofertilizer on biophysical characteristics and growth of coffee seedlings in a greenhouse. Res. Chem. Intermed. 44, 4889–4901. Wang, M., Zhang, G., Zhou, L., Wang, D., Zhong, N., Cai, D., Wu, Z., 2016. Fabrication of pH-controlled-release ferrous foliar fertilizer with high adhesion capacity based on nanobiomaterial. ACS Sustain. Chem. Eng. 4, 6800–6808. Wan-Jun, S., Wei-Wei, S., Sai-Yan, G., Yi-Tong, L., Yong-Song, C., Pei, Z., 2010. Effects of nanopesticide chlorfenapyr on mice. Toxicol. Environ. Chem. 92, 1901–1907. Wanyika, H., 2013. Sustained release of fungicide metalaxyl by mesoporous silica nanospheres. J. Nanopart. Res. 15, 1831. Xu, G., Sun, J.N., Shao, H.B., Chang, S.X., 2014. Biochar had effects on phosphorus sorption and desorption in three soils with differing acidity. Ecol. Eng. 62, 54–60. Yan, J., Huang, K., Wang, Y., Liu, S., 2005. Study on anti-pollution nano-preparation of dimethomorph and its performance. Chin. Sci. Bull. 50, 108–112. Yang, F.L., Li, X.G., Zhu, F., Lei, C.L., 2009. Structural characterization of nanoparticles loaded with garlic essential oil and their insecticidal activity against Tribolium castaneum (Herbst) (Coleoptera: Tenebrionidae). J. Agric. Food Chem. 57, 10156–10162. Zhou, L., Zhao, P., Chi, Y., Wang, D., Wang, P., Liu, N., Cai, D., Wu, Z., Zhong, N., 2017. Controlling the hydrolysis and loss of nitrogen fertilizer (urea) by using a nanocomposite. ChemSusChem 10, 2068–2079. Zhou, M., Xiong, Z., Yang, D., Pang, Y., Wang, D., Qiu, X., 2018. Preparation of slow release nanopesticide microspheres from benzoyl lignin. Holzforschung 72, 599–607.

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Nanomaterials for gene delivery and editing in plants: Challenges and future perspective

6

Mohamed A. Gada,b,*, Ming-ju Lib, Farah K. Ahmedc, Hassan Almoammard,e a

Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt bInstitute of Agricultural Environment and Resources, Yunnan Academy of Agricultural Sciences, Kunming, China cBiotechnology English Program, Faculty of Agriculture, Ain Shams University, Cairo, € € Department of Biology, Institute of Microbiology, Zurich, Switzerland Egypt dETH Zurich, e National Centre for Biotechnology, King Abdulaziz City for Science and Technology (KACST), Riyadh, Saudi Arabia

6.1 Introduction Nanotechnology plays an important role in agriculture, including pesticide delivery such as avermectin using porous hollow silica (15 nm) (Li et al., 2007), fertilizer delivery such as NPK controlled delivery using chitosan (78 nm) (Corradini et al., 2010), genetic material delivery such as DNA using gold (10–15 nm) (Torney et al., 2007a,b), pesticide sensors such as paraoxon using silica (100–500 nm) (Ramanathan et al., 2009), and pesticide degradation such as imidacloprid using titanium oxide (30 nm) (Guan et al., 2008). The field of nanotechnology has witnessed impressive advances in many aspects such as the synthesis of nano-scale matter and the use of its exotic physicochemical and optoelectronic properties. Nanogenomicsbased strategies has enabled plant breeders better accuracy breeding has opened up interesting new opportunities for selecting and transferring genes, which has not only minimized the time required to eradicate unneeded genes but has also allowed the breeder to access important genes from distant plants. Singh et al. (2011) found that nanotechnology provides a good model to explore important properties of metal in the shape of nanoparticles that have future applications in diagnostics, cell labeling, biomarker contrast agents, antimicrobial agents, and nanodrug systems. Some metallic nanomaterials such as silver and gold are recognized as plasmonic particles have a remarkable ability to absorb and scatter light outside of their physical cross-sections. This ringing frequency depends on the particle shape, size, *Corresponding author Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems. https://doi.org/10.1016/B978-0-12-821354-4.00006-6 # 2020 Elsevier Inc. All rights reserved.

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electron distribution, particle consistency, and the surrounding dielectric conditions. It supplies the beneficial information for the properties of the particles. Nanomaterials exhibit transitional dimensions between bulk materials, molecules, and atoms. Nanoparticles can be engineered and they are called intentional and unintentional. They can be referred to as nanocrystals when they have a crystal structure and as quantum dots (QDs) if they are semiconducting (Masciangioli and Zhang, 2003). Engineered nanoparticles cover a wide range of substances that include elemental particles and inorganic compounds such as zinc sulfide (ZnS). Metallic nanoparticles are formed from elements such as nickel, iron, zinc, gold, titanium, silver, palladium, platinum, and iridium (Connor et al., 2005). Materials used in QDs include inorganic cadmium selenide (Green and Howman, 2005). Inorganic nanomaterials are considered less toxic and possess versatile properties such as more availability, excellent biocompatibility, functionally rich, higher potential in target delivery, controlled release of target drugs, and driving forces for delivery (Kim et al., 2006). Nowadays, there are numerous nanomaterials including gold nanoparticles, starch nanoparticles, single-walled carbon nanotubes (SWCNTs), silica nanoparticles, QDs, and magnetic nanoparticles that have been extensively applied in the interdisciplinary fields of molecular genetics and genomics. A complete evaluation of the trendy research on specific nonviral transport materials for the shipping of clustered regularly interspaced short palindromic repeat (CRISPR-Cas) devices is offered, which include lipid nanoparticles, polymeric materials, hydrogels, gold nanoparticles, graphene oxide (GO), metal-organic frameworks, cell-penetrating peptides (CPP), black phosphorus DNA, and DNA. A change in physicochemical characters of nanocarriers, protoplasts, and plasma membranes might also extensively enhance the liposomal- and nanoparticle-encapsulated gene into plant cell (Rai et al., 2015). In this chapter, in addition to the status of gene delivery utilizing various nanomaterials for gene transfer in plants, we will also highlight the challenges and prospects of the CRISPR/Cas9 system combined with nanotechnology for futuristic plant biotechnology (Fig. 6.1).

6.2 Nanoparticle synthesis Three methods are used to synthesize nanomaterials: Chemical depreciation is the dominant method for nanoparticle synthesis using inorganic and organic reduction factors. The operation requires three main constituents: a reducing agent, a metal origin, and a covering/settling factor. Stubbs et al. (2016) reported that nanoparticle synthesis involves the microemulsion process, UV origin photo lowering irradiation procedures, and electrochemical artificial procedures. Chemical procedures have the merit of a big yield in contrast to physical procedures. The advantages of physical synthetic procedures in contrast to chemical procedures include physical processes, the symmetry of nanoparticle delivery, and the absence of solvent contamination. NPs in emulsion has generated the

6.3 Phytonanotechnology and engineered nanoparticles

FIG. 6.1 Nanomaterials used for CRISPR-Cas plant genome editing and gene delivery.

use of laser ablation of mineral bulk particles (Eftaihab et al., 2010). However, the defects of the physical process involve time, harmful environmental effects, and required space. Biological processes of nanoparticle synthesis control the biological molecules and enzymes. Jayaweera et al. (2017) found that microorganisms such as fungi have the ability to produce nanomaterials through a biological process. For example, silver NPs have been produced from Pseudomonas sp. Eftaihab et al. (2010) reported that the merits of these processes are the strong constancy of the Ag nanoparticles, which is different from that produced by the chemical process. The advantages of biological processes include less cost and a safer process compared to other processes for nanoparticle synthesis.

6.3 Phytonanotechnology and engineered nanoparticles The implementation of engineered nanoparticles in agriculture has the potency to change normal plant production techniques, enhance the target-specific delivery of biomolecules (nucleic acids, activators, and proteins), and organize the usage of agrochemicals (pesticides and nitrogenous fertilizers). Nel et al. (2006) found that engineered NPs have specific physicochemical characteristics (less surface area, enhanced reactivity, irregular surface structure). Nair et al. (2010) determined that nanoparticles can have time-controlled, programmed, target-specific,

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multifunctional capabilities while also being self-organized. ENPs can deliver agrochemicals in an “on-demand” way, either for defense against pathogenic microorganisms or for nutritional need. In addition, nanoparticles play an important role in genetic material and protein transmission.

6.4 Bioconjugation Bioconjugation means that the structure is formed of a metal substance and adsorbed or chemically adhered biomacromolecules. In view of the many-sided physicochemical features of inorganic nanomaterials involving broad availability and abundant functionality, in combination with their distinct optical, catalytic, and electronic features, the conjugation of biological molecules and inorganic nanomaterials has created a new way in the expansion of advanced functional materials with obviously enhanced properties and broad applications. Several inorganic nanomaterials containing metals, metal oxides, and Quantum Dots (QDs) have been produced by different synthetic methods and immobilized or hybridized with biomolecules such as DNA, antibodies, and enzymes, each through noncovalent or covalent interactions. The mechanism in the formation of conjugates, biological molecules, and inorganic nanoparticles remains incompletely unclear. It can include electrostatic interactions among positively charged regions of biomolecules and a negatively charged particle, hydrophobic interactions, and covalent binding of the nanomaterial to the sulfhydryl groups (dSH) of the biomolecule. Bioconjugated compounds can open a new route as an active antimicrobial factor by their mode of action. If a pesticide-resistant microorganism is immune to a particular pesticide molecule, then the nanomaterial can show its impact against the microorganism by attacking the site and mode of action.

6.5 Gene delivery The main and inherent challenge confronting plant gene delivery is biomolecule transfer into plant cells through the inflexible and multilayered cellular wall. Contemporary techniques suffer from a host of various boundaries, low transformation efficiencies, toxicity, and inevitable DNA integration into the plant host genome. Nanomaterials are the most appropriate candidates to eradicate the current limitations of delivering biomolecules into plants. Nanomaterials have been investigated for gene transport into plant cells. Gene delivery plays an important role in the evolution of pathogens and pests in crops through modification of gene behavior (Gelvin, 2003). Gene vectors are mostly divided into two divisions: biological and synthetic vehicles. In the biological part, viral vectors give active delivery (Takahashi et al., 2009; Walther and Stein, 2000). Conventional synthetic vehicles involving cationic lipids (Cho et al., 2010), dendrimers (Dufes et al., 2005), and polymers (Wu et al., 2012) have been greatly used for intracellular gene delivery. An

6.5 Gene delivery

efficient nanocarrier is required to supply strong protection for DNA to avoid lysis with nuclease enzymes, effective penetration inside cell tissues, and deliverance of the genetic material in its active form inside the cell nucleus (Thomas and Klibanov, 2003). Mesoporous silica nanoparticles are able to deliver genetic material inside plant cells (Torney et al., 2007a,b). Conventional gene delivery methods have some disadvantages such as less integrity of the transferred DNA, cell destruction, restricted range of the plant species, and toxicity, so engineered nanoparticles provide a new vehicle for the transfer of nucleic acid, activators, and proteins inside plant cells as well as additional safety. Torney et al. (2007a,b) reported that the use of silica nanoparticles to transfer genetic materials inside tobacco cells offers a distinct advantage. Martin-Ortigosa et al. (2014) found that enzymes or proteins can be transferred by mesoporous silica nanoparticles (MSNs) in plants, and they can also be beneficial for phytochemical analyses and gene alterations. In addition to MSNs (Hussain et al., 2013; Martin-Ortigosa et al., 2014), Au nanoparticles (Martin-Ortigosa et al., 2012a; Wu et al., 2011), QDs (Etxeberria et al., 2006), carbon-coated magnetic nanoparticles (Corredor et al., 2009; Gonza´lez-Melendi et al., 2008), and starch nanoparticles (Liu et al., 2008a,b) can be used for gene delivery in plants. The engineered nanoparticles have some advantages such as simple in use, efficacious, capable of co-delivering several biomolecules to the specific site such as genes, nucleic acid (Torney et al., 2007a,b), and proteins (Martin-Ortigosa et al., 2012b). Nanoparticles can be taken up by plants and transferred to other plant cells by utilizing different insoluble engineered nanoparticles, such as silica NPs, QDs, and titanium dioxide NPs. Engineered nanoparticles offer modern methods for transferring bioactive materials such as gene delivery, cellular differentiation, and visualizing (Fig. 6.2). Using nanoparticle-bear visualizing factors such as fluorescence (Liu et al., 2009a,b; Serag et al., 2011a,b), researchers may notice the motion of the delivered gene. Inorganic nanoparticles are produced as synthetic vehicles that offer various advantages relative to conventional lipid-based vehicles, involving tunable size and surface characteristics, multifunctional abilities, and the ability to translate the physical characteristics of the metal core to the delivery vector (Arsianti et al., 2010; Chen et al., 2005; Harashima et al., 2012; Kam et al., 2005; Lee et al., 2009; Prato et al., 2004). Inorganic nanoparticles are described as gene delivery vectors such as:

6.5.1 Quantum dots QDs of Cd, Se, or ZnS nanoparticles with conjugated amino acids are recognized as traveling through the vascular system of plants (Schwab et al., 2016). Quantum dots (QDs) are brilliant fluorescent materials for bioimaging, tracking, gene insertion and drug delivery applications (Jamieson et al. 2007). The issue of using these particles is their toxicity, which is restrained by their implementations in agriculture systems. These substances displayed extremely effective QD cellular labeling as compared

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FIG. 6.2 Nanocarrier-mediated delivery of bioactive molecules into plant cells. Modified from Loh, X.J., Lee, T.C., Dou, Q., Deen, G.R., 2016. Utilizing inorganic nanocarriers for gene delivery. Biomaterials Sci. 4 (1), 70–86 with permission from Elsevier.

to ordinary techniques. QDs have been applied to the integration of genetic cloth transduction, ratiometric oxygen sensing, and cell-precise labeling.

6.5.2 Silica nanoparticles MSNs have without difficulty functionalizable surfaces and rich textural properties, inclusive of tunable pore size (2–20 nm), huge surface area (>1000 m2 g 1), and pore volume. MSN applications have been established in many genetic engineering fields. The pioneering work of using MSNs to transfer some active biomaterials into plant cells was achieved in vivo by Dr. Kan Wang (Martin-Ortigosa et al., 2012b). MSNs were used to codeliver DNA and chemical substances (Torney et al., 2007a,b) further to DNA and proteins (Martin-Ortigosa et al., 2012b) to plant cells by biolistics. Martin-Ortigosa et al. used MSNs as carriers to deliver Cre recombinase into maize (Zea mays) cells (Martin-Ortigosa et al., 2014). For example, the MSN study from The novel structures of organically functionalized MSNs with 3-nm can offer innovative possibilities in target-specific delivery of proteins, nucleotides and chemicals in plant biotechnology (Torney et al., 2007a,b). Silica in its nanoforms, such as nanosilica and mesoporous silica nanoparticles, is particularly crucial in the delivery genes and plasmid cells. Magnetic nanoparticles particularly release their load in

6.5 Gene delivery

the plant cells (Zhu et al., 2008). Functionalized MSNs were employed to expand an MSN-mediated plant transient gene expression system. Within the MSN device, nanoparticles served as transgenic carriers to deliver foreign parts from DNA into intact Arabidopsis thaliana roots without the aid of mechanical force. Gene expression is detected inside the epidermal layer and within more internal cortical and endodermal root tissues via each fluorescence and antibody labeling (Chang et al., 2013). These particles are effective materials in agricultural implementations, such as transferring genetic materials and drugs to the proposed site in the plant. This is due to their potential to penetrate plant cells, synthesis at cost-effective rates, and material consistency. Mesoporous silica nanoparticles have low toxicity and additionally are more efficient in the protection of the genetic material from lysis inside plant tissues (Li et al., 2018). The main and promising technique of genome modifying mediated thru MSNs has been recently proposed. MSNs was applied as carriers to transfer Cre recombinase in maize embryos, carrying loxP sites combined into chromosomal DNA. After the biolistic introduction of engineered MSNs in plant tissues, the loxP was properly recombined into maize cells (Valenstein et al., 2013).

6.5.3 CNMs for gene delivery and genome editing Unlike mammalian cells, genetic transformation in a plant cell is complex; plant cell walls act as a sturdy barrier that inhibits the entry of every other external agent. The cellular wall is made from pass-connected polysaccharides, which are different among plant and animal cells. The plant cellular wall structure limits the use of any sort of nanomaterial for genetic cargo delivery. In an investigation, the uptake of fluorescent QDs directly into the plant cells became completed after 24 h of starving; however, unfortunately, the gene was no longer delivered (Etxeberria et al., 2006). Liu et al. (2009a,b) mentioned the SWNT penetration into walled plant cells, Nicotiana tabacum bright yellow (by way of 2) cells, a popular plant cell version that validated efficaciously delivered DNA and small dye molecules into intact plant cells. Serag et al., 2011a carried out the capability of multiwalled CNTs (MWCNTs) to traverse through a plant cell membrane via escape endocytosis. Further, MWCNTs are capable of localizing within the area of the nucleus, plastids, and vacuoles. With the use of two types of carbon nanotubes, SWCNTs at a concentration of 20 μg/mL and MWCNTs at a concentration of 15 μg/mL, the N. tabacum L. protoplasts were genetically transferred with the plasmid construct pGreen 0029. The SWCNT-based nanocarriers verified their applicability for the transformation of protoplasts and walled plant cells (Burlaka et al., 2015). The engineered peptide with its unique cationic and hydrophobic domains and the arginine functionalized with SWCNTs (Arg-SWCNTs) because of its nanocylindrical form can pass through plant cell barriers. Engineered chimeric peptides and Arg-SWCNTs were examined as easy, rapid, and secure gene providers for tobacco intact root cell transfection. Arg-SWCNTs could effectively transfer GFP-expressing plasmids to root cells (Golestanipour et al., 2018). Efficacious diffusion-based plasmid DNA and small interfering RNA (siRNA) are delivered into various mature species of plants with

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a set of pristine and chemically functionalized high aspect ratio nanomaterials (Demirer et al., 2018a,b). Demirer et al. (2018a,b) evolved and optimized a nanomaterial-based delivery tool that could transfer functional biomolecules into each model and crop plant species with high efficiency. For the first time, we demonstrated effective transient gene expression and silencing in mature plants thru CNT-based delivery of purposeful biomolecules. Demirer et al. (2018a,b) proved that pristine and chemically functional nanotubes efficaciously deliver DNA and protein expression without transgene integration in mature plants of Nicotiana benthamiana, Eruca sativa, Triticum aestivum, and Gossypium hirsutum leaves and arugula protoplasts. CNTs not only facilitated the delivery of biomolecules into intact plant cells, but they additionally protected the polynucleotides from nuclease degradation. Kwak et al. (2019) tried a novel method to deliver transgenes into the chloroplast, particularly via nanotubes. In his study, he designed chitosan-complexed SWCNTs that selectively delivered plasmid DNA to the chloroplasts of mature E. sativa, Nasturtiu mofficinale, N. tabacum, and Spinacia oleracea plants and in isolated A. thaliana mesophyll protoplasts. The delivery was a success and exhibited transient expression. Kwak and coworkers indicated gene delivery in plants via visualization of the transitive expression of a marker gene, following infusion of the nanoparticle carriers to the leaf lamina. Kwak produced four groups of chitosan-complexed SWCNTs by using noncovalent coating and covalent alteration of the nanotube sidewall to reinforce plasmid DNA (pDNA) loading and deliver overall performance to the chloroplasts. Nontoxic chitosan-wrapped SWCNTs may navigate plant cell walls, the plasma membrane, and double lipid bilayers of chloroplasts, thanks to their excessive surface charge. Chitosan can be complicated by negatively charged pDNA through electrostatic exchanges to preserve DNA from nuclease degradation. This nanoparticle-mediated chloroplast transgene delivery method may additionally have vast applications because it is simple, cheap, and applicable throughout different species (Lyu, 2019). CNT-mediated DNA and RNA delivery to plants is simpler and quicker than agrobacterium-mediated plant transformation, amenable to multiplexing, and can be applied on a large scale, allowing its broad-scale adoption (Demirer et al., 2018a,b). Some inorganic nanoparticles are natural capability CRISPR component carriers due to the fact that they’ve already been used for similar purposes. Examples of these contain AuNPs, CNTs, bare mesoporous silica nanoparticles (MSNPs), and dense silica nanoparticles (SiNPs). The use of AuNPs for CRISPR/Cas9 delivery was described earlier while CNTs (Bates and Kostarelos, 2013), MSNPs (Luo et al., 2014), and SiNPs (Luo and Saltzman, 2000) have been used for many gene delivery applications; the use of these carriers for Cas9 delivery has yet to be mentioned. CRISPR-Cas systems are efficiently implemented throughout an extensive range of prokaryotic and eukaryotic species for effective genome editing. In the future, the Innovative Genomics Institute (IGI) research group needs to apply new techniques to deliver CRISPR-Cas9 genome editing methods. The carbon nanotube would be lined with DNA that codes for the Cas9 protein and the guide RNA, which work together to edit a particular gene (Demirer et al., 2018a,b). The genome editing

6.5 Gene delivery

tools are presented to edit the plant’s DNA, leaving no footprint. Which means that unlike with some current plant genome-editing strategies, no strange DNA would be inserted into the plant’s genome. Nanomaterials consisting of carbon nanotubes show an awesome capacity to function as delivery tools of various genetic materials inside plant cells and plastids because of their potential to navigate the plant cell wall, cellular membrane, and organelle membranes. The enhancement and sizable adoption of CNTs in plant mobile biology call for further research into internalization mechanisms, the limits of what CNTs can convey and supply efficaciously, a detailed analysis of cytotoxicity, and the CNT destiny in cells after transporting their cargo (Demirer et al., 2018a,b). Our destination activities will explore these elements of CNT-mediated shipping to broaden an inexpensive, facile, and robust delivery method that could transfer genetic fabric into all phenotypes of any plant species with excessive efficiency. This, in sequence, will increase the proficiency of plant genome engineering systems with several applications within agriculture, therapeutics, the environment, and the pharmaceutical and power industries.

6.5.4 Gold nanoparticles Gold nanoparticles (AuNPs) are utilized because of their ability to become carriers of multifunctional gene vendors as well as their ease of synthesis, biocompatibility, and well-described surface chemistry. The nano-sized composite carrier has numerous advantages over different techniques due to its small size as well as matrices embedded with gold NPs (AuNPs) and their own higher transformation performance. Some research groups have demonstrated the use of DNA-functionalized gold nanoparticles for both the delivery of nucleic acid therapeutics and the modulation of gene expression in plant cells. AuNPs can bind with DNA or peptides via electrostatic magnetism and deliver their inner plant cells (Cunningham et al., 2018; Hao et al., 2013; Mortazavi and Zohrabi, 2018; Rosi et al., 2006; Ye and Loh, 2013; Ye et al., 2015). Rosi et al. (2006) determined that the shipping of DNA by the use of AuNPs revealed splendid gene delivery efficiency. Those nanoparticles established a maximal knockdown of gene expression, more immunity to nuclease, a complex bonding affinity for target DNA, and irregular toxicity in comparison to different gene vehicles. There are few reviews on the applications of gold nanoparticles for gene transfer in rice cells (Rai et al., 2012). The mycogenic intracellular gold nanoparticles (5–25nm) synthesized by Aspergillus ochraceus combined with carbon nanoparticles have been used effectively to deliver plasmid DNA to Nicotina tabacum via a gene gun (Vijayakumar et al., 2010). The very same work also explained efficient DNA delivery into the monocot Oryza sativa and a hard dicotyledon tree species, Leucaena leucocephala, with minimal plant cell damage. The nano-sized composite carrier has several merits over commercial micrometer-sized gold particles used in gene gun delivery. First, due to their small size, matrices embedded with gold nanoparticles have higher transformation efficiency. Additionally, they need less gold and plasmid to obtain the same transformation level efficiency. Moreover, this approach has comparatively low toxicity to plant cells

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(Vijayakumar et al., 2010). Nevertheless, gold-nanoparticle-embedded carbon matrices still need the support of a gene gun to successfully transfer DNA genetic material into plant cells. The biolistic cotransformation system using gold nanoparticles can be applied as a successful technique for gene delivery into rice varieties. Magnetic gold nanoparticles (mGNPs) with uniform length and morphology synthesized by way of our sonication treatment approach have been covalently with fluorescein isothiocyanate (FITC) molecules. Driven by an exterior magnetic field, FITC-labeled nanoparticles have been delivered into plant cells with and without cell wall partitions (Hao et al., 2013). Moreover, it requires less gold and plasmid to gain equal transformation performance. The technique notably lowers the toxicity of plant cells (Cunningham et al., 2018). Separate plasmids have been used within the transformation and have been correctly included inside the genome of an aromatic Iranian rice cultivar. The transgenic traces didn’t show any atypical physiologic characteristics and confirmed a growth pattern much like that of the nontransgenic parental line (Mortazavi and Zohrabi, 2018). Gold nanoparticles with their high surface-to-volume ratio, easy DNA attainable geometry inside monolayers, and tunable hydrophilic characteristics offer a promising platform for gene transport. A gold-nanoparticle-based nonviral vector acts as the gene delivery device inclusive of double-stranded DNA covalently linked to NIR-absorbing, plasmon-resonant gold nanoshells.

6.5.5 Magnetic nanoparticles Later, distinctive sorts of nanoparticles have been progressively utilized in plant transformation applications that can act as a transgenic vehicle for DNA, RNA, and oligonucleotides in various plant cells (Dyab et al., 2018; Rai et al., 2012). But the investigation of nanovendors for gene transport in plants remains a promising field, with an awful lot of potential for the future of plant biotechnology and genome editing. Magnetic nanoparticles right now are the nanomaterial sorts broadly used as special biomolecular providers for enzymes, proteins, and nucleic acids, assisted through an exterior magnetic field (Cordero et al., 2017). Employing these sorts of nanoparticles was examined in industrial biological implementations consisting of biosensors and diagnostics. These particles were suggested for different approaches, such as chemical and protein immobilization (Cao et al., 2003). Magnetic nanomaterials are applied as vectors for genetic fabric transduction; on this approach, the gene is mixed with nanoparticles and delivered to a targeted location in the interior of plant cells. Liu and his group moreover extensively utilized particular fluorescent-labeled enhanced nanoparticles as a gene shipping device to deliver specific genes in plant cells (Agotegaray et al., 2016; Liu et al., 2008a,b). Such gene-nanoparticle conjugation was designed in such a way that it binds and transports shuttle genes throughout the natural obstacles of plant cells similar to the cell wall, cell membrane, and nuclear membrane of the plant cells through inducing on-the-spot small pore channels with the assist of ultrasound waves. Via this method, researchers investigated how diverse specific genes can be effortlessly combined on the fluorescence-labeled nanoparticle surface at identical times and transported into

6.7 Future perspectives

plant cells. Alternatively, different elements depending on the kind of plant organ and its anatomy may have an effect on nanoparticle dissemination. Part of this kind of research was targeted at designing precise magnetic providers for unique treatment needs, and several secure and effective magnetic nanocarriers were formed (Hola et al., 2015; Mishra et al., 2015). A successful strong genetic transformation in plants has been carried out in cotton flowers by magnetic nanoparticles (MNPs). A β-glucuronidase (GUS) reporter gene–MNP complex was penetrated into cotton pollen grains by way of magnetic force, without compromising pollen viability. Through pollination with magnetofected pollen, cotton transgenic plants were effectively produced and exogenous DNA was positively combined into the genome, successfully expressed, and stably inherited in the offspring acquired with the assistance of selfing cross (Zhao et al., 2017). On the grounds of in prior report reviews that indicated the use of magnetic nanoparticle-based total gene transfer, diverse mechanistic ideas may be suggested to make the efficiency of this unique nonviral gene-blanketed biotransformation method better. The magnetic nanoparticle offers a vast field for gene delivery in plant studies, in particular in plant disorder treatment (Mohamed and Abd-Elsalam, 2019.)

6.6 Challenges The effective and extensive applications of novel hybrid nanomaterials in molecular genetic nanotechnology depend substantially on robust nanoparticle synthesis and engineering methodologies. The development steps of nanomaterials in agroecosystem applications include design, synthesis, surface variation, and bioconjugation. Each of these steps is essential in figuring out the general performance of nanoparticles. There are still many troubles and challenges that need to be addressed and conquered. As an example, no matter the current development at the bioconjugation of nanomaterials, researchers still want better techniques to attain reasonable reproducibility, robust surface coating, and bendy functionalization and bioconjugation techniques due to the complex surface chemistry of nanomaterials. Furthermore, the possible toxicity of some nanomaterials to the human body still needs clarification. To overcome those issues, surface modifications and progressed hybrid nanomaterials are taken into consideration. After immobilization of different functional and biocompatible compounds, nanomaterials would produce fewer agglomerations and less injury toward cells while displaying greater effectiveness for research in vivo. In the meantime, the regular manner for assembling nanomaterials and oligonucleotides should help to facilitate the recognition of target molecules. DNA-templated or as-prepared hybrid nanomaterials may additionally be a solution.

6.7 Future perspectives Nanobiotechnology offers appealing tools for delivering and modifying some bioactive materials because nanoparticles can be accurately tailored to deliver a specific biomolecule to the plant cell, tissue, or organism of interest (Du et al.,

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2012). Several recent reviews has proposed, however, that nanotechnologies may additionally conquer the barrier of the cell wall and decrease the drawbacks associated with present transgene delivery systems ( Joldersma and Liu, 2018). Demirer et al. (2018a,b) and Mitter and coworkers has each produced proof that positively charged nanoparticles are able to be linked with the negatively charged backbones of nucleic acids and directed into the plant cell (Mitter et al., 2017). During the journey into and inside the cell, nanoparticles protect DNA from enzymatic assault; however, on delivery to the cellular nucleus, the nanoparticles liberate the external nucleic acids. The mechanisms explaining the release and delivery of the transgene into the normal genetic processing machinery of the plant aren’t yet understood; however, the implications are thought-provoking. A successful stable genetic transformation has been accomplished in cotton vegetation by magnetic nanoparticles (MNPs). A β-glucuronidase (GUS) reporter gene–MNP complex has been infiltrated into cotton pollen grains with the aid of magnetic force, without compromising pollen viability (Fig. 6.3). Throughout pollination via magnetofected pollen, cotton

FIG. 6.3 A diagram illustrating the processes and principles of the pollen magnetofection protocol developed to insert a DNA nanoparticle complex into plants via pollen grains. Reproduced from Zhao, X., Meng, Z., Wang, Y., Chen, W., Sun, C., Cui, B., et al., 2017. Pollen magnetofection for genetic modification with magnetic nanoparticles as gene carriers. Nat. Plants 3, 956–964 with permission from Springer.

6.8 Conclusion

transgenic plants were efficaciously generated and exogenous DNA became effectively integrated into the genome, efficiently expressed, and stably inherited within the offspring obtained with the aid of selfing cross (Zhao et al., 2017). The primarily pollen-based transformation technology in cotton is a “pollen magnetofection” to at once produce transgenic seeds devoid of tissue culture. In this system, magnetic nanoparticles loaded with pure plasmid DNA carrying purposeful genes have been added into pollen by pollen apertures in the occurrence of a magnetic discipline. Later, these magnetofected pollens have been used for pollination to provide modified seeds. Pollen magnetofection is a genotype-unbiased transformation system; moreover, exogenous DNA turns out to be well integrated into the genome and stably expressed within the successive generations (Zhang et al., 2019). Regardless of the significant growth in plant molecular genetics, the delivery of exogenous DNA and/ or enzymes for genome modifying remains a huge challenge. New strategies based totally on nanoparticle-mediated clustered frequently interspersed palindromic repeats–CRISPR related protein (CRISPR-Cas9) technology, as those were tested in other organic systems (Glass et al., 2018; Lee et al., 2017; Sanzari et al., 2019; Wan et al., 2019). Past and recent research on nanoparticles primarily based on CRISPR/Cas9 gadget delivery for genome modifying was discussed in detail (Deng et al., 2019). Identify nanoparticle composites that are exceptionally efficient for plant cell internalization, and make use of those nanoparticles to deliver DNA, RNA, and Cas9-gRNA RNP to plants and calli in a species-independent manner (Glass et al., 2018; Mohamed and Abd-Elsalam, 2019). Recently, an innovative nanoplex-mediated plant transformation method may open up novel potentials in gene transfer in plants, which will enable developing a great number of transgenic plants. A new technique for gene transformation using amino acids improved AuNPs, where a plant cell-penetrating amino acid (CPA) nanoplex (AuNPs-CPAs-pDNA-CPAs) was employed as a gene vehicle for gene transfer. The nanoplex may be applied to effective gene and protein transporters. It is an appreciated method for the transfer of genes of interest or significant industry proteins into tobacco plants or other plant species for higher yield (Bansod et al., 2019). CRISPR systems, hybrid nanomaterials, and pollen magnetofection are rapidly becoming more effective, flexible, and accurate to encounter numerous requirements for targeted gene amendments. These advances are paving the way to design dream plants for the future (Bansod et al., 2019; Deng et al., 2019; Mao et al., 2019; Zhang et al., 2019).

6.8 Conclusion A nanoparticle-mediated transgene delivery technique will simplify plant biotechnology, as this type of system offers a simple and low-cost procedure to accomplish multiple requirements in excessive throughput reports, particularly when these nanoparticles pass in plant life spontaneously. The main existing applications of

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nanomaterials for gene delivery and editing in some crops may be open different and safer possibilities for smart insertion of biomolecules for new approaches in plant genetic engineering. Thus, there is a still need for the improvement of nano- or microparticles, and delivery methods for biolistic gene transfer in various plants to enhance seed growth or boost plant promotion and crop protection. More research is also required to enhance the regeneration and plant transformation responses of a wide variety of plant tissues and cultivars. Pollen magnetofection is easy, quick, culture-free, genotype-independent and with the capacity of multigene delivery. Current methods can transform virtually all crops, tremendously facilitating the breeding procedures of new types of transgenic plants. Hybrid nanomaterials and pollen magnetofection exposed a new age in agri-food sectors because they have essential roles such as the synthesis of new antimicrobials and recombinant protein in plant cells, engineering crops for better production and cleaner biofuels, fertilizers, increasing soil health, and developing crops that are protected from drought, pests, herbicides, and disease. Focusing on how these nanomaterials have the ability to passively permeate the cell walls can help us develop much better tools in the foreseeable future so that we are able to implement other fascinating methods such as CRISPR for the production of modified crops. However, we may still find several important challenges ahead. We may answer a few of these challenges by incorporating options for the efficient distribution of varied genes along with other editing tools to many plants, the design and fabrication of novel hybrid nanomaterials, pollen magnetofection, and CRISPR strategies.

Acknowledgment The author gratefully acknowledges the TYSP (Egypt-18-001) supported by the Ministry of Science and Technology of China for the postdoctoral position and also to the authority of the Plant Pathology Research Institute, Agriculture Research Centre, Giza, Egypt, for granting study leave during the work.

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Further reading

Walther, W., Stein, U., 2000. Viral vectors for gene transfer: a review of their use in the treatment of human diseases. Drugs 60, 249–271. Wan, T., Niu, D., Wu, C., Xu, F.-J., Church, G., Ping, Y., 2019. Material solutions for delivery of CRISPR/Cas-based genome editing tools: current status and future outlook. Mater. Today 26, 40–66. https://doi.org/10.1016/j.mattod.2018.12.003. Wu, J., Du, H., Liao, X., Zhao, Y., Li, L., Yang, L., 2011. An improved particle bombardment for the generation of transgenic plants by direct immobilization of releasable Tn5 transposases onto gold particles. Plant Mol. Biol. 77, 117–127. Wu, J., Yamanouchi, D., Liu, B., Chu, C.C., 2012. Biodegradable arginine-based poly (ether ester amide)s as a non-viral DNA delivery vector and their structure–function study. J. Mater. Chem. 22, 18983–18991. Ye, E., Loh, X.J., 2013. Polymeric hydrogels and nanoparticles: a merging and emerging field. Aust. J. Chem. 66 (9), 997–1007. Ye, E., Regulacio, M.D., Zhang, S.Y., Loh, X.J., Han, M.Y., 2015. Anisotropically branched metal nanostructures. Chem. Soc. Rev. 44 (17), 6001–6017. Zhang, R., Meng, Z., Abid, M.A., Zhao, X., 2019. Novel pollen magnetofection system for transformation of cotton plant with magnetic nanoparticles as gene carriers. In: Transgenic Cotton. Humana Press, New York, NY, pp. 47–54. Zhao, X., Meng, Z., Wang, Y., Chen, W., Sun, C., Cui, B., et al., 2017. Pollen magnetofection for genetic modification with magnetic nanoparticles as gene carriers. Nat. Plants 3, 956–964. Zhu, A., Yuan, L., Liao, T., 2008. Suspension of Fe3O4 nanoparticles stabilized by chitosan and o-carboxymethylchitosan. Int. J. Pharm. 350 (1–2), 361–368.

Further reading Deng, C.X., Sieling, F., Pan, H., Cui, J., 2004. Ultrasound-induced cell membrane porosity. Ultrasound Med. Biol. 30 (4), 519–526. Koo, Y., Wang, J., Zhang, Q., Zhu, H., Chehab, E.W., Colvin, V.L., Alvarez, P.J., Braam, J., 2015. Fluorescence reports intact quantum dot uptake into roots and translocation to leaves of Arabidopsis thaliana and subsequent ingestion by insect herbivores. Environ. Sci. Technol. 49, 626–632. Kurepa, J., Paunesku, T., Vogt, S., Arora, H., Rabatic, B.M., Lu, J., Wanzer, M.B., Woloschak, G.E., Smalle, J.A., 2010. Uptake and distribution of ultra-small anatase TiO2 alizarin reds nanoconjugates in Arabidopsis thaliana. Nano Lett. 10, 2296–2302. Loh, X.J., Lee, T.C., Dou, Q., Deen, G.R., 2016. Utilising inorganic nanocarriers for gene delivery. Biomater. Sci. 4 (1), 70–86. Seeni, A., Sirelkhatim, A., Mahmud, S., 2015. Review on zinc oxide nanoparticles: antibacterial activity and toxicity mechanism. Nano-Micro Lett. 7 (3), 219–242. Slomberg, D.L., Schoenfisch, M.H., 2012. Silica nanoparticle phytotoxicity to Arabidopsis thaliana. Environ. Sci. Technol. 46, 10247–10254. Yoon, T.J., Lee, W., Oh, Y.S., Lee, J.K., 2003. Magnetic nanoparticles as a catalyst vehicle for simple and easy recycling. New J. Chem. 27 (2), 227–229. Zhai, G., et al., 2014. Transport of gold nanoparticles through plasmodesmata and precipitation of gold ions in woody poplar. Environ. Sci. Technol. Lett. 1, 146–151.

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Hybrid nanomaterials for water purification

7

Muhammad Zahida,*, Nimra Nadeema, Noor Tahira, Farid-Un-Nisaa, Muhammad Irfan Majeeda, Asim-Manshab, Syed Ali Raza Naqvib, Tajamal Hussainc a

Department of Chemistry, University of Agriculture Faisalabad, Faisalabad, Pakistan Department of Chemistry, Government College University Faisalabad, Faisalabad, Pakistan c Institute of Chemistry, University of the Punjab, Lahore, Pakistan

b

7.1 Introduction The availability of clean drinking water is the most important parameter in determining the quality of life of human society. This important factor has been and will continue to be responsible for wars in various places in the world. This threatening aspect should be enough for researchers to develop and optimize potential wastewater treatment approaches to remove both biological as well as chemical contaminations. Wastewater treatment technologies such as ozonation, irradiation (UV, etc.), and chlorination are being extensively used for the removal of bacterial contaminations. However, the removal of chemical contamination is more challenging. Among organic contaminants, agricultural chemicals, pesticides, industrial fuels, and solvents can be removed using activated carbon, ozone/UV, or plasma technologies (Yuan, 2008). Nanomaterials are excellent materials for wastewater treatment due to their potential characteristics such as small size, large surface area, high porosity, high catalysis, highly reactive, tunable molecular size, hydrophobicity, ease of separation, and regeneration. These important features of nanomaterials (NMs) make them able to be used as a pollutant adsorbent. To achieve multiple features of nanomaterials at one site, engineering nanotechnology is being extensively evaluated by researchers to make binary, ternary, polymer, and various support-based nanocomposites. In this chapter, multifunctional hybrid nanomaterials as well as their classification and synthetic approaches are discussed. The evaluation of the photocatalytic potential of these hybrid nanomaterials (HNMs) is discussed in detail. The effectiveness of various supports such as biomass, graphene oxide, reduced graphene oxide, fly ash, polymer, etc., is assessed for their application in wastewater treatment. *Corresponding author Multifunctional Hybrid Nanomaterials for Sustainable Agri-food and Ecosystems. https://doi.org/10.1016/B978-0-12-821354-4.00007-8 # 2020 Elsevier Inc. All rights reserved.

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7.2 Photocatalytic compounds and their hybrid nanomaterials for wastewater treatment For over a decade, extensive research has been done to develop novel photocatalytic nanohybrids as emerging materials for wastewater treatment. Advanced strategies based on including a wide range of metal oxides and sulfides has allowed the design of hybrid heterostructures that increase the photocatalytic performances of these semiconductor materials. A synthesis approach may affects on the photocatalytic efficiency of hybrid materials. The effective synthesis method will result in the development of HNMs with controllable properties. Substantial advancements in understanding the morphology and composition of nanocrystals are a landmark in the research and development of binary or ternary hybrid semiconductor materials for wastewater treatment and energy generation (Choudhary et al., 2018).

7.2.1 Enhancement of photocatalytic activity by fabrication of hybrid heterostructures 7.2.1.1 Single component-based semiconductor photocatalysts The synthesis of an effective and photostable catalyst depends on numerous requirements, including that the band gap of the semiconductor should be large enough to provide electrons and for effective absorption overlap with the solar spectrum. Second, there should be a comprehensive mechanism for charge carrier separation and the transportation process. Single transition metal oxides (TMOs) remain the research focus for photocatalysis and water splitting, owing to their low cost and excellent chemical stability (Haque et al., 2018). Later on, single-component semiconductor materials were employed by coupling with supports or cocatalysts. But, in some cases, single component-based photocatalysts are not likely to satisfy the requirements for the photocatalytic process to occur. These single-component semiconductor materials were found to be ineffective and less active for light-mediated pollutant degradation (Zaleska, 2008).

7.2.1.2 Binary component-based semiconductor photocatalysts The efficiency of photocatalytic materials can be enhanced by using a combination of semiconductor materials. Crystalline metal oxides such as TiO2 and ZnO and sulfides such as CdS and ZnS in their bare, modified, and doped forms have remained the most used and explored semiconductor materials in photocatalysis for more than a decade. These semiconductor materials are effective due to their ecologically benign nature for the mineralization of toxic contaminants. Many research studies have been initiated to study other binary and ternary oxides and sulfides that are visible-light active ( Jacobsson and Edvinsson, 2012). The combining of two or more semiconductor materials results in designing hybrid heterostructures, which are potentially beneficial in photocatalysis. The reaction chemistry of HNMs has extensively been investigated by studying their growth kinetics. The light response of

7.2 Photocatalytic compounds and their hybrid nanomaterials

photocatalysts can be extended by developing novel hybrid semiconducting materials (Thangavel et al., 2017).

7.2.1.3 Ternary component-based semiconductor photocatalysts The use of ternary hybrid semiconductors shows an extended photocatalytic response by coupling two or more semiconductor materials having different band gaps. Such use also helps in retarding the recombination of charge carriers. Various methods for the development of hybrid materials include doping with nonmetals, rare earth metals, transition metals, dye sensitization, and surface alteration. The semiconductor materials can be prepared by coupling with unsupported materials, which include adsorbents such as agriculture wastes, core-shell materials, coal fly ash, and mesoporous silica, to reform a hybrid composite (Liu et al., 2016a,b). The most widely used method for the synthesis of semiconductor hybrid materials is by coprecipitation, in which a single or binary component is used with suitable support. These hybrid three-dimensional (3D) composites enhance the visible light response of the photocatalyst and exhibit improved quantum efficiency (Reddy et al., 2015). Apart from this, the application of these hybrid composites makes it favorable to use materials with low energy activation and low-cost irradiation sources such as light-emitting diodes and UV light lamps. This section of the chapter comprises the types of hybrid semiconductor materials and their synthesis methods.

7.2.2 Binary compounds and their hybrid nanomaterials 7.2.2.1 Metal oxide-based hybrids Binary hybrid photocatalysts are classified according to the nature of semiconductor materials, as shown in Fig. 7.1. Many simple transition metal binary oxides such as ZnO, TiO2, WO3, and Fe2O3 have occasionally been studied over the past decades because of their photocatalytic efficiency. These metal oxides involve different interface transfer processes of the charge carrier. The photochemical, optoelectronic, and catalytic properties of these oxides make them excellent semiconductor materials for photocatalysts. Coupling Ti2O with carbon-based inorganic materials such as carbon nanotubes and with sheet-like graphene materials enhanced the photocatalytic activity of the binary composites. Composites of binary oxides with inorganic materials showed very high photocatalytic activity. Coupling boron nitride with Ti2O showed excellent photocatalytic degradation efficiency for organic pollutants. The mechanism of hybrid formation revealed that boron nitride promotes charge separation and the improved adsorption of pollutants (Zhou et al., 2018).

7.2.2.2 Chalcogenide-based hybrid nanomaterials Metal chalcogenides are studied due to their abundance in the earth. Many transition metal chalcogenides (sulfides and selenides) are considered effective catalysts for the degradation of recalcitrant pollutants, owing to their narrow gaps and suitable band potentials that coincide with the visible light region of the solar spectrum. Initially, CdS and ZnS, having band gaps of 2.4 eV and 3.6 eV, respectively, were the

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Coupling of two or more single component semiconductors Colloidal compounds based hybrids

Metal oxides based hybrids Hybrid semiconductor photocatalysts

Iron oxide based magnetic hybrids

Chalcogenides based hybrids

Binary hybrid nanomaterials

Ternary hybrid nanomaterials

FIG. 7.1 Classification of hybrid semiconductor photocatalysts.

most-studied materials for the degradation of hazardous pollutants and for photovoltaic devices. Later studies showed that CdS is unstable under irradiation and undergoes photocorrosion, not only destroying the photocatalyst but also releasing toxic cadmium ions in solution (Yu et al., 2011). However, ZnS remained inert in corrosive environments, but its wide band-gap energy hinders its applications for visible light catalysis. Hence, to overcome these shortcomings, hybrid materials with these single sulfides were developed either by coupling or by the incorporation of coating materials. Transition metal dichalcogenides and other heavy metal sulfides such as Bi2S3, ZnS, and MoS2 have been extensively researched for the photocatalytic mineralization of pollutants (Bai et al., 2014). These transition metal dichalcogenides have shown remarkable development in the synthesis of hybrid composites for wastewater treatment. Doping binary chalcogenides with transition metals to form new hybrids has shown an increase in the degradation efficiency of dyes. Doping ZnS nanopowders with iron showed strong photocatalytic activity in visible light by determining the degradation of methylene blue (Chauhan et al., 2013). The usage of twodimensional (2D) nanomaterials as cocatalysts in the degradation of toxic substances using light irradiation is an attractive, and ecofriendly process. The use of molybdenum disulfide (MoS2) as a cocatalyst with metal tungstate to form a binary hybrid

7.2 Photocatalytic compounds and their hybrid nanomaterials

exhibited enhanced efficiency in dye degradation compared to the individual metal tungstate (Thangavel et al., 2017). Molybdates and tungsten-based chalcogenides are characteristic layered 2D transition metal chalcogenides and were employed as emerging photocatalytic materials. Elemental doping has proved to be an effective method for changing the surface properties and band structures of the transition metal chalcogenides for effective visible light harvesting and improvement of redox activities (Haque et al., 2018).

7.2.2.3 Iron oxide-based hybrids The separation of catalysts from massive volumes of treated solutions is timeconsuming and expensive. Hence, it is extremely necessary to make photocatalysts that can be collected and reused. Those photocatalysts that are separated simply under the influence of an external magnetic field make a new group of magnetic binary hybrid materials (Shekofteh-Gohari and Habibi-Yangjeh, 2016). Numerous heterogeneous systems constructed on iron oxides, iron hydroxides, zeolites, and pillared clays have been considered for use in environmental remediation processes. The catalytic efficiency of these magnetic hybrids depends upon the generation of hydroxyl radicals by the Fenton-like process and several other factors such as the oxidation state, surface area, crystallinity, temperature, and pH. Incorporating magnetic particles into semiconductor photocatalysts helps to retain the performance of hybrid photocatalysts and to allow renewable exploitation through magnetic force separation (Liu, 2012).

7.2.2.4 Hybrid colloidal nanostructures Colloidal nanoparticles are microscopic substances inhabiting regions among atomistic and macroscopic worlds. The chemical, physical, and optoelectronic properties of these metals and semiconductor materials manifest the alteration from the molecular limit to the solid state, providing standard methods for experimental and theoretical research of side effects. The control of shape, composition, and size allows altering the properties of these hybrid materials (Costi et al., 2010). The enhanced properties of colloidal hybrids make them effective powerful tools of wet chemistry, biological tagging, electrooptical applications, medical diagnostics, and solar energy harvesting. Metallic contacts have been used for integration on semiconductor devices by engaging very innovative top-down synthesis methods. The design of colloidal semiconductor hybrid structures leads to new opportunities for controlling dynamics for the conversion of solar energy and light harvesting applications. Colloidal hybrid Au-CdSe pentapods were synthesized by a chemical method and these pentapods showed enhanced photocatalytic activity (Haldar et al., 2012). Colloidal hybrids systems such as TiO2-Au as well as CdS-Pt and CdS-Au nanoparticles were synthesized, and their functioning for water splitting and hydrogen production was investigated. Numerous templated techniques have been used to manufacture colloidal plasmonic particles, which resulted in the formation of carbon nanotubes, nanorods, and nanowires ( Jones et al., 2011).

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The recent improvement in the development of ternary compounds has proved to be an effective approach to overcome the basic limitations of the binary compounds. The decade-long research has revealed new ternary compounds and their hybrid materials, which are suitable to extend the visible light response of the photocatalysts. Semiconductor photocatalysis gives viable solutions to counter the grave problems of energy shortage and pollution. On the other hand, the effective photo-response of many single or binary semiconductor materials is restricted due to the quick recombination of charge carriers. Therefore, the development of visible light effective hybrid photocatalysts, which can overcome this problem, remains the main challenge. Ternary compound-based composites give a wide prospect for the excitation by two or more photons of visible light active materials. These materials possess fewer energy photons and the exploitation of the heterojunction to drive the electronic procedures in the desired direction. Subsequently, this helps in the photoexcitation of limited electronic states for better selectivity. Most of these new ternary compounds are mainly studied for water splitting and the degradation of pollutants under visible or solar light. Apart from degradation, these ternary hybrid compounds have been efficient in the fields of energy storage and conversion (Sha et al., 2016).

7.2.2.5 Tungstate-based ternary hybrids Tungstate-based ternary materials with a narrow band gap are a favorable candidate for the degradation of pollutants in visible light. Tungstates are an important class of visible light responsive photocatalysts for the photocatalytic degradation of pollutants from wastewater. The recombination of photo-induced electron-hole pairs and a narrow light response range to the solar spectrum of single or binary metal tungstates restrict their wide applications. Ternary metal tungstates (M-WO4) are explored for environmental purification and energy storage applications, owing to their ecofriendliness and high stability (Ke et al., 2018). These transition metal-doped tungstates are a new class of ternary compound-based nanohybrids that are drawing attention because of their technological properties such as ionic conductivity, ferro-elasticity, and photoluminescence. Moreover, these hybrid tungstates have significant stability in acidic environments, making them a promising candidate for the treatment of wastewater polluted by organic acids. These tungstates with unique structures and morphologies display diverse properties. The morphology and structure are important aspects to tune the electronic properties, which ultimately affect photocatalytic performance. Controllable synthesis on hybrid tungstate nanostructures with desired morphology is mandatory to achieve the related properties well (Yi et al., 2018). A combination of single and binary tungstate with cocatalysts or another visible light catalyst results in the enhanced degradation efficiency of these ternary hybrids. As compared to a binary heterojunction, these heterojunctions comprising ternary tungstates can more efficiently separate and transfer photogenerated charge carriers and increase the range of light absorption (Zhang et al., 2018). Ternary tungstatebased hybrids also include rare earth metals and noble metal-doped tungstates. These

7.2 Photocatalytic compounds and their hybrid nanomaterials

are considered tungstate-based ceramic materials of mixed oxides, which are used in various technological applications such as the development of sensors, electrochromic devices, scintillators, photoluminescent materials, and lasers (De Santana et al., 2014). Many novel heterostructured ternary systems comprising tungstates have been fabricated using hydro/solvothermal, coprecipitation, sol-gel, and microwave-assisted sonication methods.

7.2.2.6 Molybdate-based ternary hybrids Among the new generation of visible light active hybrid semiconductors, molybdates are an important class of ternary semiconductor material. Extensive research has been done on combinations of molybdates to form ternary hybrid photocatalysts, including plasmonic metal-based ternary molybdates, bismuth-based ternary molybdates, and transition metal-based ternary molybdates. The formation of heterojunctions is an effective way for the synthesis of new ternary hybrid materials. Novel heterojunctions of ternary tungstates and molybdates along with doping of plasmonic metals show enhanced photocatalytic degradation of organic compounds (Lv et al., 2017). The coupling of silver molybdate and bismuth molybdate formed flowers such asAg2MoO4/Bi2MoO6 heterojunctions, which enhanced the photocatalytic efficiency of individual components. Hybrid composites of molybdates (sulfides and oxides) with supports and cocatalysts such as graphene oxide, reduced graphene oxide, and noncarbon adsorbents have been studied. The improved photocatalytic degradation of dyes has been observed by coupling molybdenum oxide along with reduced graphene oxide and magnetite (Anjaneyulu et al., 2018).

7.2.2.7 Vanadate-based ternary hybrids Ternary vanadate one-dimensional (1D) HNMs show countless applications in numerous fields such as photocatalysis, lithium-ion batteries, and electrochemical sensors because of their excellent electrochemical and photocatalytic properties. Vanadates have received significant attention in photocatalysis because of their fascinating structural properties. Vanadates are particularly characterized by a narrow band gap and easy methods of preparation (Z Pei et al., 2014). Usually, pristine vanadate undergoes photocorrosion, less quantum yield, and inadequate sunlight absorption, resulting in the poor performance of the photocatalyst. Recent research has revealed that by constructing a heterojunction structure of vanadates, noble metal loading such as silver and copper and cocatalyst binding can increase the photocatalytic performance of the vanadates. The fabrication of ternary hybrids of silver metavanadates shows very strong absorption in visible light, leading to the enhanced degradation efficiency of pollutants (Guo et al., 2018). This fabrication of hybrid heterostructures has been shown to enhance the photostability of ternary vanadates while speeding up charge separation and their transportation, therefore extending the lifetime of the charge carriers. The layered-type vanadates such as BiVO4 have attracted considerable attention as visible light assisted photocatalysts. Ternary bismuth vanadate (BiVO4) exists in three phases, crystalline, monoclinic, and the scheelite type. Various silver vanadates have been synthesized through a low-temperature

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hydrothermal method. Studies have shown that the structures of these silver vanadates can be tuned by varying the hydrothermal time and temperature. Silver and graphene codoped BiVO4 ternary systems showed enhanced photocatalytic activity (Xu et al., 2015).

7.2.2.8 Ferrite-based ternary hybrids Ferrites can be listed among semiconductors that show a narrow band gap. There are numerous synthesis methods for their preparation such as hydrothermal, microwaveassisted, sonochemical, sol-gel, and solid-state reactions. These hybrid photocatalysts have improved properties that allow their use in environmental remediation. Because of the magnetic properties of ferrites, they are easily separated from the reaction suspension. Hybrid ternary ferrites are prepared either through doping with transition metals or coupling with other binary or ternary metals (Shekofteh-Gohari and Habibi-Yangjeh, 2016). Metal ferrites can be coupled with graphitic carbon nitride and multiwalled carbon nanotubes (MWCNTs) to form high-performance hybrid photocatalysts (Shu et al., 2018).

7.2.3 Synthesis methods for hybrid photocatalytic materials 7.2.3.1 Hydrothermal method The word “hydrothermal” generally refers to the heterogeneous reactions that occur in the presence of aqueous solvents and mineralizers under conditions of high temperature and pressure. This synthesis method is carried out in steel-made pressure vessels called autoclaves. These autoclaves are Teflon-lined and work under conditions of controlled temperature and pressure. The key principle is primarily the dissolution and recrystallization process. The hydrothermal temperature that exceeds the boiling point of water reaches the pressure of vapor saturation. The internal pressure that is produced in the autoclave depends largely on the reaction temperature and the amount of solution used in the autoclaves. The most significant parameters that are considered while selecting an appropriate autoclave for hydrothermal treatment are the temperature and pressure conditions of the experiment and the corrosion resistance in that temperature and pressure range for a given solvent or fluid. The corrosion resistance remains a major factor for the autoclave material if the reaction is taking place directly in the vessel. Until recently, the hydrothermal method has remained the most commonly used method for the synthesis of hybrid nanoparticles. The hydrothermal method generally makes use of deionized water as the main reaction medium. The raw materials for the reaction are mixed by stirring until a homogenous solution is obtained, which is poured in the Teflon-lined hydrothermal autoclave that is sealed and heated to a particular reaction temperature. The middletemperature liquid controls the hydrothermal method. The consumption of energy remains relatively low during the process. Adjustments in the reaction temperature, time, pH, reactant concentration, and numerous other factors can help in the active control of crystal growth characteristics, thus, obtaining a product with controlled particle size and desired crystal structure. The catalysts prepared through the

7.2 Photocatalytic compounds and their hybrid nanomaterials

hydrothermal method have a good crystal structure and show uniform particle size (Guo et al., 2018). The wide applicability of the hydrothermal process makes it the easiest among all the synthesis methods to control the morphology and orientation of crystal growth that eventually affect the photocatalytic properties of samples. Many hybrid nanostructures and the thin film of supported materials have been fabricated using the hydrothermal method (Varshney et al., 2016).

7.2.3.2 Solvothermal method The solvothermal method for the synthesis of photocatalytic hybrid materials originates from the hydrothermal technique, with a nonaqueous solvent as the reaction medium. The temperature for the solvothermal method can be raised to higher levels because of a variety of organic solvents with higher boiling points, as compared to the hydrothermal process. This is because of the variety of organic solvents with high boiling points. Normally, the nanoparticle size, shape, distribution, and crystallinity can be improved and controlled using the solvothermal technique. The role of solvents is vital in defining crystal morphology. Solvents that have diverse chemical and physical properties affect the reactivity, diffusion behavior, and solubility of reacting species. Particularly, coordinating the ability or polarity of the solvent can affect the morphology. The solvothermal method is also used for the synthesis of 2D or 3D layered and nonlayered oxide- and sulfide-based binary and ternary hybrids. These 2D and 3D assembled structures can considerably improve the photocatalytic performance because of their enhanced active surface area and increased interaction between the photon energy and matter (Alsaif et al., 2016).

7.2.3.3 Sol-gel method The sol-gel process for the synthesis of HNMs has become the most commonly used method. The sol-gel technique is widely used for the synthesis of hybrid photocatalytic materials. Sol-gel techniques comprise colloidal solutions that may be gelatinized or present in the liquid phase. During this process, a sol that is prepared by mixing water with organic or inorganic metal salts is made into a colloidal suspension. Further, hydrolysis and polymerization transform the liquid sol into a gel. The modification of various metal oxides to make them suitable for specific applications can help to regulate different factors such as pH, the precursor nature, the reaction time, and the amount of water/solvent. The homogeneous mixing of metal ions at a molecular level is the main benefit of the sol-gel method, which improves the development of polycrystalline particles with exceptional properties. Furthermore, a variety of dopants can be introduced during any stage of the process. The introduction of these active dopants in sol during the gelation stage permits doping elements to develop direct interaction with the support, which enhances the photoefficiency of the hybrid photocatalysts. The solvothermal process for the synthesis of hybrid nanostructures has the advantages of homogeneity, consistency, reproducibility, and control of the reacting system. A hybrid system of TiO2 with single-walled carbon nanotubes (SWCNTs) and MWCNTs, prepared through sol-gel, showed excellent photocatalytic degradation of organic pollutants (Koli et al., 2017).

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7.2.3.4 Coprecipitation method The coprecipitation method is usually carried out by combining all reaction materials into a solution and subsequently aging the reacting system at a definite temperature for obtaining the desired precipitates. This method is simple, low-cost, and repeatable, making it suitable for the extensive synthesis of photocatalysts. But the method is usually time-consuming because the aging of the precipitate takes more than a day (Guo et al., 2018). Coprecipitation is usually carried out in solution having soluble salts comprising one or more ions by the addition of a precipitating agent (for instance, CO3 2
, OH
, etc.). In particular circumstances, a solution containing precursors is hydrolyzed to form insoluble oxides, hydroxides, and salts, which precipitate. The original anions in solution are carried away, which is followed by dehydration or heat decomposition obtaining a required precipitate. In operation, this is a simple synthesis method with little necessities of equipment. However, it is not possible to get nanoparticles with desired morphology with the coprecipitation method, due to less control on the preparation of particle size and nonuniformity in surface properties (Montini et al., 2010).

7.2.3.5 Sonochemical synthesis Sonochemistry is basically a new interdisciplinary method for the synthesis of nanohybrids, which mainly refers to the acceleration of chemical reactions or reaction events by means of acoustic pressure with the purpose of increasing the reaction rate or attaining completely novel reaction products. The use of ultrasound can speed up and change the reaction process by improving the reaction yield, ultimately leading to new chemical reactions (Patel et al., 2013). For the last several years, increasing research interest has been applied to the potential of ultrasound for the synthesis of hybrid photocatalysts. The applications of ultrasound synthesis under definite conditions allow the possibility of making nanocomposites in a short time and under mild conditions. Chemical effects due to ultrasound are not due to direct contact with the molecular species. The use of ultrasound in the synthesis of hybrid structures of transition metals, oxides, alloys, and carbides shows a vital role in uniform dispersion and the loading of nanoparticles on the support. The cavity produced because of ultrasonic irradiation collapses, resulting in the production of confined hot spots. The temperature of these localized spots is very high, nearly about 10,000 K with pressures of about 1000 atm. Under these extreme conditions, numerous chemical reactions and physical changes take place, resulting in the formation of nanostructured materials (Shende et al., 2018).

7.2.3.6 Microwave method The microwave (MW) synthesis method is extensively used as a means of activating energy to stimulate numerous chemical reactions. Considering the advantages of this technique in the field of photocatalysis such as higher yields, increases in the reaction rate, and solvent-free reactions, this technique provides cleaner and easier workup for the synthesis of several hybrid photocatalysts. The microwave-supported reactions are determined by the ability to react a mixture to absorb microwave energy

7.3 Support-based hybrid nanomaterials

that depends on the nature of solvents for the reaction (Liu et al., 2013). The capacity of a material or solvent to alter microwave energy into heat is determined by the term loss tangent (δ). Molecules and solvents having high tanδ values show good microwave-absorbing capacity. The term” tangent loss factor” is also frequently described as “dissipation factor” or “dielectric loss tangent.” The word “loss” represents input microwave energy that is lost to the sample due to heat dissipation. Therefore, microwave energy is transferred primarily due to dielectric loss and not by convection or conduction. Microwave-assisted synthesis has certain advantages over other synthesis methods because of the efficient and fast heating, phase purity, faster kinetics, reliability, and higher yields. In addition to this, it effectively controls the distribution of particle size and morphology in the production of nanoporous products and inorganic solids (Peng et al., 2012).

7.3 Support-based hybrid nanomaterials HNMs are multiphase domain materials, having at least one domain in the nanostructure range. The intellectual properties of NMs can be enhanced after compositing them with the multicomponent system to form HNMs, and these multiphase domain materials provide the advantages of two or even more different materials. The remarkable properties of HNMs can be achieved by the insertion of highly effective, stable, and cost-effective supports, as shown in Fig. 7.2. The main advantage of using support-based hybrid nanomaterials (S-HNMs) is the combined effect of adsorption and photocatalysis at one place, as shown in Fig. 7.3.

7.3.1 Organic-inorganic HNMs HNMs having the combination of both organic and inorganic NMs are called organic-inorganic HNMs. The carbonaceous and polymeric materials are organic moieties, whereas among inorganic materials, the antimicrobial agents such as ZnO and Ag NPs have potential applications in pathogen removal from water. The number of publications indicates the importance of nanotechnology in wastewater treatment. The problems related to inorganic materials include cost, human exposure, and environmental toxicity, which can be overcome by using organic supports with TiO2, silica, and Ag. These organic supports are cost effective and can offer potential wastewater remediation particularly in developing countries. The HNMs are thought to be among the interesting candidates for several applications. The processing of purely inorganic materials usually requires hightemperature treatment, whereas HNMs offer polymer-like handling. The ease of handling offered by HNMs is either due to the cross-linking of small precursor inorganic materials, the same as in polymerization reactions, or because of their major organic content. From an economical perspective, bulk HNMs offer their applications in a special area such as biomaterial sectors. However, their fabrication as thin films from

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Industrial (waste/by product)

Natural Natural zeolites Agricultural Shells (husks) Saw dust

Fly ash

Chitin

palm oil ash

Peat

Shale oil ash

Wood/coal

Corncob waste

Red mud

Egg shell etc.

Blast furnace sludge etc.

Straw etc.

Peat Wheat straw

Fly ash

Natural zeolite Red mud

Corncob

Adsorbent/support for water purification

FIG. 7.2 Classification of supports depending upon their origin.

cheaper materials could result in their property enhancement by simple surface treatment such as scratch-resistant coating.

7.3.2 Various supports and their role in WWT A number of treatment technologies for wastewater treatment are available, and adsorption is the most effective one. The effectiveness of the adsorbent could be justified after comparing it with a number of other supports. Various supports (Fig. 7.2) in hybrid nanomaterials have been studied for their application in wastewater treatment as shown in Table 7.1.

7.3.2.1 Graphene-supported HNMs Graphene is a layer of graphite that is just a single atom thick with potential applications in environmental protection. Graphene-supported HNMs have been synthesized and used extensively by researchers for the governance of water environments. The chemical oxidation-reduction, mechanical peeling, and conversion of carbon

Exhibit photocatalysis Reduces leaching of NMS

• • • •

High adsorptive surface area Enhances conductivity

Excellent properties for WWT

Properties

Zeolites

CNTs Graphene

Fly ash

Support based hybrid nanomat erials

+ Hybird nanomaterials Doped HNMs Ternary

Polymeric

Relatively small conc. required

Properties

• • • • •

Low leaching of nanomateri als

Support reduced nanomater ials proportion

After treatment

BOD controlled COD controlled TDS controlled Color removal

Small particle size Large surface area Photocatalysis Relativety small quantity required Easy recovery

7.3 Support-based hybrid nanomaterials

Support/adsorbent

Binary

Enhanced photocata lysis

Excellent adsorption

FIG. 7.3

167

Role of support in enhancement of various physicochemical properties of nanomaterials (NMs) for wastewater treatment (WWT).

Table 7.1 Various support-based hybrid nanomaterials and their applications in wastewater treatment. Support

Hybrid nanomaterials

Synthesis approach

Applications

Reusability

Reference

CNTs

Multilayer CNTs composite membranes Alumina-CNT membrane

–

Oily WWT

–

Yan et al. (2019)

–

Cadmium removal

–

Modified phase separation technique induced by temperature Chemical modification of CNCs

Salt rejection

Reused without significant damage in efficiency

Shahzad et al. (2018) Dhand et al. (2019)

Wastewater pretreatment from licorice processing

–

Jonoobi et al. (2019)

Sol-gel

Photodegradation of MB dye

–

EDTA-modified sawdust nanocomposites loaded with Fe3O4 GO-CuFe2O4

Synthesis through green biogenic process

Dye adsorption (brilliant green) and methylene blue

Hydrothermal

Arsenic removal

GO-NF

Chemical coprecipitation

U(VI) and Th(IV) removal

64% and 80% adsorption for MB and BG after five cycles No change in up to nine cycles Stable within five cycles

Gupta et al. (2015) Kataria and Garg (2019)

G-MnFe2O4

Solvothermal process

Sulfur-doped SnFe2O4/ graphene nanohybrids

Facile solvothermal

Cadmium Cd(II) and lead Pb(II) adsorption Photocatalytic degradation of chlortetracycline

GO-Fe3O4

One-pot ultrasonically assisted reverse coprecipitation Coprecipitating Coprecipitation and subsequent heat treatment One-step hydrothermal synthesis Urea thermal condensation loaded with NiFe2O4 nanoparticles

PVDF-CNT membrane composite Cellulose

Sawdust

Graphene Graphene oxide (GO)

Graphitic carbon nitride (GCN)

Polyethersulfone-based modified cellulose nanocomposite membranes CA/TPNC

GO-Fe3O4 GCN-antimony-doped tin oxide (g-CN)/ATO hybrid nano-composite g-C3N4@Ni-Mg-Al-LDH GCN/NiFe2O4

Carbofuran and nitenpyram removal

Acid orange 7 removal VOCs, toluene, benzene, styrene, xylene, and chloroform removal

– 70% photocatalytic efficiency after reuse for five cycles Stable within five cycles

Wu et al. (2018) Lingamdinne et al. (2017) Chella et al. (2015) Jia et al. (2017)

Tabasum et al. (2018)

U(VI) adsorption

Minor change Adsorption efficiency remains almost the same over four cycles –

Zubir et al. (2014) Ojha et al. (2019)

Zou et al. (2017)

Mineralization of oxytetracycline (OTC) antibiotic

Recycle efficiency up to 10 catalytic cycles

Sudhaik et al. (2018)

Reduced graphene oxide (rGO)

CoFe2O4/rGO

One-pot solvothermal

Methylene blue removal

Minor change

Bi2Fe4O9/rGO

Facile one-step hydrothermal method Chemical deposition

Methyl violet (MV) removal

–

Q. Wu et al. (2016) Sun et al. (2014)

–

Yao et al. (2014)

Ultrasonic treatment

Organic dyes (methylene blue, methyl orange, methyl violet, rhodamine B, and orange II) Bisphenol A (BPA)

–

Soltani and Lee (2016) Meidanchi and Akhavan (2014) Sonar et al. (2014) Lin et al. (2014) Liu et al. (2016b)

MnFe2O4-rGO

Fly ash (FA)

BiFeO3/reduced graphene oxide ZnFe2O4/reduced graphene oxide (rGO) FA/NiFe2O4

Hydrothermal reaction

Methyl orange and rhodamine B

–

Coprecipitation

Congo red dye removal

10%–15%

PVP/BiOBr/FACs Ag@AgCl-TiO2/FAC

One-pot solvothermal Two-step approach

Rhodamine B Rhodamine B

g-C3N4/N-TiO2/FACs

Hydrolysis

Methyl orange (MO)

TiO2/ZnFe2O4/AFAC

Sol-gel

Rhodamine B

Sulfophthalocyanine/TiO2/ FAC

Sol-gel

Methylene blue

– 79.59% efficient after fourth cycle 68% efficient after seventh cycle Minor decrease after three consecutive uses –

Zhao et al. (2017) Fan et al. (2018) Huo et al. (2009)

CA/TPNC, nanocomposite of cellulose acetate and tin (IV) phosphate; CNCs, cellulose nanocrystals; g-C3N4@Ni-Mg-Al-LDH, nanocomposites composed of graphitic carbon nitride and layered double hydroxides; GONF, graphene oxide and nickel ferrite composites; PVP, polyvinylpyrrolidone; TiO2/ZnFe2O4/AFAC, activated fly ash cenosphere (AFAC) supporting TiO2coated ZnFe2O4; PVDF, poly(vinylidene fluoride).

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nanotubes are common graphene synthesis methods due to the large surface area. Graphene (G) and reduced graphene oxide (rGO) have been used for the adsorption of pollutants such as surfactants, dyes, heavy metals, pesticides, etc. In a comparative study among GO, rGO, and other adsorptive materials, the results showed that GO and rGO had maximum adsorption capacity for nanoionic surfactants (TX-100) (Prediger et al., 2018). Antibiotics are being extensively used and hence pose serious toxicity issues, especially for aquatic life. Although traditional treatment technologies have been reported to solve this issue, they show insufficient activity toward the removal of some antibiotics. The electrostatic properties of graphene-based hybrid nanomaterials (GHNMs) may provide stronger adsorption of tetracycline. For example, graphene and CNTs, both common carbon nanomaterials, have been used for the effective adsorptive removal of tetracycline (Zheng et al., 2018). Similarly, a hybrid film with a composition of rGO/G-C3N4 was prepared and used against salt ions such as Na+ in water. The photocatalytic reduction method was used for the synthesis of rGO, whereas the hybrid films were synthesized by using vacuum filtration and UV radiation. By considering the effectiveness of the films, it could be concluded that these films are potential candidates to be used as next-generation separation films (Zhu et al., 2019). These GHNMs are thus potential materials in wastewater treatment. The use of environmentally friendly black Fe(II) as a reducing agent can significantly increase the stability and chemical properties of GHNMs in water (Qu et al., 2016).

7.3.2.2 Activated carbon supported HNMs Another type of HNMs with properties of both adsorption and photocatalysis is the TiO2-supported activated carbon hybrid material (TiO2/AC/HNM). The synergistic effect of adsorption and photocatalysis is responsible for the high popularity of these supportive hybrid materials. These hybrid materials offer efficient mass transfer for TiO2 applications. The proximity between the generated hydroxyl radicals and the concentrated contaminants is responsible for the high-performance applications of these hybrid materials and the increase in photocatalysis is attributed to the high photonic efficiency. The support provided by activated carbon (AC) results in the easy separation of TiO2 nanoparticles from treated water. A publication by Lim et al. (2011) reviewed the performance of AC-supported hybrid TiO2 nanomaterials. The key characteristics of HNMs are: (a) Easy separation. (b) Enhanced photocatalytic degradation. (c) Low deactivation. These characteristics make these materials reliable and versatile HNMs as compared to simple TiO2. The activity comparison between bare TiO2 and AC-supported TiO2 results in the 25% and 100% removal of methylene blue (MB) in 1 h and 3 h, respectively (Liu et al., 2006). Bare TiO2 shows a narrow light response for catalysis; however doping AC/TiO2 results in high and appealing photocatalysis. Doping extends the light response region

7.3 Support-based hybrid nanomaterials

of these HNMs. Many publications utilized doped AC/TiO2 HNMs for the initiation of photocatalysis in solar light (Dong et al., 2012, 2015; Yap and Lim, 2011, 2012). Besides the benefits offered by AC/TiO2 HNMs, there are certain strictures that need to be addressed for pilot-scale applications of these HNMs. Strictures such as mechanical and photo stability, regeneration, and fouling require considerable attention. Recently, the functionalization of AC/TiO2 with diethylenetriamine (AC/TiO2DETA) resulted in a significant enhancement in adsorption as compared to AC/TiO2. However, to further enhance the adsorption efficiency of these HNMs, more efforts are required. To extend the light response region of photocatalytic materials, sulfur and carbon are suitable candidates that can narrow the band gap to less than 3.2 eV. The chemistry behind narrowing the band gap includes the creation of trap sites between the conduction band gap (CB) and the valence band (VB). The presence of these trap sites results in the generation of electron/hole (e
/h+) pairs, even at low energy. For this reason, carbon is very popular in making photocatalytic nanoparticles and thin films (Ahmad et al., 2016).

7.3.2.3 Fly ash supported HNMs Coal-firing power plants generate aluminosilicate-rich byproducts known as fly ash (FA). This fly ash is low density, unique, cheap, nanotoxic, and has abundant hollow particles. Fly ash has potential applications in the construction industry, road manufacturing, and other applications, including cement additives, concrete admixture, and highway ice control. A large amount of fly ash is produced by industrial sectors, and this poses serious environmental and waste management issues. Therefore, the development and implementation of potential alternatives is urgently needed. In this respect, the cenospheres of fly ash can be used for evaluating the adsorption capacity of water vapors and are suitable to lower the temperature of surfaces under irradiation. Additionally, fly ash is a potential candidate to be used as a support/substrate (Mushtaq et al., 2019). The recent development in the catalytic system consisting of TiO2-supported fly ash has been investigated. The coating of fly ash with 10 wt% TiO2 with anatase crystal structures with a particle size of 9 nm. has been reported. This showed 67.5% and 63% removal of NO at 400°C and 300°C, respectively (Asl et al., 2018). After increasing the share of TiO2 up to 25 wt% to that of the fly ash, Visa and Duta (2013) reported much higher adsorption of copper and cadmium ions. The use of fly ash cenospheres as a carrier for the photocatalytic floating system of cobalt sulfophtalocyanine-sensitized TiO2 sol has also been reported. This floating photocatalytic system showed effective activity for MB degradation at the balanced extent of cobalt sulfophtalocyanine. In another study, the visible light-assisted degradation activity of poly-o-phenylenediamine/ TiO2/fly ash composites has been tested. At optimized conditions of pH ¼ 3 and a time of polymerization at about 40 min, a 60% degradation of antibiotic roxithromycin was achieved, which reflects the viability of composites. The modification of TiO2-loaded fly ash by H2O2 results in the enhanced degradation efficiency of MB (Huo et al., 2009). The visible light-assisted photocatalytic degradation efficiency of the floating photocatalytic system of fly ash cenosphere-loaded AgCl/TiO2 films was found to

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be up to 94.96% within 180 min against Rhodamine B dye. The effect of the wt% of TiO2 and the calcination temperature on the photocatalytic and structural properties of TiO2-supported coal fly ash samples was analyzed for the degradation of methyl orange (Surolia et al., 2010). Similarly, phenol removal (94.35%) was achieved within the irradiation time of 4 h by using TiO2/fly ash composites (Shi et al., 2011). The deposition of Fe(III)-doped TiO2 film on fly ash cenospheres was carried out and investigated for the photocatalytic degradation of MB (Wang et al., 2011). The doping of a composite with Fe(III) increases the degradation efficiency by 33% after calcination of a composite at 450°C. Guozhong (2004) reported the synthesis of ZnO-supported fly ash composites for evaluating their photocatalytic degradation efficiency against model pollutants and for the evaporation of hydrophilic surfaces. For the characterization of a ZnOfly ash hybrid, several analytical techniques were used, including scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), nitrogen adsorption-desorption isotherm (BET), X-ray diffraction (XRD), UV-Vis DRS, and XPS. A comparative study was also conducted for the evaluation of moisture sorption between bare fly ash and ZnO-supported fly ash. The reusability of the photocatalysts was also studied (Guozhong, 2004).

7.3.2.4 Some other supports used Besides all the above-mentioned adsorbents used for the synthesis of supported HNMs, the other low-cost adsorbents such as biomass and agricultural waste peels have been reported for wastewater treatment come with a number of drawbacks such as the high quantity required, sludge formation, and a long reaction time (Danish and Ahmad, 2018). Some other adsorbents in the literature are also presented here. Chitosan is another important material used as an adsorbent. The functional groups present in chitosan (hydroxyl and amino group) are responsible for adsorptive interactions between various pollutants such as pesticides, drugs/pharmaceuticals, phenols, ions, metals, dyes, etc. (Edwards et al., 2015). Highly porous and low-cost materials are also suitable candidates to be used as water purifiers. The use of nanotechnology in making nanoadsorbents of bentonite and its hybrids was also reported (Bialczyk et al., 2017). A series of nanomaterials (NMs) with unique physicochemical properties is being extensively used as nanoadsorbents. Nanomaterials, nanocomposites, hydrogel nanocomposites, boron nitride NMs, and many others were used and are being used for wastewater treatment (WWT). A comparative study between them and other traditional adsorbents was also conducted for environmental applications.

7.3.3 Physicochemical interactions between support and adsorbent The physical and chemical interactions between the adsorbate and adsorbents are also very important. These interactions include ion-exchange, chemisorption (Fig. 7.4), electrostatic interactions, surface complexation, π-π interactions, and H-bonding.

7.3 Support-based hybrid nanomaterials

Adsorbed pollutants

Chemisorption (Ea=20–500 kJ/mol)

Chemisorbed pollutants ultimately degraded

Physisorption (Ea =