Agri-Waste and Microbes for Production of Sustainable Nanomaterials 0128235756, 9780128235751

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Table of contents :
Front Cover
Agri-Waste and Microbes for Production of Sustainable Nanomaterials
Copyright
Contents
Contributors
Preface
Series preface
Chapter 1 Sustainable strategies for producing large-scale nanomaterials: A note from the editors
1 Introduction
2 Green synthesis nanomaterials
2.1 Agri-waste mediated nanoparticles
2.2 Microbes
3 Enzymes mediated nano synthesis
4 Protein-mediated nano synthesis
5 Polysaccharide mediated nano synthesis
6 Large-scale production of nanoparticles
7 Advantages
8 Future perspectives
9 Conclusion
References
Part I: Agri-waste for production of nanomaterials
Chapter 2 Synthesis of metal nanoparticles by microbes and biocompatible green reagents
1 Introduction
2 Synthesis by microorganisms
2.1 Fungi
2.2 Yeast
2.3 Algae
2.4 Bacteria
2.5 Actinomycetes
3 Synthesis by biocompatible green reagents
3.1 Ascorbic acid
3.2 Biopolymers
3.3 Amino acids and proteins
3.4 Sugars
4 Factors affecting biogenic synthesis of MNPs
4.1 Effect of pH
4.2 Effect of temperature
4.3 Effect of reactants concentration
4.4 Effect of time
5 Conclusion and future perspectives
References
Chapter 3 Plant and agri-waste- mediated synthesis of metal nanoparticles
1 Introduction
2 Synthesis from plant materials
2.1 Leaf extract
2.2 Fruit extract
2.3 Seed extract
2.4 Bark extract
2.5 Root extract
2.6 Flower extract
3 Synthesis from agri-waste
4 Factors influencing the biosynthesis of nanoparticles
4.1 pH of solution
4.2 Extract from plants/biomass dosage
4.3 Effect of precursor salt solution
4.4 Reaction temperature
4.5 Period of reaction time
4.6 Capping agents
4.7 Pressure
4.8 Environment
5 Conclusion and future prospective
References
Chapter 4 Plant-mediated copper nanoparticles for agri-ecosystem applications
1 Introduction
2 Synthesis of copper nanoparticles
2.1 Synthesis from plants
2.2 Synthesis from agriculture waste and other wastes
2.3 Mechanism of copper nanoparticle formation
3 Implementation of Cu-NPs in agriculture
4 Phytotoxicity and interaction with soil community
5 Application of copper nanoparticles
5.1 Biotic stress
5.1.1 Fungicidal effect
5.1.2 Bactericidal effect
5.1.3 Insecticidal effect
5.1.4 Nematicidal effect
5.1.5 Mechanism of antimicrobial activity of CuNPs
5.2 Abiotic stress
5.2.1 Salinity
5.2.2 Drought
5.2.3 Mineral toxicity
6 Conclusion and prospects
References
Chapter 5 Synthesis of silica nanoparticles from agricultural waste
1 Introduction
2 Agricultural waste
3 Effects of agricultural wastes
4 Silica nanoparticles
4.1 Synthesis of nanosilica
4.2 Characterization of synthesized nanosilica
4.3 Benefits of silica nanoparticles
4.4 Nanosilica applications in agriculture and the environment
5 Conclusion
References
Further reading
Chapter 6 Biomolecule-assisted biogenic synthesis of metallic nanoparticles
1 Introduction
2 Categories of biomolecules used in biosynthesis of nanoparticles
2.1 Synthesis of nanoparticles using carbohydrates
2.2 Synthesis of nanoparticles using proteins
2.2.1 Silk fibroin
2.2.2 Keratin
2.2.3 Gelatin
2.2.4 Elastin
2.2.5 Zein
2.2.6 Soy protein
2.2.7 Milk protein
2.2.8 Gliadin and legumin
2.2.9 Albumin
2.3 Synthesis of nanoparticles using enzymes
2.3.1 Protease
2.3.2 Keratinases
2.3.3 Amylase
2.3.4 Xylanase
2.3.5 Laccase
2.3.6 Cellulase
2.4 Synthesis of nanoparticles using vitamins
3 Conclusion and future prospects
References
Chapter 7 Bacterial and fungal mediated synthesis, characterization and applications of AgNPs
1 Introduction
2 Green synthesis of AgNPs
2.1 Plant mediated synthesis
2.2 Algae mediated synthesis
2.3 Bacteria mediated synthesis of AgNPs
2.3.1 Applications of bacteria mediated synthesis of AgNPs
2.4 Fungal mediated synthesis of AgNPs
3 Conclusion
References
Chapter 8 Agro-waste materials: Sustainable substrates in nanotechnology
1 Introduction
2 Horticultural wastes
2.1 Aquacultural wastes
2.2 Extraction of agro-waste for nanoparticle synthesis
2.3 Composition and use of agro-waste for synthesis
3 Synthesis of various nanoparticles using agricultural wastes
3.1 Hydrothermal synthesis
4 Carbon dots, a major nanomaterial from agricultural wastes
4.1 Nanocellulose, another important product of agricultural waste
5 Nanocomposites from wastes and their applications
6 Shortcomings and future perspective
Acknowledgments
References
Chapter 9 Synthesis of eco-friendly graphene from agricultural wastes
1 Introduction
2 Modified Hummer’s method
3 Graphene synthesis from agricultural wastes
3.1 Sugarcane bagasse
3.2 Durian rind and sugarcane bagasse
3.3 Rice husk
3.4 Coconut shell and carbonized wood
3.5 Coconut husks, coconut shell, rice husk and sugarcane bagasse
3.6 Mango peel
3.7 Banana peel
3.8 Rice husk, sugarcane bagasse and waste newspaper
3.9 Papaya seeds
3.10 Rice straw
3.11 Chocolate, grass, plastics, cockroaches, cookies and dog feces
3.12 Rice bran, sugarcane bagasse, orange peel
3.13 Jujube seeds
3.14 Wood of the black mulberry tree, leaf of plane trees, sugarcane bagasse, fruit rind of oranges, newspapers, chicken ...
3.15 Tea waste
3.16 Seaweed fibers
3.17 Palm oil waste
4 Conclusions
References
Chapter 10 Fruit peel waste-to-wealth: Bionanomaterials production and their applications in agroecosystems
1 Introduction
2 Fruit peel physicochemical and biochemical characters
3 Synthesis of metallic nanoparticles from fruit peel
3.1 Gold nanoparticles
3.2 Silver nanoparticles
3.3 Carbon nanomaterials
3.4 Copper nanoparticles
3.5 Silica nanoparticles
3.6 Titanium dioxide nanoparticles
3.7 Zinc nanoparticles
4 Bioactive compounds in fruit peels hybrid with nanomaterials
5 Synthesis mechanisms
6 Further prospective and challenges
7 Conclusion
References
Chapter 11 Eggshell and fish/shrimp wastes for synthesis of bio-nanoparticles
1 Introduction
2 Chemical composition of eggshells and fish/shrimp waste
2.1 Eggshells
2.2 Fish scales
2.3 Shrimp shells
3 Synthesis of nanoparticles from eggshells and fish/shrimp waste
3.1 Mechano-milling
3.2 Coprecipitation
3.3 Solvothermal/hydrothermal
3.4 Sonochemical method
3.5 Irradiation method
3.6 Sol-gel method
4 Properties of fish/shrimp waste and eggshell derived nanoparticles
4.1 Antimicrobial activity
4.2 Catalytic properties
4.3 Absorbing properties
4.4 Biocompatibility
4.5 Other properties
5 Applications
5.1 Catalytic application
5.2 Food industry
5.3 Environmental remediation
5.4 Biomedical application
5.5 Fuel additives
6 Application of modeling and optimization techniques for nanoparticles
7 Conclusions
Acknowledgments
References
Chapter 12 Vegetables waste for biosynthesis of various nanoparticles
1 Introduction
2 Green synthesis process for nanomaterials
2.1 Physical and chemical process
2.1.1 Ball-milling process
2.1.2 Microwave irradiation process
2.1.3 Photocatalysis
2.1.4 Hydrothermal process
2.1.5 Ultrasound-assisted synthesis
2.1.6 Magnetic field-assisted synthesis
3 Vegetable wastes as nanofactories
4 Synthesis of carbon-based nanomaterials from vegetable waste
5 Biosynthesis of NPs from vegetable wastes
5.1 Antimicrobial activity of biosynthesis of NPs from vegetable wastes
5.2 Dye degradation using biosynthesis of NPs from vegetable wastes
5.3 Another application of biosynthesis of NPs from vegetable wastes
6 Mechanism of nanoparticle formation
7 Morphology control of plant extract nanoparticles
8 Conclusion
Acknowledgment
References
Part II: Microorganisms for nanomaterials synthesis
Chapter 13 Microbes and agricultural waste: A safe resource for the production of bionanomaterials
1 Introduction
2 Microbial nanostructures
2.1 Metallic nanostructures
2.2 Compound-based nanoparticles
2.3 Organic and inorganic composites
3 Agro-based nanostructures
3.1 Metal nanoparticles
3.2 Nanocomposites
3.3 Aerogels
3.4 Magnetic and biochar-based nanoparticles
3.5 Silica nanoparticles
4 Mechanisms of nanostructures
4.1 Enzymes
4.1.1 Intracellular
4.1.2 Extracellular
4.2 E-shuttle quinone
4.3 Exopolysaccharides
5 Conclusion
References
Chapter 14 Microbial synthesis of magnetic nanomaterials
1 Introduction
2 General synthesis of nanoparticles
2.1 Top-down approaches
2.2 Bottom-up approaches
2.2.1 Physical methods
2.2.2 Chemical methods
2.2.2.1 Sol-gel method
2.2.2.2 Microemulsion method
2.2.2.3 Hydrothermal method
2.2.2.4 Polyol method
3 Chemical synthesis of magnetic nanoparticles
3.1 Co-precipitation method
3.2 Reduction method
3.3 Thermal decomposition
3.4 The biogenic approach
3.4.1 Plant extract
3.4.2 Microbial route of synthesis: General procedure and different approaches
3.4.2.1 Bacteria
3.4.2.2 Algae
3.4.2.3 Fungi
4 Magnetic nanoparticles: Synthesis and applications
4.1 Ferromagnetic metals
4.1.1 Iron
4.1.2 Nickel
4.1.3 Cobalt
4.2 Paramagnetic metals
4.2.1 Aluminum oxide
4.2.2 Magnesium
4.2.3 Lithium
4.2.4 Platinum
4.2.5 Palladium
4.2.6 Strontium
4.2.7 Selenium
4.2.8 Titanium
4.2.9 Zirconium
5 Conclusion and further outlook
References
Chapter 15 Mycogenic nanoparticles: Synthesis, characterizations and applications
1 Introduction
2 Myconanotechnoloy: Fungi as a potential source for mycogenic nanoparticles
3 Intracellular and extracellular synthesis of mycogenic nanoparticle with types
4 Mechanism of mycogenic nanoparticle biosynthesis
5 Characterization of mycogenic nanoparticles
5.1 UV-visible spectrophotometer
5.2 Fourier transform infrared spectroscopy
5.3 Atomic surface microscopy
5.4 Transmission electron microscopy (TEM)
5.5 X-ray diffraction technique
5.6 Scanning electron microscope (SEM)
5.7 Energy dispersive X-ray spectroscopy
6 Applications of mycogenic nanoparticles
6.1 Agriculture
6.2 Medicine
7 Conclusions
References
Chapter 16 Actinomycetes-assisted nanoparticles: Synthesis and applications
1 Introduction
2 Isolation of actinomycetes
3 Actinomycete assisted synthesis of nanoparticles
3.1 Extracellular vs intracellular synthesis
3.1.1 Silver nanoparticles (AgNPs)
3.1.2 Gold nanoparticles (AuNPs)
3.1.3 Copper nanoparticles (CuNPs)
3.1.4 Selenium nanoparticles (SeNPs)
3.1.5 Other metals
3.2 Characterization of nanoparticles
3.2.1 UV-vis spectroscopy (UV-vis)
3.2.2 Transmission electron microscopy (TEM)
3.2.3 Scanning electron microscopy (SEM)
3.2.4 Fourier-transform infrared spectroscopy (FTIR)
3.2.5 X-ray diffraction (XRD)
3.2.6 Energy dispersive X-ray diffraction (EDX/EDAX/EDS)
3.2.7 Dynamic light scattering (DLS)
3.2.8 Atomic force microscopy (AFM)
3.2.9 Other techniques
4 Applications of actinomycete synthesized nanoparticles
4.1 Agriculture
4.2 Catalytic activity (nanocatalyst)
4.3 Antimicrobial activity
4.4 Anti-oxidant properties
4.5 Anti-malarial and anti-parasitic activity
4.6 Dye degradation
4.7 Anti-biofouling activity
4.8 Larvicidal activity
4.9 Cytotoxicity and anticancer activity
4.10 Other applications
5 Toxicity of nanoparticles
6 Conclusion
References
Chapter 17 Biosynthesis of Silver Nanoparticles: Synthesis, mechanism, and characterization
1 Introduction
2 Methods of preparation of silver nanoparticle
2.1 Physical methods
2.2 Chemical methods
2.3 Photochemical method
2.4 Biosynthesis silver nanoparticles
3 Mechanism of biosynthesis of silver nanoparticles
4 Characterization techniques of silver nanoparticles
4.1 UV–visible spectroscopy
4.2 Fourier transform infrared spectroscopy (FTIR)
4.3 X-ray diffractometry (XRD)
4.4 X-ray photoelectron spectroscopy (XPS)
4.5 Scanning electron microscopy (SEM)
4.6 Transmission electron microscopy (TEM)
4.7 Dynamic light scattering (DLS)
4.8 Atomic force microscopy (AFM)
4.9 Localized surface plasmon resonance (LSPR):
5 Conclusion
References
Chapter 18 Agri-food and environmental applications of bionanomaterials produced from agri-waste and microbes
1 Introduction
2 Agri-food applications
2.1 Nano-pesticides
2.2 Nano-fertilizers
2.3 Nano-sensors in plant system
2.4 Nano-additives
2.5 Food packaging
2.6 Nano-carriers for gene delivery into plants
3 Environmental applications
3.1 Nano-sensors
3.2 Wastewater treatment
3.3 Pollutant degradations
4 Conclusion
References
Chapter 19 Benign fabrication of metallic/metal oxide nanoparticles from algae
1 Introduction
2 Preference for plants
3 Algae
4 Nanoparticles from microalgae
4.1 Metal NPs
4.2 Metal oxide NPs
5 Nanoparticles synthesized by macroalgae
5.1 Metal NPs
5.2 Production of metal oxide NPs
6 Possible mechanism
7 Diatoms
8 Future outlook
9 Conclusion
Acknowledgments
References
Chapter 20 Biogenic metal sulfide nanoparticles synthesis and applications for biomedical and environmental technology
1 Introduction
2 Metal nanoparticles
3 Metal sulfide nanoparticles
3.1 Cadmium sulfide nanoparticles
3.2 Copper sulfide nanoparticles
3.2.1 Zinc sulfide nanoparticles
3.3 Iron sulfide nanoparticles
3.4 Silver sulfide nanoparticles
3.5 Arsenic sulfide nanoparticles
3.6 Gold sulfide nanoparticles
3.7 Bismuth sulfide nanoparticles
3.8 Manganese sulfide nanoparticles
4 Conclusion
References
Chapter 21 Microbial-mediated copper nanoparticles synthesis, characterization, and applications
1 Introduction
2 Copper nanoparticles
3 Techniques for the synthesis of copper nanoparticles
4 Need for microbial-mediated synthesis of copper nanoparticles
5 Microbial-mediated synthesis of copper nanoparticles
5.1 Bacteria
5.2 Actinomycetes
5.3 Fungi
5.4 Yeast
5.5 Algae
5.6 Viruses
6 Characterization of copper nanoparticles
6.1 Nanoparticle formation analysis
6.2 Extraction of nanoparticles
6.3 Tracking of nanoparticles
6.4 Morphology and size analysis
6.4.1 Transmission electron microscopy
6.4.2 Scanning electron microscopy
6.4.3 Atomic force microscopy
6.5 Surface charge analysis
6.5.1 Zeta potential analysis
6.6 Optical properties
6.6.1 Fourier transform infrared spectroscopy
6.7 Thermal properties
6.7.1 Differential scanning calorimetry
6.7.2 Thermal gravimetric analysis
6.8 Elemental composition analysis
6.8.1 Energy dispersive X-ray
6.8.2 X-ray absorption spectroscopy
6.9 Structure analysis
6.9.1 X-ray diffractometer
6.9.2 X-ray photoelectron spectroscopy
6.10 Magnetic properties analysis
6.10.1 Vibrating sample magnetometry
6.10.2 Superconducting quantum interference device
6.11 Surface hydrophobicity assessment
7 Applications of CuNPs
7.1 Antimicrobial activity
7.2 E-waste management
8 Conclusion
References
Chapter 22 Green nanomaterials produced by agro-waste and microbes: Mechanisms and risk assessment
1 Introduction
2 Green nanomaterials from agriculture waste
2.1 Green nanomaterials from grain straw
2.1.1 Metal nanoparticles from grain straw and their applications
2.1.2 Cellulosic nanomaterials from grain straw and their applications
2.2 Green nanomaterials from sugarcane bagasse
2.2.1 Metal nanoparticles from sugarcane bagasse and their applications
2.2.2 Cellulosic nanomaterials from sugarcane bagasse and their applications
2.3 Green nanomaterials from grain hulls
2.3.1 Application of silica nanoparticles obtained from rice hulls
2.3.2 Nobel metal nanoparticles from rice hulls and their applications
2.4 Green nanomaterials from cotton stalk
2.5 Green nanomaterials from corncob
3 Green nanomaterials from microbial biomass
4 Conclusion
References
Chapter 23 Frontier and perspective outlook on agrowaste nanoparticles for healthcare and environment
1 Introduction
2 Nanoparticle synthesis using agricultural waste
3 Applications
3.1 Biomedical applications of nanoparticle synthesized using agricultural waste
3.2 Nanoparticles in healthcare
3.3 Nanoparticles for environmental applications
4 Limitations of nanotechnology in healthcare
5 Conclusion
References
Chapter 24 Mechanistic approach on the synthesis of metallic nanoparticles from microbes
1 Introduction
2 Synthesis of nanoparticles
2.1 Biological synthesis
2.2 Mechanism of nanoparticle synthesis
2.2.1 Bacteria
2.2.2 Fungi
2.2.3 Actinomycetes
2.2.4 Yeast
3 Conclusion
References
Chapter 25 Microbially synthesized nanoparticles: A promising future for insecticidal efficacy studies
1 Introduction
2 Types of nanoparticles
3 Synthesis of nanoparticles
3.1 Green synthesis of nanoparticles
3.2 Plant-mediated nanoparticles
4 Microbial synthesis of nanoparticles
4.1 Bacteria-mediated nanoparticles
4.2 Actinomycetes-mediated nanoparticles
4.3 Fungi-mediated nanoparticles
4.4 Algae-mediated nanoparticles
5 Mechanism of nanoparticle formation
6 Insecticidal efficacy of microbial-mediated nanoparticles
7 Future perspectives
8 Conclusion
References
Chapter 26 Biomedical applications of ginsenosides nanoparticles synthesized using microbes
1 Introduction
2 Probiotics
2.1 Versatile clinical applications of the probiotics
2.2 Probiotic mediated nanoparticle synthesis
3 Mechanisms of the microbial synthesis of nanoparticles
3.1 Intracellular method
3.2 Extracellular method
3.3 Optimization of the microbial nanoparticle synthesis
4 Biomedical applications of nanoparticles
5 Bacteria based nanoparticles
6 Ginseng
6.1 Ginsenosides and its types
6.2 Multifaceted roles of the ginsenosides
6.3 Need of the ginsenoside nanosystems
6.4 Ginsenosides-based micro/nanocarriers
6.4.1 Emulsion systems
6.4.1.1 Microemulsions
6.4.1.2 Nanoemulsions
6.4.2 Polymer microparticles
6.4.3 Polymer nanoparticles
6.4.4 Liposomes
6.4.5 Ethosomes and transfersomes
6.4.6 Niosomes
7 Microbial synthesis of the ginsenoside nanoparticles and applications
8 Futuristic views
9 Conclusion
References
Chapter 27 Synthesis of selenium nanoparticles by using microorganisms and agri-based products
1 Introduction
2 Synthesis of SeNPs
2.1 Physical methods
2.2 Chemical methods
2.3 Biological synthesis of SeNPs
2.3.1 Synthesis of SeNPs by bacteria
2.3.2 Synthesis of SeNPs by fungus, yeast and actinomycetes
2.3.3 Mushroom mediated synthesis of SeNPs
2.4 Mechanism of microbial synthesis of SeNPs
2.4.1 Selenate reductase
2.4.2 Selenite reductases
2.5 Agro-based synthesis of SeNPs
2.5.1 Synthesis of SeNPs by plant leaves
2.5.2 Fruit-based synthesis of SeNPs
2.5.3 Flower based synthesis of SeNPs
2.5.4 Other agro materials based synthesis of SeNPs
2.6 Mechanism of agro-based materials synthesis of SeNPs
3 Characterizations of SeNPs
4 Applications of SeNPs
5 Conclusions
References
Further reading
Chapter 28 Plant-meditated methods for synthesis of silver nanoparticles
1 Introduction
2 Types of green approaches for Ag-nanomaterials
2.1 Biological method
2.2 Photochemical method
3 Green synthesis
4 Applications of silver nanoparticles
5 Conclusions
References
Chapter 29 Rice wastes for green production and sustainable nanomaterials: An overview
1 Introduction
2 Types of rice wastes
2.1 Rice straw
2.2 Rice husk
2.3 Rice bran
3 Amount of rice wastes
4 Utilization of rice-waste
5 Agric-waste as green sources of nanoparticles
6 Nanomaterials extracted from rice wastes
6.1 Silica nanoparticles (SiNPs)
6.2 Carbon nanotubes (CNTs)
6.3 Cellulose nanofibers (CNF)
6.4 Other nanoparticles
7 Applications of rice bio nanomaterials
8 Conclusion future perspectives
References
Index
Back Cover
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Agri-Waste and Microbes for Production of Sustainable Nanomaterials

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Nanobiotechnology for Plant Protection

­Agri-Waste and Microbes for Production of Sustainable Nanomaterials Edited by

Kamel A. Abd-Elsalam

Research Professor, Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt

Dr. Rajiv Periakaruppan

Assistant Professor, Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India

S. Rajeshkumar

Associate Professor, Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India

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 Copyright © 2022 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: 978-0-12-823575-1

For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

Publisher: Nikki Levy Acquisitions Editor: Simon Holt Editorial Project Manager: Rafael G Trombaco Production Project Manager: Selvaraj Raviraj Cover designer: Greg Harris Typeset by STRAIVE, India

Contents Contributors.............................................................................................................xxi Preface....................................................................................................................xxix Series preface.........................................................................................................xxxi

CHAPTER 1 Sustainable strategies for producing large-scale nanomaterials: A note from the editors...........................1 1 2

3 4 5 6 7 8 9

Kamel A. Abd-Elsalam, S. Rajeshkumar, and Rajiv Periakaruppan Introduction...................................................................................... 1 Green synthesis nanomaterials........................................................ 2 2.1 Agri-waste mediated nanoparticles........................................... 2 2.2 Microbes................................................................................... 3 Enzymes mediated nano synthesis................................................... 5 Protein-mediated nano synthesis..................................................... 6 Polysaccharide mediated nano synthesis......................................... 6 Large-scale production of nanoparticles.......................................... 7 Advantages....................................................................................... 8 Future perspectives.......................................................................... 9 Conclusion..................................................................................... 10 References...................................................................................... 10

PART I Agri-waste for production of nanomaterials CHAPTER 2 Synthesis of metal nanoparticles by microbes and biocompatible green reagents................................17 1 2

3

Vijay Devra Introduction.................................................................................... 17 Synthesis by microorganisms........................................................ 19 2.1 Fungi.......................................................................................19 2.2 Yeast........................................................................................ 21 2.3 Algae....................................................................................... 26 2.4 Bacteria................................................................................... 27 2.5 Actinomycetes........................................................................ 28 Synthesis by biocompatible green reagents................................... 28 3.1 Ascorbic acid.......................................................................... 28 3.2 Biopolymers............................................................................ 29 3.3 Amino acids and proteins....................................................... 30 3.4 Sugars..................................................................................... 31

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5

Factors affecting biogenic synthesis of MNPs..............................34 4.1 Effect of pH............................................................................ 34 4.2 Effect of temperature.............................................................. 34 4.3 Effect of reactants concentration............................................ 35 4.4 Effect of time.......................................................................... 35 Conclusion and future perspectives............................................... 37 References...................................................................................... 37

CHAPTER 3 Plant and agri-waste-mediated synthesis of metal nanoparticles.....................................................47 1 2

3 4

5

Vijay Devra Introduction.................................................................................... 47 Synthesis from plant materials....................................................... 49 2.1 Leaf extract............................................................................. 49 2.2 Fruit extract............................................................................. 54 2.3 Seed extract............................................................................. 54 2.4 Bark extract............................................................................. 55 2.5 Root extract............................................................................. 58 2.6 Flower extract......................................................................... 58 Synthesis from agri-waste.............................................................. 58 Factors influencing the biosynthesis of nanoparticles................... 60 4.1 pH of solution......................................................................... 60 4.2 Extract from plants/biomass dosage....................................... 62 4.3 Effect of precursor salt solution.............................................. 64 4.4 Reaction temperature.............................................................. 64 4.5 Period of reaction time............................................................ 65 4.6 Capping agents........................................................................ 67 4.7 Pressure................................................................................... 67 4.8 Environment............................................................................ 67 Conclusion and future prospective................................................68 References...................................................................................... 68

CHAPTER 4 Plant-mediated copper nanoparticles for agri-ecosystem applications.....................................79 1 2

3

Heba I. Mohamed, Tony Kevork Sajyan, Roshan Shaalan, Rami Bejjani, Youssef Najib Sassine, and Abdul Basit Introduction.................................................................................... 79 Synthesis of copper nanoparticles................................................. 80 2.1 Synthesis from plants.............................................................. 81 2.2 Synthesis from agriculture waste and other wastes................ 84 2.3 Mechanism of copper nanoparticle formation........................ 85 Implementation of Cu-NPs in agriculture...................................... 86

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6

Phytotoxicity and interaction with soil community....................... 92 Application of copper nanoparticles.............................................. 93 5.1 Biotic stress............................................................................. 93 5.2 Abiotic stress........................................................................ 101 Conclusion and prospects............................................................ 104 References.................................................................................... 105

CHAPTER 5 Synthesis of silica nanoparticles from agricultural waste........................................................... 121 1 2 3 4

5

Evidence Akhayere and Doga Kavaz Introduction.................................................................................. 121 Agricultural waste........................................................................ 123 Effects of agricultural wastes....................................................... 126 Silica nanoparticles...................................................................... 126 4.1 Synthesis of nanosilica......................................................... 128 4.2 Characterization of synthesized nanosilica........................... 128 4.3 Benefits of silica nanoparticles............................................. 131 4.4 Nanosilica applications in agriculture and the environment.... 132 Conclusion................................................................................... 134 References.................................................................................... 134 Further reading............................................................................. 138

CHAPTER 6 Biomolecule-assisted biogenic synthesis of metallic nanoparticles................................................... 139 1 2

3

Satinder Pal Kaur Malhotra and Mousa A. Alghuthaymi Introduction.................................................................................. 139 Categories of biomolecules used in biosynthesis of nanoparticles................................................................................ 140 2.1 Synthesis of nanoparticles using carbohydrates................... 140 2.2 Synthesis of nanoparticles using proteins............................. 143 2.3 Synthesis of nanoparticles using enzymes............................ 149 2.4 Synthesis of nanoparticles using vitamins............................ 153 Conclusion and future prospects.................................................. 153 References.................................................................................... 154

CHAPTER 7 Bacterial and fungal mediated synthesis, characterization and applications of AgNPs.............. 165 1 2

S. Rajeshkumar, M. Jeevitha, D. Sheba, and M. Nagalingam Introduction.................................................................................. 165 Green synthesis of AgNPs........................................................... 166 2.1 Plant mediated synthesis....................................................... 166 2.2 Algae mediated synthesis..................................................... 168

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2.3 Bacteria mediated synthesis of AgNPs................................. 171 2.4 Fungal mediated synthesis of AgNPs................................... 177 Conclusion................................................................................... 178 References.................................................................................... 182

CHAPTER 8 Agro-waste materials: Sustainable substrates in nanotechnology............................................................... 187 1 2

3 4

5 6

Elias E. Elemike, Anthony C. Ekennia, Damian C. Onwudiwe, and Rachael O. Ezeani Introduction.................................................................................. 187 Horticultural wastes..................................................................... 189 2.1 Aquacultural wastes.............................................................. 190 2.2 Extraction of agro-waste for nanoparticle synthesis............. 191 2.3 Composition and use of agro-waste for synthesis................ 191 Synthesis of various nanoparticles using agricultural wastes...... 196 3.1 Hydrothermal synthesis........................................................ 200 Carbon dots, a major nanomaterial from agricultural wastes...... 201 4.1 Nanocellulose, another important product of agricultural waste..................................................................................... 204 Nanocomposites from wastes and their applications................... 205 Shortcomings and future perspective........................................... 207 Acknowledgments....................................................................... 208 References.................................................................................... 208

CHAPTER 9 Synthesis of eco-friendly graphene from agricultural wastes......................................................... 215 1 2 3

Rajendran Rajakumari, Sabu Thomas, and Nandakumar Kalarikkal Introduction.................................................................................. 215 Modified Hummer’s method........................................................ 216 Graphene synthesis from agricultural wastes.............................. 217 3.1 Sugarcane bagasse.............................................................. 217 3.2 Durian rind and sugarcane bagasse..................................... 218 3.3 Rice husk............................................................................. 218 3.4 Coconut shell and carbonized wood................................... 218 3.5 Coconut husks, coconut shell, rice husk and sugarcane bagasse................................................................................ 219 3.6 Mango peel.......................................................................... 220 3.7 Banana peel......................................................................... 221 3.8 Rice husk, sugarcane bagasse and waste newspaper.......... 222 3.9 Papaya seeds....................................................................... 222 3.10 Rice straw........................................................................... 222

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3.11 Chocolate, grass, plastics, cockroaches, cookies and dog feces............................................................................. 224 3.12 Rice bran, sugarcane bagasse, orange peel......................... 224 3.13 Jujube seeds........................................................................ 225 3.14 Wood of the black mulberry tree, leaf of plane trees, sugarcane bagasse, fruit rind of oranges, newspapers, chicken bone and cow dung................................................ 225 3.15 Tea waste............................................................................. 226 3.16 Seaweed fibers.................................................................... 227 3.17 Palm oil waste..................................................................... 227 Conclusions.................................................................................. 228 References.................................................................................... 228

CHAPTER 10 Fruit peel waste-to-wealth: Bionanomaterials production and their applications in agroecosystems............................................................... 231 1 2 3

4 5 6 7

Manal M. Ahmed, Marwa T. Badawy, Farah K. Ahmed, Anu Kalia, and Kamel A. Abd-Elsalam Introduction.................................................................................. 231 Fruit peel physicochemical and biochemical characters............. 232 Synthesis of metallic nanoparticles from fruit peel..................... 234 3.1 Gold nanoparticles................................................................ 235 3.2 Silver nanoparticles..............................................................236 3.3 Carbon nanomaterials........................................................... 237 3.4 Copper nanoparticles............................................................ 238 3.5 Silica nanoparticles............................................................... 241 3.6 Titanium dioxide nanoparticles............................................ 241 3.7 Zinc nanoparticles................................................................. 242 Bioactive compounds in fruit peels hybrid with nanomaterials..244 Synthesis mechanisms................................................................. 245 Further prospective and challenges.............................................. 247 Conclusion................................................................................... 248 References.................................................................................... 248

CHAPTER 11 Eggshell and fish/shrimp wastes for synthesis of bio-nanoparticles....................................................... 259 1 2

Monika Yadav, Nidhi Pareek, and Vivekanand Vivekanand Introduction.................................................................................. 259 Chemical composition of eggshells and fish/shrimp waste......... 260 2.1 Eggshells............................................................................... 260 2.2 Fish scales............................................................................. 260 2.3 Shrimp shells........................................................................ 261

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Synthesis of nanoparticles from eggshells and fish/shrimp waste..... 261 3.1 Mechano-milling................................................................... 263 3.2 Coprecipitation..................................................................... 263 3.3 Solvothermal/hydrothermal.................................................. 264 3.4 Sonochemical method........................................................... 265 3.5 Irradiation method................................................................ 265 3.6 Sol-gel method...................................................................... 266 Properties of fish/shrimp waste and eggshell derived nanoparticles................................................................................ 267 4.1 Antimicrobial activity........................................................... 267 4.2 Catalytic properties............................................................... 270 4.3 Absorbing properties............................................................ 270 4.4 Biocompatibility................................................................... 270 4.5 Other properties.................................................................... 271 Applications................................................................................. 271 5.1 Catalytic application............................................................. 271 5.2 Food industry........................................................................ 271 5.3 Environmental remediation................................................... 272 5.4 Biomedical application......................................................... 272 5.5 Fuel additives........................................................................ 273 Application of modeling and optimization techniques for nanoparticles................................................................................ 275 Conclusions.................................................................................. 276 Acknowledgments....................................................................... 276 References.................................................................................... 276

CHAPTER 12 Vegetables waste for biosynthesis of various nanoparticles................................................................... 281 1 2 3 4 5

Rishabh Anand Omar, Divya Chauhan, Neetu Talreja, R.V. Mangalaraja, and Mohammad Ashfaq Introduction.................................................................................. 281 Green synthesis process for nanomaterials.................................. 283 2.1 Physical and chemical process.............................................. 283 Vegetable wastes as nanofactories............................................... 285 Synthesis of carbon-based nanomaterials from vegetable waste...... 286 Biosynthesis of NPs from vegetable wastes................................ 287 5.1 Antimicrobial activity of biosynthesis of NPs from vegetable wastes...................................................................287 5.2 Dye degradation using biosynthesis of NPs from vegetable wastes...................................................................288 5.3 Another application of biosynthesis of NPs from vegetable wastes...................................................................289

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Mechanism of nanoparticle formation......................................... 291 Morphology control of plant extract nanoparticles.....................291 Conclusion................................................................................... 292 Acknowledgment......................................................................... 292 References.................................................................................... 292

PART II Microorganisms for nanomaterials synthesis CHAPTER 13 Microbes and agricultural waste: A safe resource for the production of bionanomaterials............................................................ 301

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Vishal Ahuja, Jeyabalan Sangeetha, Anand Torvi, Devarajan Thangadurai, Arun Kashivishwanath Shettar, Muniswamy David, and Shivasharana Chandrabanda Thimmappa Introduction.................................................................................. 301 Microbial nanostructures............................................................. 302 2.1 Metallic nanostructures......................................................... 305 2.2 Compound-based nanoparticles............................................ 306 2.3 Organic and inorganic composites........................................ 307 Agro-based nanostructures.......................................................... 307 3.1 Metal nanoparticles............................................................... 307 3.2 Nanocomposites.................................................................... 310 3.3 Aerogels................................................................................ 310 3.4 Magnetic and biochar-based nanoparticles........................... 310 3.5 Silica nanoparticles............................................................... 311 Mechanisms of nanostructures.................................................... 312 4.1 Enzymes................................................................................ 312 4.2 E-shuttle quinone.................................................................. 314 4.3 Exopolysaccharides.............................................................. 314 Conclusion................................................................................... 316 References.................................................................................... 316

CHAPTER 14 Microbial synthesis of magnetic nanomaterials........ 323 1 2

3

Sadia Saif, Syed Farooq Adil, Amna Chaudhry, and Mujeeb Khan Introduction.................................................................................. 323 General synthesis of nanoparticles.............................................. 324 2.1 Top-down approaches........................................................... 325 2.2 Bottom-up approaches.......................................................... 325 Chemical synthesis of magnetic nanoparticles............................ 328 3.1 Co-precipitation method....................................................... 329 3.2 Reduction method................................................................. 329

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3.3 Thermal decomposition........................................................ 330 3.4 The biogenic approach.......................................................... 330 Magnetic nanoparticles: Synthesis and applications................... 334 4.1 Ferromagnetic metals............................................................ 334 4.2 Paramagnetic metals............................................................. 338 Conclusion and further outlook................................................... 346 References.................................................................................... 346

CHAPTER 15 Mycogenic nanoparticles: Synthesis, characterizations and applications............................. 357 1 2 3 4 5

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Jeyapragash Danaraj, Rajiv Periakaruppan, R. Usha, C.K. Venil, and Ashwag Shami Introduction.................................................................................. 357 Myconanotechnoloy: Fungi as a potential source for mycogenic nanoparticles............................................................. 358 Intracellular and extracellular synthesis of mycogenic nanoparticle with types................................................................ 360 Mechanism of mycogenic nanoparticle biosynthesis.................. 360 Characterization of mycogenic nanoparticles.............................. 364 5.1 UV-visible spectrophotometer.............................................. 365 5.2 Fourier transform infrared spectroscopy............................... 365 5.3 Atomic surface microscopy.................................................. 365 5.4 Transmission electron microscopy (TEM)........................... 365 5.5 X-ray diffraction technique................................................... 366 5.6 Scanning electron microscope (SEM).................................. 366 5.7 Energy dispersive X-ray spectroscopy.................................. 366 Applications of mycogenic nanoparticles.................................... 366 6.1 Agriculture............................................................................ 366 6.2 Medicine............................................................................... 367 Conclusions.................................................................................. 367 References.................................................................................... 369

CHAPTER 16 Actinomycetes-assisted nanoparticles: Synthesis and applications........................................... 375 1 2 3

Subha Priya Venkateswaran, Vignesh Kumar Palaniswamy, R. Vishvanand, and Rajiv Periakaruppan Introduction.................................................................................. 375 Isolation of actinomycetes........................................................... 378 Actinomycete assisted synthesis of nanoparticles....................... 378 3.1 Extracellular vs intracellular synthesis................................. 380 3.2 Characterization of nanoparticles......................................... 384

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Applications of actinomycete synthesized nanoparticles................................................................................ 386 4.1 Agriculture.......................................................................... 386 4.2 Catalytic activity (nanocatalyst)......................................... 386 4.3 Antimicrobial activity......................................................... 386 4.4 Anti-oxidant properties....................................................... 389 4.5 Anti-malarial and anti-parasitic activity............................. 389 4.6 Dye degradation.................................................................. 389 4.7 Anti-biofouling activity...................................................... 389 4.8 Larvicidal activity............................................................... 389 4.9 Cytotoxicity and anticancer activity................................... 389 4.10 Other applications............................................................... 390 Toxicity of nanoparticles............................................................. 390 Conclusion................................................................................... 390 References.................................................................................... 391

CHAPTER 17 Biosynthesis of Silver Nanoparticles: Synthesis, mechanism, and characterization................................ 397 1 2

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Santwana Padhi and Anindita Behera Introduction.................................................................................. 397 Methods of preparation of silver nanoparticle............................. 399 2.1 Physical methods.................................................................. 399 2.2 Chemical methods................................................................ 400 2.3 Photochemical method.......................................................... 408 2.4 Biosynthesis silver nanoparticles.......................................... 408 Mechanism of biosynthesis of silver nanoparticles................................................................................ 416 Characterization techniques of silver nanoparticles................................................................................ 421 4.1 UV–visible spectroscopy...................................................... 421 4.2 Fourier transform infrared spectroscopy (FTIR).................. 421 4.3 X-ray diffractometry (XRD)................................................. 422 4.4 X-ray photoelectron spectroscopy (XPS)............................. 422 4.5 Scanning electron microscopy (SEM).................................. 422 4.6 Transmission electron microscopy (TEM)........................... 422 4.7 Dynamic light scattering (DLS)............................................ 423 4.8 Atomic force microscopy (AFM)......................................... 423 4.9 Localized surface plasmon resonance (LSPR):.................... 423 Conclusion................................................................................... 424 References.................................................................................... 424

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CHAPTER 18 Agri-food and environmental applications of bionanomaterials produced from agri-waste and microbes........................................................................... 441 1 2

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Marwa T. Badawy, Manal Mostafa, Mohamed S. Khalil, and Kamel A. Abd-Elsalam Introduction.................................................................................. 441 Agri-food applications................................................................. 442 2.1 Nano-pesticides..................................................................... 442 2.2 Nano-fertilizers..................................................................... 444 2.3 Nano-sensors in plant system............................................... 446 2.4 Nano-additives...................................................................... 447 2.5 Food packaging..................................................................... 448 2.6 Nano-carriers for gene delivery into plants.......................... 449 Environmental applications......................................................... 451 3.1 Nano-sensors......................................................................... 451 3.2 Wastewater treatment............................................................ 453 3.3 Pollutant degradations..........................................................455 Conclusion................................................................................... 455 References.................................................................................... 456

CHAPTER 19 Benign fabrication of metallic/metal oxide nanoparticles from algae............................................... 465 Paulkumar Kanniah, Parvathiraja Chelliah, Jesi Reeta Thangapandi, Emmanuel Joshua Jebasingh Sathiya Balasingh Thangapandi, Murugan Kasi, and Sudhakar Sivasubramaniam 1 2 3 4

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6 7 8 9

Introduction.................................................................................. 465 Preference for plants.................................................................... 466 Algae............................................................................................ 467 Nanoparticles from microalgae.................................................... 468 4.1 Metal NPs............................................................................. 468 4.2 Metal oxide NPs................................................................... 471 Nanoparticles synthesized by macroalgae................................... 472 5.1 Metal NPs............................................................................. 472 5.2 Production of metal oxide NPs............................................. 476 Possible mechanism..................................................................... 479 Diatoms........................................................................................ 482 Future outlook.............................................................................. 483 Conclusion................................................................................... 483 Acknowledgments....................................................................... 484 References.................................................................................... 484

Contents

CHAPTER 20 Biogenic metal sulfide nanoparticles synthesis and applications for biomedical and environmental technology........................................................................ 495

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S. Ragu Nandhakumar, S. Rajeshkumar, R.S. Anand, Vamshikrishna Malyla, Kamal Dua, Devaraj Ezhilarasan, and T. Lakshmi Introduction.................................................................................. 495 Metal nanoparticles...................................................................... 496 Metal sulfide nanoparticles.......................................................... 496 3.1 Cadmium sulfide nanoparticles............................................ 496 3.2 Copper sulfide nanoparticles................................................ 498 3.3 Iron sulfide nanoparticles...................................................... 499 3.4 Silver sulfide nanoparticles................................................... 499 3.5 Arsenic sulfide nanoparticles................................................ 500 3.6 Gold sulfide nanoparticles.................................................... 501 3.7 Bismuth sulfide nanoparticles............................................... 503 3.8 Manganese sulfide nanoparticles.......................................... 503 Conclusion................................................................................... 504 References.................................................................................... 504

CHAPTER 21 Microbial-mediated copper nanoparticles synthesis, characterization, and applications........... 507 1 2 3 4 5

6

Nandhini Palani and Ramya Dinesh Elangovan Introduction.................................................................................. 507 Copper nanoparticles................................................................... 508 Techniques for the synthesis of copper nanoparticles................. 509 Need for microbial-mediated synthesis of copper nanoparticles................................................................................ 511 Microbial-mediated synthesis of copper nanoparticles............... 511 5.1 Bacteria................................................................................. 512 5.2 Actinomycetes...................................................................... 513 5.3 Fungi.....................................................................................513 5.4 Yeast...................................................................................... 516 5.5 Algae..................................................................................... 516 5.6 Viruses.................................................................................. 517 Characterization of copper nanoparticles.................................... 517 6.1 Nanoparticle formation analysis......................................... 518 6.2 Extraction of nanoparticles................................................. 518 6.3 Tracking of nanoparticles.................................................... 521 6.4 Morphology and size analysis............................................. 521 6.5 Surface charge analysis....................................................... 522

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6.6 Optical properties................................................................ 522 6.7 Thermal properties.............................................................. 523 6.8 Elemental composition analysis.......................................... 524 6.9 Structure analysis................................................................ 524 6.10 Magnetic properties analysis.............................................. 525 6.11 Surface hydrophobicity assessment.................................... 525 Applications of CuNPs................................................................ 525 7.1 Antimicrobial activity........................................................... 525 7.2 E-waste management............................................................ 526 Conclusion................................................................................... 526 References.................................................................................... 527

CHAPTER 22 Green nanomaterials produced by agro-waste and microbes: Mechanisms and risk assessment............. 535 1 2

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Parteek Prasher, Mousmee Sharma, and Harish Mudila Introduction.................................................................................. 535 Green nanomaterials from agriculture waste............................... 536 2.1 Green nanomaterials from grain straw.................................536 2.2 Green nanomaterials from sugarcane bagasse...................... 539 2.3 Green nanomaterials from grain hulls.................................. 542 2.4 Green nanomaterials from cotton stalk................................. 544 2.5 Green nanomaterials from corncob...................................... 545 Green nanomaterials from microbial biomass............................. 547 Conclusion................................................................................... 553 References.................................................................................... 553

CHAPTER 23 Frontier and perspective outlook on agrowaste nanoparticles for healthcare and environment.......... 563

1 2 3

4 5

Devaraj Ezhilarasan, Duraisamy Revathi, Subramanian Raghunandhakumar, S. Rajeshkumar, A. Anbukumaran, and P. Vanathi Introduction.................................................................................. 563 Nanoparticle synthesis using agricultural waste.......................... 564 Applications................................................................................. 565 3.1 Biomedical applications of nanoparticle synthesized using agricultural waste........................................................ 565 3.2 Nanoparticles in healthcare................................................... 565 3.3 Nanoparticles for environmental applications...................... 567 Limitations of nanotechnology in healthcare.............................. 568 Conclusion................................................................................... 570 References.................................................................................... 571

Contents

CHAPTER 24 Mechanistic approach on the synthesis of metallic nanoparticles from microbes......................... 577 1 2

3

Nisha Elizabeth Sunny, A. Kaviya, and S. Venkat Kumar Introduction.................................................................................. 577 Synthesis of nanoparticles........................................................... 578 2.1 Biological synthesis.............................................................. 579 2.2 Mechanism of nanoparticle synthesis................................... 580 Conclusion................................................................................... 592 References.................................................................................... 592

CHAPTER 25 Microbially synthesized nanoparticles: A promising future for insecticidal efficacy studies... 603 1 2 3

4

5 6 7 8

Chandrasekaran Rajkuberan, John Joseph, and Rajiv Periakaruppan Introduction.................................................................................. 603 Types of nanoparticles................................................................. 604 Synthesis of nanoparticles........................................................... 605 3.1 Green synthesis of nanoparticles.......................................... 606 3.2 Plant-mediated nanoparticles................................................ 607 Microbial synthesis of nanoparticles........................................... 607 4.1 Bacteria-mediated nanoparticles........................................... 607 4.2 Actinomycetes-mediated nanoparticles................................ 608 4.3 Fungi-mediated nanoparticles............................................... 609 4.4 Algae-mediated nanoparticles.............................................. 610 Mechanism of nanoparticle formation......................................... 611 Insecticidal efficacy of microbial-mediated nanoparticles.......... 613 Future perspectives...................................................................... 616 Conclusion................................................................................... 618 References.................................................................................... 618

CHAPTER 26 Biomedical applications of ginsenosides nanoparticles synthesized using microbes................ 625

1 2

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Sri Renuakdevi Balusamy, Santhiya Karuppieh, Sumathi Venkat, Lakshmi Thangavelu, Yeon Ju Kim, and Haribalan Perumalsamy Introduction.................................................................................. 625 Probiotics..................................................................................... 626 2.1 Versatile clinical applications of the probiotics.................... 627 2.2 Probiotic mediated nanoparticle synthesis............................ 629 Mechanisms of the microbial synthesis of nanoparticles............ 631 3.1 Intracellular method.............................................................. 634

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3.2 Extracellular method............................................................. 636 3.3 Optimization of the microbial nanoparticle synthesis.......... 637 Biomedical applications of nanoparticles.................................... 637 Bacteria based nanoparticles........................................................ 639 Ginseng........................................................................................ 640 6.1 Ginsenosides and its types.................................................... 640 6.2 Multifaceted roles of the ginsenosides.................................641 6.3 Need of the ginsenoside nanosystems.................................. 642 6.4 Ginsenosides-based micro/nanocarriers............................... 642 Microbial synthesis of the ginsenoside nanoparticles and applications.................................................................................. 646 Futuristic views............................................................................ 648 Conclusion................................................................................... 648 References.................................................................................... 649

CHAPTER 27 Synthesis of selenium nanoparticles by using microorganisms and agri-based products.................. 655 1 2

3 4 5

Bhagavanth Reddy G. and Rajkumar Bandi Introduction.................................................................................. 655 Synthesis of SeNPs...................................................................... 657 2.1 Physical methods.................................................................. 657 2.2 Chemical methods................................................................ 658 2.3 Biological synthesis of SeNPs.............................................. 658 2.4 Mechanism of microbial synthesis of SeNPs....................... 663 2.5 Agro-based synthesis of SeNPs............................................ 665 2.6 Mechanism of agro-based materials synthesis of SeNPs..... 670 Characterizations of SeNPs......................................................... 670 Applications of SeNPs................................................................. 671 Conclusions.................................................................................. 673 References.................................................................................... 674 Further reading............................................................................. 683

CHAPTER 28 Plant-meditated methods for synthesis of silver nanoparticles................................................................... 685 1 2

3

Manviri Rani, Jyoti Yadav, Meenu, Keshu, and Uma Shanker Introduction.................................................................................. 685 Types of green approaches for Ag-nanomaterials........................ 686 2.1 Biological method................................................................. 686 2.2 Photochemical method.......................................................... 688 Green synthesis............................................................................ 688

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Applications of silver nanoparticles............................................ 698 Conclusions.................................................................................. 698 References.................................................................................... 699

CHAPTER 29 Rice wastes for green production and sustainable nanomaterials: An overview.......................................... 707 1 2

3 4 5 6

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Hussien AboDalam, Vijay Devra, Farah K. Ahmed, Bin Li, and Kamel A. Abd-Elsalam Introduction.................................................................................. 707 Types of rice wastes..................................................................... 708 2.1 Rice straw............................................................................. 708 2.2 Rice husk.............................................................................. 709 2.3 Rice bran............................................................................... 709 Amount of rice wastes................................................................. 709 Utilization of rice-waste..............................................................710 Agric-waste as green sources of nanoparticles............................ 712 Nanomaterials extracted from rice wastes................................... 714 6.1 Silica nanoparticles (SiNPs)................................................. 714 6.2 Carbon nanotubes (CNTs).................................................... 715 6.3 Cellulose nanofibers (CNF).................................................. 717 6.4 Other nanoparticles............................................................... 718 Applications of rice bio nanomaterials........................................ 719 Conclusion future perspectives.................................................... 722 References.................................................................................... 723

Index....................................................................................................................... 729

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Contributors Kamel A. Abd-Elsalam Plant Pathology Research Institute, Agricultural Research Center (ARC); Plant Pathology Department, Faculty of Agriculture, Cairo University, Giza, Egypt Hussien AboDalam Plant Pathology Department, Faculty of Agriculture, Cairo University, Giza, Egypt A. Anbukumaran Department of Microbiology, Urumu Dhanalaksmi College, Tiruchirappalli, Tamil Nadu, India Syed Farooq Adil Department of Chemistry, College of Science, King Saud University, Riyadh, Kingdom of Saudi Arabia Farah K. Ahmed Biotechnology English Program, Faculty of Agriculture, Cairo University, Giza, Egypt Manal M. Ahmed Organic Egypt, Heliopolis University for Sustainable Development, Cairo; Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt Vishal Ahuja Department of Biotechnology, Himachal Pradesh University, Shimla, Himachal Pradesh, India Evidence Akhayere Department of Environmental Science; Environmental Research Centre, Cyprus International University, Nicosia, Mersin, Turkey Mousa A. Alghuthaymi Biology Department, Science and Humanities College, Shaqra University, Alquwayiyah, Saudi Arabia R.S. Anand Centre for Biotechnology, Alagappa College of Technology, Anna University, Chennai,Tamil Nadu, India Mohammad Ashfaq Advanced Ceramics and Nanotechnology Laboratory, Department of Materials Engineering, Faculty of Engineering, University of Concepción, Concepción, Chile; School of Life Science, BS Abdur Rahaman Institute of Science and Technology, Chennai, India Marwa T. Badawy Department of Biology, School of Sciences and Engineering, The American University in Cairo, New Cairo, Egypt

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Contributors

Sri Renuakdevi Balusamy Department of Food Science and Biotechnology, Sejong University, Seoul, Republic of Korea Abdul Basit Department of Horticulture, Faculty of Crop Production Sciences, The University of Agriculture Peshawar, Peshawar, Pakistan Anindita Behera School of Pharmaceutical Sciences, Siksha ‘O’ Anusandhan Deemed to be University, Bhubaneswar, Odisha, India Rami Bejjani Department of Plant Production, Faculty of Agriculture, Lebanese University, Beirut, Lebanon; University of Forestry, Sofia, Bulgaria Bhagavanth Reddy G. Department of Chemistry, PG Center Wanaparthy, Palamuru University, Wanaparthy, Telangana, India Amna Chaudhry Department of Environmental Sciences, Kinnaird College for Women, Lahore, Punjab, Pakistan Divya Chauhan Department of Chemical and Biomedical Engineering, University of South Florida, Tampa, FL, United States Parvathiraja Chelliah Department of Physics, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Jeyapragash Danaraj Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India Muniswamy David Department of Zoology, Karnatak University, Dharwad, Karnataka, India Vijay Devra Department of Chemistry, J.D.B. Govt. P. G. Girls College, Kota, Rajasthan, India Kamal Dua Discipline of Pharmacy, Graduate School of Health, University of Technology Sydney, Ultimo, NSW, Australia Anthony C. Ekennia Department of Chemistry, Alex Ekwueme Federal University Ndufu-Alike Ikwo, Abakaliki, Ebonyi State, Nigeria Ramya Dinesh Elangovan Department of Microbiology, Indian Council for Medical Research-National Institute of Epidemiology, Chennai, India

Contributors

Elias E. Elemike Department of Chemistry, College of Science, Federal University of Petroleum Resources, Effurun, Delta State, Nigeria Rachael O. Ezeani Department of Chemistry, College of Science, Federal University of Petroleum Resources, Effurun, Delta State, Nigeria Devaraj Ezhilarasan Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India M. Jeevitha Department of Periodontics, Saveetha Dental College, SIMATS, Saveetha University, Chennai, Tamil Nadu, India John Joseph Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India Nandakumar Kalarikkal International and Inter-University Centre for Nanoscience and Nanotechnology; School of Pure and Applied Physics, Mahatma Gandhi University, Kottayam, Kerala, India Anu Kalia Electron Microscopy and Nanoscience Laboratory, Department of Soil Science, Punjab Agricultural University, Ludhiana, India Paulkumar Kanniah Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Santhiya Karuppieh Department of Biochemistry, Biotechnology and Bioinformatics, Avinashilingam Institute for Home Science and Higher Education for Women, Coimbatore, Tamil Nadu, India Murugan Kasi Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Doga Kavaz Environmental Research Centre; Department of Bioengineering, Cyprus International University, Nicosia, Mersin, Turkey A. Kaviya School of Biosciences and Technology, Vellore Institute of Technology, Vellore, Tamil Nadu, India Keshu Department of Chemistry, Dr B R Ambedkar National Institute of Technology, Jalandhar, Punjab, India

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Contributors

Mohamed S. Khalil Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt Mujeeb Khan Department of Chemistry, College of Science, King Saud University, Riyadh, Kingdom of Saudi Arabia Yeon Ju Kim Graduate School of Biotechnology, College of Life Sciences, Kyung Hee University, Yongin, Republic of Korea T. Lakshmi Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India Bin Li State Key Laboratory of Rice Biology and Ministry of Agriculture Key Laboratory of Molecular Biology of Crop Pathogens and Insects, Institute of Biotechnology, Zhejiang University, Hangzhou, China Satinder Pal Kaur Malhotra Faculty of Science and Technology, ICFAI Tech School, ICFAI University Dehradun, Dehradun, India Vamshikrishna Malyla Centre for Biotechnology, Alagappa College of Technology, Anna University, Chennai,Tamil Nadu, India R.V. Mangalaraja Advanced Ceramics and Nanotechnology Laboratory, Department of Materials Engineering, Faculty of Engineering, University of Concepción, Concepción, Chile Meenu Department of Chemistry, Malaviya National Institute of Technology, Jaipur, Rajasthan, India Heba I. Mohamed Biological and Geological Sciences Department, Faculty of Education, Ain Shams University, Cairo, Egypt Manal Mostafa Organic Egypt, Heliopolis University for Sustainable Development, Cairo, Egypt Harish Mudila Department of Chemistry, Lovely Professional University, Jalandhar, India M. Nagalingam Department of Bio-Chemistry, Indo-American College, Cheyyar, Tamil Nadu, India S. Ragu Nandhakumar Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India

Contributors

Rishabh Anand Omar Centre for Environmental Science and Engineering, Indian Institute of Technology Kanpur, Kanpur, India Damian C. Onwudiwe Material Science Innovation and Modelling (MaSIM) Research Focus Area; Department of Chemistry, School of Mathematics and Physical Sciences, Faculty of Agriculture, Science and Technology, North-West University, Mmabatho, South Africa Santwana Padhi KIIT Technology Business Incubator, KIIT Deemed to be University, Bhubaneswar, Odisha, India Nandhini Palani National Reference Laboratory, National Institute for Research in Tuberculosis, Chennai, India Vignesh Kumar Palaniswamy Department of Chemistry, KGiSL Institute of Technology, Coimbatore, Tamil Nadu, India Nidhi Pareek Department of Microbiology, School of Life Sciences, Central University of Rajasthan Bandarsindri, Kishangarh, Ajmer, Rajasthan, India Rajiv Periakaruppan Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India Haribalan Perumalsamy Graduate School of Biotechnology, College of Life Sciences, Kyung Hee University, Yongin; Research Institute for Convergence of Basic Science, Hanyang University, Seoul, Republic of Korea Parteek Prasher UGC Sponsored Centre for Advanced Studies, Department of Chemistry, Guru Nanak Dev University, Amritsar; Department of Chemistry, University of Petroleum & Energy Studies, Dehradun, India Subramanian Raghunandhakumar Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India Rajendran Rajakumari International and Inter-University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India S. Rajeshkumar Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India

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Contributors

Chandrasekaran Rajkuberan Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India Rajkumar Bandi Department of Chemistry, Osmania University, Hyderabad, India Manviri Rani Department of Chemistry, Malaviya National Institute of Technology, Jaipur, Rajasthan, India Duraisamy Revathi Department of Prosthodontics, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India Sadia Saif Department of Environmental Sciences, Kinnaird College for Women, Lahore, Punjab, Pakistan Tony Kevork Sajyan Department of Plant Production, Faculty of Agriculture, Lebanese University, Beirut, Lebanon Jeyabalan Sangeetha Department of Environmental Science, Central University of Kerala, Kasaragod, Kerala, India Youssef Najib Sassine Department of Plant Production, Faculty of Agriculture, Lebanese University, Beirut, Lebanon; Department of Agricultural Biotechnology, College of Agricultural and Food Sciences, King Faisal University, Al Ahsa, Kingdom of Saudi Arabia Roshan Shaalan Department of Plant Production, Faculty of Agriculture, Lebanese University, Beirut, Lebanon; University of Forestry, Sofia, Bulgaria Uma Shanker Department of Chemistry, Dr B R Ambedkar National Institute of Technology, Jalandhar, Punjab, India Mousmee Sharma UGC Sponsored Centre for Advanced Studies, Department of Chemistry, Guru Nanak Dev University, Amritsar; Department of Chemistry, Uttaranchal University, Dehradun, India D. Sheba PAPRSB Institute of Health Sciences, Universiti Brunei Darussalam, Gadong, Brunei Darussalam Arun Kashivishwanath Shettar Department of Applied Genetics, Karnatak University, Dharwad, Karnataka, India

Contributors

Sudhakar Sivasubramaniam Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Nisha Elizabeth Sunny School of Biosciences and Technology, Vellore Institute of Technology, Vellore, Tamil Nadu, India Neetu Talreja Advanced Ceramics and Nanotechnology Laboratory, Department of Materials Engineering, Faculty of Engineering, University of Concepción, Concepción, Chile Devarajan Thangadurai Department of Botany, Karnatak University, Dharwad, Karnataka, India Emmanuel Joshua Jebasingh Sathiya Balasingh Thangapandi Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Jesi Reeta Thangapandi Department of Biotechnology, Manonmaniam Sundaranar University, Tirunelveli, Tamil Nadu, India Lakshmi Thangavelu Department of Pharmacology, Saveetha Dental College and Hospitals, Saveetha University, SIMATS, Chennai, Tamil Nadu, India Shivasharana Chandrabanda Thimmappa Department of Microbiology and Biotechnology, Karnatak University, Dharwad, Karnataka, India Sabu Thomas International and Inter-University Centre for Nanoscience and Nanotechnology; School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, India Anand Torvi Centre of Nano and Material Science, Jain University, Bangalore, Karnataka, India R. Usha Department of Microbiology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India P. Vanathi Department of Biotechnology, Sri Ramakrishna College of Arts and Science, Coimbatore, Tamil Nadu, India C.K. Venil Department of Biotechnology, Anna University Regional Campus, Coimbatore, Tamil Nadu, India

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Contributors

Sumathi Venkat Department of Biochemistry, Biotechnology and Bioinformatics, Avinashilingam Institute for Home Science and Higher Education for Women, Coimbatore, Tamil Nadu, India S. Venkat Kumar School of Biosciences and Technology, Vellore Institute of Technology, Vellore, Tamil Nadu, India Subha Priya Venkateswaran Department of Biotechnology, Rathnavel Subramaniam College of Arts and Science, Coimbatore, Tamil Nadu, India R. Vishvanand Department of Biotechnology, Rathnavel Subramaniam College of Arts and Science, Coimbatore, Tamil Nadu, India Vivekanand Vivekanand Centre for Energy and Environment, Malaviya National Institute of Technology, Jaipur, Rajasthan, India Jyoti Yadav Department of Chemistry, Malaviya National Institute of Technology, Jaipur, Rajasthan, India Monika Yadav Centre for Energy and Environment, Malaviya National Institute of Technology, Jaipur, Rajasthan, India

Preface The main goal of this book is to assess the most recent trends in producing bionanomaterials from agricultural waste and microorganisms. The book title Agri-Waste and Microbes for Production of Sustainable Nanomaterials indicates that in 29 chapters this book has collected the knowledge, discoveries, and fruitful findings of green synthesis of various nanomaterials using microorganisms and agricultural waste. Present book has been divided into two parts. Part I is focused on production of nanomaterials from agric-waste like metallic, copper, silica, cellulose, nanopolymers, and nano/ microplastics. Part II reviews appropriate biological methods such as agricultural and microbial synthesis of metallic/metal oxide, magnetic, silver, copper, nanomaterials, nano-ginseng, and nanonutrients, etc. Synthesis of nanocellulose from agri-wastes is a probable alternative for waste treatment methods and developing new biosensors and antimicrobial agents. Silicon nanoparticles have been predicted to become one of the professional ingredients for improving crop yields. With modern advances and extended work in enhancing nanomaterial synthesis performance and discovery of their biomedical, environmental, and agricultural applications, it is hoped that the execution of these methods on a large scale and their industrial applications in different fields will take place in the near future. The use of agro-waste and microbes not only minimizes the cost of nanomaterial production but also decreases the need to apply dangerous chemicals; in addition, it encourages “green synthesis” and a strong step toward agricultural sustainable development. This book represents the fifth volume in the series titled “Nanobiotechnology for Plant Protection,” the original book series approved by Elsevier. The present volume contains 29 chapters written by eminent authors from Australia, Egypt, Bulgaria, Chile, Republic of Korea, Nigeria, South Africa, India, Kingdom of Saudi Arabia, Pakistan, Turkey, and the United States. The 29 chapters have been written by professionals and experts with outstanding knowledge on the use of agri-waste and microbes for the production of green nanomaterials. This book follows a multidisciplinary approach and will be very useful for academics, teachers and scholars, agro-food environmental scientists working in agrochemicals, nanotechnology, materials sciences, genetics, chemistry, physics, plant sciences, chemical processing, microbiology, plant physiology, biotechnology, and other stakeholders such as indus. This book follows a multidisciplinary approach and will be very useful for academics, teachers and scholars, agro-food environmental scientists working in agrochemicals, nanotechnology, materials sciences, genetics, chemistry, physics, plant sciences, chemical processing, microbiology, plant physiology, biotechnology, and other stakeholders such as industrial waste management companies. Expected readers of this book would include scholars, graduate students, postgraduate students, and researchers in agrochemical firms and from diverse fields of science and technology. A study of this nature is important to start a database to formalize the practice of nanotechnology. Only very few institutions around the world s­ pecialize in agricultural and ­microbial ­nanotechnology. So we look forward to providing a positive, insightful, and innovative viewpoint not only to experienced

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readers but also to ­technology decision makers with limited experience in this field We are most indebted to the publisher for compiling this set of high-quality manuscripts. We thank all the writers who have written the chapters of this book and have provided comments and valuable insights to the edited version. Writing this book would not have been possible without their involvement and devotion. We express our heartfelt gratitude to the staff at Elsevier, in particular to Simon Holt, Rafael Trombaco (Editorial Project Manager), Megan Ball (Executive Editor), Nirmala Arumugam, and Narmatha Mohan, for their great support and efforts to publish this volume. We thank all the reviewers who have extended their precious time to comment on the chapters. We also thank our families for their continued advice and encouragement. Kamel A. Abd-Elsalam Agricultural Research Center, Giza, Egypt Rajiv Periakaruppan Karpagam Academy of Higher Education, Coimbatore, India S. Rajeshkumar Saveetha Dental College and Hospital, Chennai, India

Series preface The field application of engineered nanomaterials (ENMs) has not yet been well investigated for plant promotion and protection in an agro-environment, and many of the most effective components have been studied only theoretically or using prototypes, which makes it hard to evaluate the utility of ENMs for plant promotion and protection. Nanotechnology applications in the food industry involve encapsulation and delivery of materials to targeted sites, developing flavor, introducing nano-antimicrobial agents in food, improving shelf life, sensing contamination, improving food preservatives, monitoring, tracing, and logo protection. The list of environmental problems that the world faces is very long, but the strategies to fix these problems are relatively few. Scientists from all over the world are developing nanomaterials that could use selected nanomaterials to capture poisonous pollutants from water and degrade solid waste into useful products. The market intake of nanomaterials is increasing, and the Freedonia Group has predicted that the market for nanostructures will grow to $100 billion by 2025. Nanotechnology research and development has been steadily increasing across all scientific disciplines and industries. Based on this background, the scientific series entitled “Nanobiotechnology for Plant Protection” was inspired by the desire of the editor, Kamel A. Abd-Elsalam, to put together detailed, up-to-date, and applicable studies on nanobiotechnology applications in the field of agro-ecosystems to foster awareness and extend our view of future perspectives. The main appeal of this book series is its specific focus on plant protection in agri-food and environment, which is one of the most topical issues of the many challenges faced by humanity today. The discovery and highlighting of new book inputs, based on nanobiotechnology, that can be used at lower application rates will be critical to the sustainability of eco-agriculture. The research carried out in the related fields is scattered and not in a single place. This book series will cover applications in the agri-food and environment sectors, which is the new topic of research in the field of nanobiotechnology. This book series will present a comprehensive account of the literature on specific nanomaterials and their applications in agriculture, food, and environment. Readers will be able to gather information from a single book series. Students, teachers, researchers from colleges, universities, research institutes, and industry will benefit from this book series. Four specific features make this book series one of a kind. First, this book series has a very specific editorial focus, and researchers can locate nanotechnology information precisely without looking through the entire text. Second, and more importantly, this series offers a crucial evaluation of the content material along with nanomaterials, technologies, applications, methods and equipment, and safety and regulatory aspects in agri-food and environmental sciences. Third, this series offers readers a concise description of the content material; it offers nanoscientists clarity and in-depth information. Finally, this series presents researchers with insights on new discoveries. The current series gives researchers a sense of what to do, what they would need to do, and how to do it properly—by

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finding others who have done it. The fifth book in this series entitled Agri-Waste and Microbes for Production of Sustainable Nanomaterials has gathered the know-how, mechanisms, and green production of various nanomaterials by using agri-waste and microorganisms. The expected readership for this book series would be researchers in the field of environmental science, food, and agriculture science. Some readers may also include chemists, material scientists, government regulatory agencies, agro and food industry players, and academicians. Readers from industry may also be interested in this series. This book series will be useful to a wide audience of food, agriculture, and environmental science researchers, including undergraduate and graduate students and postgraduates. In addition, agricultural producers could benefit from the applied knowledge that will be highlighted in this book, which otherwise would be buried in different journals. Both primary and secondary audiences seek up-to-date knowledge of nanotechnology applications in environmental science, agriculture, and food science. It is a trending area, and many new studies are published every week. Readers need some good summaries to help them learn the latest key findings, which could be review articles and/or books. This book series will help to put these pockets of knowledge together and make it more easily accessible globally. Kamel A. Abd-Elsalam Agricultural Research Center, Giza, Egypt

CHAPTER

Sustainable strategies for producing large-scale nanomaterials: A note from the editors

1

Kamel A. Abd-Elsalama, S. Rajeshkumarb, and Rajiv Periakaruppanc a

Plant Pathology Research Institute, Agricultural Research Center (ARC), Giza, Egypt, Department of Pharmacology, Biomedical Research Unit and Laboratory Animal Research Centre, Saveetha Dental College and Hospitals, Saveetha Institute of Medical and Technical Sciences, Chennai, Tamil Nadu, India, c Department of Biotechnology, Karpagam Academy of Higher Education, Coimbatore, Tamil Nadu, India b

1 ­Introduction Nanotechnology, nanoparticles, nano materials, nanocomposite, bio nanocomposite nanobiotechnology, and bio nanotechnology are the most widely using terms nowadays. The nanotechnology mostly used in many food and agricultural areas, textile industries, renewable energy, environmental applications, electronics and communication research area, health care and biomedical applications and finally industrial applications (Abou El-Nour et al., 2010; Singh et al., 2019). Nanoparticles used in the textiles area like technical textiles, electro conductive textiles, antistain textiles, self-cleaning textiles, natural and synthetic polymer hybrid fibers and wool dressing materials (Taylor-Pashow et al., 2010). The biomedical and healthcare applications of nanoparticles are wide area especially in antibacterial, antifungal drug delivery, imaging techniques, MRI contrast agents, hyperthermic treatment, cancer therapy are contrast agents UV protection sunscreens, antioxidant, bone growth and Dental applications. In dental applications, the nanoparticles are used in periodontics, prosthodontics, public health dentistry, endodontics, orthodontics, oral surgery and oral medicine (Chen and Chatterjee, 2013). In renewable energy, the nanoparticles are used as fuel cell catalyzes, fuel additive catalyzes, dye-sensitized solar cells, hydrogen product production, photocatalyst, hydrogen storage materials, lithium-ion battery electrodes and paint on solar cells (Chen et  al., 2012). The application of nanoparticles in environmental technology is very important nowadays because of the applications in wastewater treatment like dye degradation and waste metal degradation, pollution monitoring sensors, pollutant scavengers, automotive catalysts and degradation of mini pollutants (Corsi et  al., 2018). Nano-based products are very small but the applications in different departments are very high. The role of Agri-Waste and Microbes for Production of Sustainable Nanomaterials. https://doi.org/10.1016/B978-0-12-823575-1.00023-8 Copyright © 2022 Elsevier Inc. All rights reserved.

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CHAPTER 1  Sustainable strategies for producing large-scale nanomaterials

nanoparticles and nanotechnology in agriculture is very important nowadays because Agriculture is one of the topmost areas for human kind and very wealthy development of a disease-free world (Kaphle et al., 2018). The crop growth, crop improvement, and crop protection in the form of nano-pesticides and nano fertilizer using nanotechnology. Apart from this, the nanotechnology applications in agriculture are possible in the usage of nanosensors to detect the various fungicides and pesticides present in the vegetables and fruits (Chaudhry et al., 2018). The micronutrient supply and insect pest management for that delivery of fertilizers and the nano herbicides and nanofungicides play a major role for better crop development (Priyanka and Venkatachalam, 2016). The aim of this chapter is to update and enrich the knowledge to researchers and on sustainable strategies via agricultural wastes and various microbes for synthesis or production of nanomaterials using the agricultural resources at a large-scale level and their potential application in various fields.

2 ­Green synthesis nanomaterials The synthesis of nanoparticles is a major area of research in nanoparticles preparation and nanocomposites making. The synthesis of nanoparticles is majorly classified into two types: the first one is a bottom-up approach and the second one is top-down approach (Gour and Jain, 2019). The top-down approach majorly concentrating on fluttering technique milling technique laser ablation chemical leaching mechanical milling and ball milling finally the electro exploration the physical techniques for majorly coming under this top-down approach (Yadi et  al., 2018). In the bottomup approach, the chemical mediated synthesis of nanoparticles and biosynthesis of nanoparticles are playing a major role in the nanoparticle synthesis process (Hussain et al., 2016). In the continuation of chemical synthesis of nanoparticles, the green synthesis process was developed and many biological materials are used for the synthesis of nanoparticles (Mahmoud, 2020; Rajeshkumar et  al., 2020; Shunmugam et al., 2020). The polymeric metal oxide and metal sulfide nanoparticles are mostly prepared by using these green synthesis methods (Singh et al., 2018).

2.1 ­Agri-waste mediated nanoparticles Currently, modern agriculture produces billion tons of waste accumulated in landfill sites, creating controversial consequences, rather than being reintroduced into the production chain for a novel purpose (Jimenez-Lopez et al., 2020). The accumulation of agricultural waste, i.e. corn, rice husk, rice straw, sugar cane bagasse and wheat straw, is approximately 2 billion tons worldwide (Millati et al., 2019). Soybean production reaches 460 million tons of waste per year, for instance, one of the crops which generates the most by-products (Carneiro et al., 2020). However, these agricultural residues are rich in bioactive compounds, including phénolic compounds, proteins and secondarily found secondary metabolites in plants (Sadh et al., 2019).

2 ­ Green synthesis nanomaterials

The precursors rich in carbon are used for microbial, biopolymer and chemical methods in the production of bio-based polymers. The composition of chemicals of the main agri-waste, comprising cellulose, hemicellulose, lignin, moisture, ash, carbon, nitrogen, etc., has the potential to biochemically digestible into the manufacturing of useful products such as biogas, bioethanol and other commercially useful examples such as green nanoparticles (Table 1). Synthesis of agri-waste mediated nanoparticles is approaching under green synthesis processes. Biological wastes are used as raw materials for the green synthesis of metal and metal oxide nanoparticles (Ali and Hassaan, 2017). Especially the silver nanoparticles and gold nanoparticles synthesized by using fruit peel waste such as banana peel, apple peel, and mini vegetable peel waste (Ibrahim, 2015). The agro waste such as Citrus aurantifolia peel extract, Moringa oleifera extract, pink guava waste extract, sugarcane bagasse and Timber industry wastes were used for the green synthesis of zinc oxide nanomaterials (Nava et al., 2017). The gold nanoparticle was prepared by using agricultural waste such as Garcinia mangostana peel extract and Punica granatum peel extract and the synthesized nanoparticles were used for biomedical applications such as antibacterial antifungal antioxidant and anticancer activities (Ahmad et al., 2012; Xin Lee et al., 2016). The metal oxide nanomaterials such as copper, gold and silver nanoparticles were synthesized using the Lanthanum camera and Tinospora cordifolia (Saratale et al., 2018). The agricultural waste such as straw and rice husk used for silicon dioxide nanoparticles synthesis and magnesium silicon dioxide nanoparticles preparation (Zamare et al., 2016). The sugarcane bagasse and leaves used in the green synthesis of titanium dioxide nanoparticles and magnetic iron oxide nanoparticles with the help of co-precipitation method (Vilakati et al., 2010). The extract of bamboo leaves was used for silicon dioxide nanoparticles (Vaibhav et al., 2015). The role of major agricultural waste such as sugarcane bagasse, rice husk, fruit peels, cereals bran, wood waste, grass, leaves and more and microbes like bacteria, fungi, algae, actinomyces, lichens are playing an important role in the green synthesis of nanoparticles using nanotechnology (Zamani et al., 2019).

2.2 ­Microbes The microorganisms play a very important role in the biosynthesis of different types of nanoparticles especially metal oxide metal sulfide etc. The metal nanoparticles such as gold, silver, platinum, selenium, cadmium, copper and zinc nanoparticles, metal oxide nanoparticles like iron oxide, zinc oxide, titanium dioxide, zirconium oxide, copper oxide, silver oxide, and cadmium oxide nanoparticles were synthesized by using microorganisms (Narayanan and Sakthivel, 2010). The other metal sulfide nanomaterials such as cadmium sulfide, zinc sulfide, ferrous sulfide and copper sulfide were produced using the microorganisms (Vairavel et al., 2020; Nandhini et al., 2020). The microorganisms such as fungi bacteria, yeast, actinomycetes and many microalgae were used for the different types of nanoparticles (Fig.  1). The two different methods such as intracellular and extracellular techniques are applied in metal nanoparticle synthesis (Fariq et al., 2017). Numerous reviews have shown

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Table 1  Chemical composition of common forms of agricultural waste. Chemical composition (% w/w) Agro-industrial wastes

Cellulose

Hemicellulose

Lignin

Ash (%)

Total solids (%)

Moisture (%)

Sugarcane bagasse Rice straw Corn stalks Sawdust Sugar beet waste Barley straw Cotton stalks Oat straw Soya stalks Sunflower stalks Wheat straw

30.2 39.2 61.2 45.1 26.3 33.8 58.5 39.4 34.5 42.1 32.9

56.7 23.5 19.3 28.1 18.5 21.9 14.4 27.1 24.8 29.7 24.0

13.4 36.1 6.9 24.2 2.5 13.8 21.5 17.5 19.8 13.4 8.9

1.9 12.4 10.8 1.2 4.8 11 9.98 8 10.39 11.17 6.7

91.66 98.62 97.78 98.54 87.5 – – – – – 95.6

4.8 6.58 6.40 1.12 12.4 – 7.45 – 11.84 – 7

Reprinted from Sadh, P.K., Duhan, S., Duhan, J.S., 2019. Agro-industrial wastes and their utilization using solid state fermentation: a review. Bioresour. Bioprocess. 5, 1–15.

3 ­Enzymes mediated nano synthesis

FIG. 1 Agricultural wastes and microbes employed for green production different types of nanoparticles.

that the wide commercial use of these biological agents still lies a long way from the value of algal biofactories (Jacob et al., 2020). The mechanism of action of nanoparticle synthesis by using microorganism is determined and found that the enzymes and secondary metabolites present in the microorganisms are responsible for nanoparticle synthesis for example nitrate reductase majorly involved in the silver nanoparticle synthesis from silver nitrate solution (Velusamy et al., 2016). Bacteria mediated metal nanoparticles are used in biomedical applications such as tissue engineering, tumor destruction and drug and gene delivery. Moreover, the microbial mediated nanomaterials are employed in nanobiomedicine as a fluorescent biological label especially used in diagnosis of many microbial diseases and cancer.

3 ­Enzymes mediated nano synthesis The several researchers are giving more attention on green synthesis of nanomaterials due to its biological compatibility and its economics values. The metals and nonmetals were produced using the plants and microbes and its several cellular and biomolecules. The enzymes mediated nanomaterials production is very important and essential alternative method for physical and chemical methods (Paul et al., 2020). The silver nanomaterials were synthesized by the immobilized enzymes. Silver nitrate was catalyzing by NADH-dependent nitrate reductase and silver nanomaterials were formed as end products (Talekar et al., 2016). The gold nanoparticles have been produced by Gholami-Shabani et al. (2015), and they used the purified enzymes, which derived from Escherichia coli. Moldes-Diz et al. (2018) were prepared and characterized the silica-coated magnetic nanoparticles laccase and used as nanobiocatalyst for the enzymatic biotransformation of xenobiotics. Biogenic silver ­nanomaterials were produced

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CHAPTER 1  Sustainable strategies for producing large-scale nanomaterials

using the cell filtrate (extracellular enzymes) of Trichoderma longibrachiatum, which can act as reducing and stabilizing agent (Elamawi et al., 2018). The enzymes were extracted from the Fusarium solani and Fusarium semitectum by Basavaraja et  al. (2008) and used for the reduction of silver nitrate to form the silver nanomaterials. Balaji et al. (2009) were reported the production of crystal shaped nano silver nanomaterials using the fungal protein, organic acids and polysaccharides from Cladosporium cladosporioides and Coriolus versicolor. The intracellular enzymes were employed in the griping of metallic ions from the medium (Dauthal and Mukhopadhyay, 2016). The actinomycetes likes Rhodococcus sp. and Thermomonospora sp. were involved in the intracellular synthesis of silver nanomaterials. Enzymes from Brevibacterium casei were mitigate the silver nitrate and produce the spherically shape silver nanomaterials (Kalishwaralal et al., 2017). Extracellular and intracellular microbial enzymes are known to play a significant role as reducing and stabilizing agents in the production of metal oxide and metal nanoparticles (Ovais et al., 2018).

4 ­Protein-mediated nano synthesis Recently, the researchers have focused on the synthesis of nanomaterials using the proteins from plants and microbes. Proteins are used as template for uniform nanosized inorganic materials by the nontemplated chemical synthesis. It offers the highquality nanomaterials. The natural proteins like iron-storage protein ferritin were used for nanomaterials synthesis (Voet and Tame, 2017). Bovine serum albumin (BSA) is able to synthesis nanometer-sized gold-nanocomposites with highly desirable properties (Xie et al., 2009). The rice protein conjugated nanomaterials were produced by the biological methods (using anionic and cationic forms of rice protein). The rice protein nanomaterials and rice protein conjugated silver and gold were showed the significant biocompatibility (Mandial et al., 2018). Ravindra (2009) was reported the synthesis of gold nanoparticles by employing Serrapeptase that helps as both a stabilizing and reducing agent. The 2–3 nm size confined protein mediated palladium nanoparticles were produced by Bachar et al. (2020) and the proteins were served as a template for synthesis of nanoparticles. It can alter the cells activity and improve the catalytic activity. Hence, the proteins are improving the formation and activity of the nanoparticles.

5 ­Polysaccharide mediated nano synthesis Now a days, the investigation on polysaccharide mediated nanomaterials is developing in nanobiotechnological areas such as gene delivery, cancer therapy, biosensors, drug delivery, and other environmental applications (Manivasagan and Oh, 2016). There are different types natural polysaccharides namely chitosan, chitin, alginates, agarose, mauran, and chito oligosaccharide (Lin et al., 2012). Many researchers have been synthesized the nanomaterials using the marine polysaccharides (Torres et al., 2019). The biopolymer can be modified as nanomaterials, nanogel, nanomembrane and beads, which are used in the biomedical area due to their very good b­ iocompatibility, less

6 ­ Large-scale production of nanoparticles

toxicity and easily biodegradable (Zheng et al., 2015). Hence the polysaccharide mediated nano synthesis is very important in nano biotechnology field.

6 ­Large-scale production of nanoparticles Production of nanoparticles at a large scale is a very important step forward in the nanotechnology development for future applications and industrial level outputs (Saldanha et al., 2017). The larger quantity of metal oxide nanoparticles such as zinc oxide, titanium dioxide, cerium oxide, zirconium oxide, copper oxide, aluminum oxide, nickel oxide, and iron oxide are produced for the applications in various technological fields as semiconductors, solar energy devices, magnetic resonance imaging optical devices and other biomedical applications due to the properties of electrical, mechanical, magnetic, chemical and optical properties (Yao et al., 2012). Top and down approach is mainly used in the production of nanosuspensions in large scale. There are many key parameters involved in the large-scale production of nanomaterials and nanosuspension (Yin et al., 2020). The parameters such as contamination levels, cost effective for synthesis and stability of the final product are concentrated during the manufacturing process of nanomaterials. In additions, the major techniques like milling and high-pressure homogenization playing an important role in large-scale production of nanomaterials (Falsini et al., 2018). The high energy operation and both cold and room temperature processing are the main steps of the production of the nanomaterials (Shegokar and Nakach, 2020). Gold nanoparticles are produced in large quantities by using solvated metal atom dispersion technique, and in this technology, vacuum condition is involved in the vaporization for production of gold of nanomaterials (Shah and Lu, 2018). The produced gold nanoparticles shape was spherical, and the size was 1–6 nm. The largescale produced gold nanoparticles are available in the market of Europe and America. The metal oxide and carbon nanotubes-based nanocomposites are also produced in larger quantities by various industries. Quantum dots and carbon nanocomposites are produced in large-scale level, and these are used in electronic devices, oxygen electrodes, and medical diagnosis (Costas-Mora et al., 2015). The aim of the large-scale production of biogenic nanomaterials is to identify and develop a novel process using the agricultural wastes for the production of desired nanomaterials. In lab condition, there are so many investigators were successfully produced the different metal oxide nanomaterials (Zhao et al., 2019). The usage of different agricultural resources for the production of nanoparticles may play an important role in future applications. However, large scale-up of biosynthesis of biogenic nanomaterials using agricultural waste can be challenging with respect to their economics, productivity, and reliability (Mohammadinejad and Mansoori, 2020). In future, fast reaction will improved by various parameters for biosynthesis of b­ iogenic nanomaterials without altering the physicochemical properties. The proper design and optimum temperature, pH and salinity control as well as agitation/mixing of solid-liquid mixture in the batch system. The schematic diagram was shown in Fig. 2. The sustainable nanomaterials used in agricultural applications may play an

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CHAPTER 1  Sustainable strategies for producing large-scale nanomaterials

2

Agriculture wastes

Waste by products (Phytochemicals, Polymers)

Collection

Metalic ion Solution

1

3

Biogenic Nanomaterials (Final Products) 7

Dissolved impurities Separation

Shaking Oxygen

pH Reactor 4

Foam control

Temperature

Stirring

Filteration and Centrifugation (Soild fractions)

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5

FIG. 2 Steps involved in large-scale production of biogenic nanoparticles.

important role in the food processing and technology, which includes food packaging, food processing, preservation, etc.

7 ­Advantages A few other benefits of green biogenic nanoparticle production via agri-waste and microbes include (a) atom economy, which improves reaction efficiency, (b) energy efficiency, avoiding the process of high energy use, (c) more secure chemicals to minimize process and product toxicity, (d) prevention, in all process phases, to minimize waste, (e) the use of renewables, using renewable sources of chemicals; (f) design of biodegradable and nontoxic products for degradation, (g) less dangerous synthesis, safer routes of synthesis; reduce derivatives, prevent derivatives such as protectors or stabilizers from being used, (h) Pollution prevention, i.e., preventing hazardous substances from being released, (i) safer solvents and auxiliary devices for the use of the least hazardous solvents or chemicals possible, (j) catalysis, use catalysis to improve processes such as energy consumption or efficiency, and (k) prevent accidents to minimize the risks of accidents. For example, the main advantages of biological synthesis are the use of renewable sources, safer solvents and auxiliary products, while at the same time producing safer chemicals. Among the various biological agents discussed in this chapter, a number of organisms have emerged as suitable and adaptable for use in large-scale production. Simple procedure, low use of toxic chemicals, no expensive media and materials, low electric energy, massive biomass production, high output, and protein and metabolite secretion (Fig. 3).

8 ­ Future perspectives

FIG. 3 Schematic representation of the advantages of agri-waste and microbes as a renewable producer for biogenic synthesis of metal oxide nanoparticles.

8 ­Future perspectives The current chapter clearly elaborates the preparation of nanomaterials using various microbes and agricultural wastes. Agro-industrial waste such as rice husk, cereal waste, sugar cane bagasse and fruit, in addition to different forms of microorganisms and, in particular, bacteria, algae and fungi, is used as a biological agent and has a promising potential for nanoparticle biosynthesis. Here we illustrate various aspects of the industrial development of NPs by fungi, including advantages and disadvantages. We also explore the implementation of various technologies to produce large agricultural waste and microbial protein engineering, metabolism technology and synthetic biology for high-scale manufacturing of NPs. In spite of novel inventions and developments are needs in large-scale production of the nanomaterials using the agro-waste and microorganisms. This method is cost effective because of the low usage of raw materials and easily available. Even though, the producers are in of roadmap or protocol for the large-scale preparation of nanomaterials with desirable structure and size. In future, the researchers must address the problems that have disadvantaged their way to technological success. In view of advances in these fields, the largescale manufacture of nanotechnology materials cannot be thought too soon. At the same time, there has not been enough considered, especially in environmental terms, as a result of the widespread expansion of nanomaterials production processes. In addition, the toxicity and risk assessment of nanomaterials before use or marketing will be feasible, given the high performance of the screening of such methods.

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9 ­Conclusion Microorganisms and agro-industrial waste and debris are high in nutrient composition and bioactive compounds. Such agri-waste has variability in composition, such as sugars, minerals and proteins. The use of agro-wastes as a medium for the synthesis of nanostructured materials has been shown to be an effective waste management technique. Plant- and microbial-derived compounds have demonstrated potential nanoscience practices when they have been effectively used in the synthesis with different nanoparticles of specific properties. The modern approaches for synthesis of bionanoparticles based on agro-waste and microbes are cost-effective and ecofriendly to produce various types of green nanomaterials like nanocellulose, graphene oxide. Also, silica NPs have been produced using various agro-wastes such as rice husk, corn hub, and other plant origin sources. Using sustainability techniques, such as agri-waste and microbes for the processing of large-scale nanomaterials as raw materials can help lower production costs and lead to the recycling of waste, as well as making the environment safer and environmentally friendly for waste management. The key objective of the current volume is to provide readers with a new vision for the recycling of billions of tons of agri-waste collected at landfill sites in new uses, such as the use of green nanomaterials, and to use it in a variety of sustainable applications.

­References Abou El-Nour, K.M., Eftaiha, A.A., Al-Warthan, A., Ammar, R.A., 2010. Synthesis and applications of silver nanoparticles. Arab. J. Chem. 3 (3), 135–140. Ahmad, N., Sharma, S., Rai, R., 2012. Rapid green synthesis of silver and gold nanoparticles using peels of Punica granatum. Adv. Mater. Lett. 3 (5), 376–380. Ali, H.R., Hassaan, M.A., 2017. Applications of bio-waste materials as green synthesis of nanoparticles and water purification. Adv. Mater. 6 (5), 85–101. Bachar, O., Meirovich, M.M., Kurzion, R., Yehezkeli, O., 2020. In  vivo and in  vitro protein mediated synthesis of palladium nanoparticles for hydrogenation reactions. Chem. Commun. 56 (76), 11211–11214. Balaji, D.S., Basavaraja, S., Deshpande, R., Mahesh, D.B., Prabhakar, B.K., Venkataraman, A., 2009. Extracellular biosynthesis of functionalized silver nanoparticles by strains of Cladosporium cladosporioides fungus. Colloids Surf. B Biointerfaces 68 (1), 88–92. Basavaraja, S., Balaji, S., Lagashetty, A., Rajasab, A., Venkataraman, A., 2008. 2008. Extracellular biosynthesis of silver nanoparticles using the fungus Fusarium semitectum. Mater. Res. Bull. 43, 1164–1170. Carneiro, A.M., Moreira, E.A., Bragagnolo, F.S., Borges, M.S., Pilon, A.C., Rinaldo, D., Funari, C.S., 2020. Soya agricultural waste as a rich source of isoflavones. Food Res. Int. 130, 108949. Chaudhry, N., Dwivedi, S., Chaudhry, V., Singh, A., Saquib, Q., Azam, A., Musarrat, J., 2018. Bio-inspired nanomaterials in agriculture and food: current status, foreseen applications and challenges. Microb. Pathog. 123, 196–200.

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CHAPTER 1  Sustainable strategies for producing large-scale nanomaterials

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Agri-waste for production of nanomaterials

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CHAPTER

Synthesis of metal nanoparticles by microbes and biocompatible green reagents

2 Vijay Devra

Department of Chemistry, J.D.B. Govt. P. G. Girls College, Kota, Rajasthan, India

1 ­Introduction Currently, nanotechnology has become a technology that has revolutionized every field of applied science. One of the nanotechnology networks associated with nanoscale materials with particle sizes ranging from 1 to 100 nm is the field of nanoparticles (NPs). The high surface to volume ratio along with size effects, metal nanoparticles (MNPs) show distinctive properties such as chemical, electronic, optical, magnetic and mechanical over their bulk materials (Maghsoodi et  al., 2019). Researchers have achieved considerable attention in the field of nanoparticle synthesis with controlled morphologies and important characteristics makes it an extensive area of study. One of the key priorities in chemistry that could be used for future applications has been a marked increase in the field of biosynthesis of MNPs in recent years, with control over particle size, shape and crystalline nature (Nagar and Devra, 2019). There are two approaches, one is “Top down” and another is “Bottom up” for the synthesis of nanoparticles. Top-down approach includes various physical and chemical treatments are used for size reduction from a suitable starting material (Kharisov et al., 2016; Fig. 1). The physical technique includes the use of high energy, pressure and temperature intake, while the chemical technique requires the use of dangerous and harmful chemicals that lead to environmental contamination. (Naveed Ul Haq et al., 2017). In Bottom-up approach, small entities are combined together and produce final particles in the nanometer range by chemical and biological methods. Though the time needed for fabrication of nanoparticles is longer in biological methods compared to chemical methods, the time has been reduced with consider appropriate microorganism or organism (Gahlawat and Roy, 2019). Therefore, the benefits of biological methods over physical and chemical methods are cost effective, ecofriendly, single step process for the large-scale production of nanoparticles. Biological systems can serve as ‘bio-laboratory’ for the development of pure MNPs using a biomimetic approach, the literature states. (Fang et al., 2019).

Agri-Waste and Microbes for Production of Sustainable Nanomaterials. https://doi.org/10.1016/B978-0-12-823575-1.00013-5 Copyright © 2022 Elsevier Inc. All rights reserved.

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CHAPTER 2  Synthesis of metal nanoparticles by microbes

FIG. 1 Different approches for synthesis of nanoparticles.

In the biological synthesis of metal and metal oxide NPs, microbes such as bacteria, fungi, yeast, and other biocompatible reagents play an important role. The bacteria, with the involvement of biomolecule compounds secreted or formed by the microbes, function as a nano-factory in reducing the metal ions into MNPs. As such, this has allowed for greater stabilization and dispersion of NPs. (Ali et al., 2019). In view of the increasing applications and the demand of nanomaterials, synthesis of nanoparticles (NPs) by microorganisms can be adopted once the method is explored and the basic molecular mechanisms are comprehensible. A characteristic of biosynthetic NPs is their high stability as the organisms provide their own ­biomolecular-capping agents (Chhipa, 2019). A more efficient and sustainable method for the manufacture of nanomaterials is therefore necessary to explore. The synthesis of nanomaterials is concerned with economic viability, environmental friendliness and social usability, as well as the availability of local resources. Industries must maintain a balance

2 ­ Synthesis by microorganisms

b­ etween eco-friendly processes and their profitability in order to keep the prices of the final finished nanotechnology-based goods economical for consumers. The synthesis processes focused on green nanotechnology work under green conditions, without the involvement of toxic chemicals. In this chapter, we have highlighted various biomolecules involved in the reduction of metals into their NPs.

2 ­Synthesis by microorganisms In recent years, in the field of green technology, the biosynthesis of metal/metal oxide nanoparticles utilizing microorganisms such as bacteria, fungi, algae, yeast, and actinomycetes has received attention. (Singh et al., 2016). Microbial agents serve as potential nano-industries to synthesize various metal and metal oxide nanoparticles in an environmentally sustainable and cost-effective way. Because of their natural process of detoxification of metal ions by reduction, microbes have a promising role in the synthesis of nanoparticles that can be accomplished extracellularly or intracellularly by bioaccumulation, biomineralization and biosorption. (Ali et  al., 2019). Microbes assisted synthesis of nanoparticles can be intracellular or extracellular, depending on the location (Fig. 2). The mechanism of intracellular microbial synthesis is based on electrostatic attraction. In which the passage of particular ions through the negatively charged cell wall is followed by positively charged metals and distributed through the cell wall, the enzyme present in the cell wall is converted into nontoxic MNPs. Whereas the mechanism of extracellular Microbes synthesis of nanoparticles includes enzyme produced by different prokaryotes or fungus which converts the metallic ions to metallic nanoparticles (Khandel and Shahi, 2016). The synthesis method consists of microorganism, extract; combine it with the solution of metal salt of definite concentration, optimum temperature and pH of the reaction mixture, indicating the completion of the phase by adjusting the color of the reaction mixture. The preparation of the microorganism extract involves developing the requisite test strain in an appropriate medium. The ideal test stream is collected from the extract of the microorganism and poured into the test tube for sterilization. Incubated at the optimal temperature and centrifuged in an orbital shaker. Prepared microorganism culture reacts with Metal salt solution and incubated on orbital shakers until a color change is recorded, which confirms the formation of nanoparticles.

2.1 ­Fungi Several fungal strains have been used as promising tools for the development of MNPs, such as Aspergillus, Fusarium, Penicillium, and Verticillium. (Mitra et  al., 2019). Fungi, since they are highly immune to metals and have bioaccumulation skills, have exclusive capacity over other microbes such as algae and bacteria. These are helpful in the feasible count, handling of biomass and scale-up and downstream procedures. The bioactive compounds (Hamad, 2019) manage the shape and size, and biochemical configuration of the nanoparticles. To generate FeNPs, Mohamed

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CHAPTER 2  Synthesis of metal nanoparticles by microbes

FIG. 2 Microbes assisted synthesis of nanoparticles.

et al. (2015) used Alternaria alternate fungus, which has been characterized by various spectrophotometric techniques. The nanoparticles have a cubic shape and are 9 ± 3 nm in size. These nanoparticles demonstrate antibacterial activity in relation to B.subtilis, E.coli, P. aeruginosa and Aureus. In the extracellular biomineralization of Ag + to AgNPs at a scale of 10–40 nm, Metuku et al. (2014) investigated the ability of white root fungus. Synthesized AgNPs demonstrated good antibacterial activity against different gram-positive and Gram-negative pathogenic strains of bacteria.

2 ­ Synthesis by microorganisms

The extracellular meditate nanoparticle synthesis has advantages than intracellular, that it is intracellular proteins, treatment with detergents, and ultrasound, are not essential. Various fungal strains of Fusarium oxysporum for the synthesis of AgNPs have been explained (Rajput et al., 2016). The study also summarizes that it will be useful for the creation of biosensors to understand the interaction between organic and interfacial layers. In addition, for different applications, Kitching et al. (2016) extricate the Rhizopus oryzae proteins for in  vitro AuNPs synthesis. Suryavanshi et al. (2017) investigated the synthesis of Al2O3 nanoparticles using Colletotrichem sp. in another study and nanoparticles were functionalized by essential oils revived from Eucalyptus globulus and citrus media. The study concluded that nano functionalized oil could be used against foodborne pathogens as antimicrobial agents. Another research is based on biogenic synthesis of AgNPs as potential antibiotics from fungal metabolites of Penicillium oxalicum. These nanoparticles can be utilized as potential antibiotics in the therapeutics industry. (Feroze et  al., 2019). Table  1 shows the list of different fungi has been used for the synthesis of nanoparticles.

2.2 ­Yeast Yeast is a single-celled microorganism that is very easy to handle and synthesizes various enzymes in laboratory conditions, taking into account their rapid growth by consuming basic nutrients. (Moghaddam et al., 2015). They have the innate ability to absorb a high concentration of nearby toxic metal ions. Using various detoxification processes such as bio precipitation, chelation and intracellular sequestration, yeast cells change themselves under toxic conditions. This yeast cell property was used by Apte et  al. (2013) and reported by Yarrowia lipolytic in a cell-associated manner for the biosynthesis of AgNPs. The research showed that brown pigment (melanin) derived from the yeast cell may be responsible for silver ion biomineralization. These nanoparticles exhibited anti-biofilm activity against Salmonella paratyphi pathogen. High resistivity against gram-positive Staphylococcus aureus and Gram-negative Klebsiella pneumonia has been shown to develop circular-shaped Ag/ AgCl NPs in the range of 2–10 nm supported by yeast strains. In the biomedical sector, therefore, it is highly important (Eugenio et al., 2016). Magnetic biocomposite yeast (YB-MNP) and MNPs are also produced using yeast biomass purchased from the ethanol industry. Mixed-use motor oil, fresh motor oil, and petroleum 28o API can be isolated from water by these materials using the ASTM-F 726–12 process (Debs et  al., 2019). Zhang et  al. (2016) report the green synthesis of AuNPs by the non-conventional yeast Magnusiomyces ingens. TEM images and DLS data (Dynamic Light Scattering) of M. ingenes indicated the average size of the AuNPs was 80.1 ± 9.8 and 137.8 ± 4.6 nm, respectively. According to the study results, some biomolecules, which can serve as organic ligands in the formation of AuNPs, were absorbed on the surface of nanoparticles. Sriramulu and Sumathi (2018) used an extract of Saccharomyces cerevisiae for the synthesis of 32 nm and hexagonal PdNPs. Synthesized PdNPs applied as a photocatalyst for the degradation of azo textile dye. All these studies concluded that the difference in size, shape and properties was due

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Table 1  Synthesis of metal/metal oxide nanoparticles by microbes. Microbe

NPs

Size (nm) and shape

Application

Reference

Aspergillus terreus Curvularia lunata

ZnO NPs AgNPs

28–63 nm, Spherical 10–50 nm, Spherical

Metarhizium anisopliae Cladosporium oxysporum AJP03 Fusarium oxysporum 405 Rhizopus oryzae

AgNPs

28–38 nm, shaped rod

AuNPs

72 ± 21 nm, Spherical

Anticancer activity Synergistic activity with antimicrobials Mosquitocidal activity toward Anopheles culicifacies Degradation of Rhodomine B

Baskar et al. (2015) Ramalingmam et al. (2015) Amerasan et al. (2016) Bhargava et al. (2016)

AgNPs

10–50 nm, Spherical

Colloidal stability

Rajput et al. (2016)

AuNPs

Hemcompatible activity

Kitching et al. (2016)

Colletotrichum sp.

Al2O3 NPs

16–43 nm, Spherical and flower like 30–50 nm, Spherical

Antimicrobial activity

Trichoderma harzianum Fusarium oxysporum Pleurotus ostreatus

AgNPs

20–30 nm, Spherical

Antifungal activity

Suryavanshi et al. (2017) Guilger et al. (2017)

AgNPs AuNPs

34–44 nm, Spherical 10–30 nm, Spherical and prism

Penicillium oxalicum Penicillium citreonigrum

AgNPs AgNPs

60–80 nm, Spherical 6–26 nm, Spherical

Antibacterial activity Anticancer and synergistic antimicrobial activity Antibacterial activity Antibacterial activity

Hamedi et al. (2017) El Domany et al. (2018) Feroze et al. (2019) Hamad (2019)

AgNPs AuNPs

70–180 nm, Spherical Hexagonal and triangular nanoplates

Surface plasmon enhanced applications

Fungi

Yeast Pichia pastoris Saccharomyces cerevisiae

Elahian et al. (2017) Yang et al. (2017)

Candida albicans ATCC 10231 Rhodotorula mucilaginosa Pichia kudriavzevii

AgNPs

10–20 nm, Spherical

Bonilla et al. (2017)

AgNPs

11 nm, Spherical

Bioremediation of silver ions

Salvadori et al. (2017)

ZnO NPs

10–61 nm, Hexagonal wurtzite

Antioxidant and antibacterial

Rhodotorula glutinis and Rhodotorula mucilaginosa Phaffia rhodozyma

AgNPs

15.45 ± 7.94 nm and 13.70 ± 8.21 nm

AgNPs, AuNPs

Magnusiomyces ingens LHF1 Saccharomyces cerevisiae Candida glabrata

AuNPs PdNPs

5–9 nm, Spherical and quasispherical 4–7 nm, Spherical and quasispherical 20.3–28.3 nm, Pseudo spherical 32 nm, Hexagonal

Antifungal activity, degradation of nitro phenol and methylene blue Antifungal activity

Moghaddam et al. (2017) Cunha et al. (2018)

AgNPs

2–15 nm, Spherical

Antimicrobial activity

Sriramulu and Sumathi (2018) Jalal et al. (2018)

Spirogyra varians Caulerpa racemosa Sargassum tenerrimum and Turbinaria conoides Chlorella vulgaris

AgNPs AgNPs AuNPs

35 nm, Quasi sphere 25 nm, Distorted Spherical 27–35 nm, Spherical

Antibacterial activity Degradation of methylene blue Reduction of Rhodomine B and Sulforhodamine 101

Salari et al. (2016) Edison et al. (2016) Ramakrishna et al. (2016)

AgNPs

3–15 nm, Spherical

Antibacterial activity

Cystoseira baccata

AuNPs

8.4 nm, Spherical

Anticancer activity

Chlorella vulgaris

PdNPs

5–20 nm, Spherical

Silva Ferreira et al. (2017) Gonzalez-Ballesteros et al. (2017) Arsiya et al. (2017)

Catalyst for reducing nitro-phenols Degradation of textile dyes

Ronavari et al. (2018)

Qu et al. (2018)

Algae

Continued

Table 1  Synthesis of metal/metal oxide nanoparticles by microbes—cont'd Microbe

NPs

Size (nm) and shape

Application

Reference

Galaxaura elongata

AuNPs

Antibacterial activity

Laminaria japonica

AgNPs

3.8–77.1 nm, Spherical, rods, hexagonal and triangular 31 nm, Spherical to ova;

Abdel-Raouf et al. (2017) Kim et al. (2018)

Gelidium amansii

AgNPs

27–54 nm, Spherical

Padina tetrastromatica and Turbinaria conoides Trichodesmium erythraeum Chlorella ellipsoidea

ZnO NPs

AgNPs

90–120 nm, Spherical, pentagonal, hexagonal and triangular 26.5 nm, Cubical

AgNPs

220.8 ± 31.3 nm, Spherical

Sargassum muticum

ZnO NPs

30–57 nm, Hexagonal

AgNPs

35–60 nm, Spherical and Triangular 2.5–17 nm, Spherical

Phytotoxicity and seedling growth assay Antibacterial and antibiofilm activity Antibacterial activity

Pugazhendhi et al. (2018) Rajeshkumar (2018)

Antibacterial, antioxidant and anticancer activity Photophysical, catalytic and antibacterial activity Anti-angiogenesis and antiapoptotic activity

Sathishkumar et al. (2019) Borah et al. (2020)

Antibacterial activity

Naik et al. (2017)

Antimicrobial and anti-biofouling activity

Kulkarni et al. (2015)

Sanaeimehr et al. (2018)

Bacteria Pseudomonas aeruginosa Deinococcus radiodurans Klebsiella pneumoniae, E.coli Shewanella loihica PV-4 Ochrobacterium sp. MPV1 Bacillus subtilis

AgNPs AgNPs PdNPs and PtNPs

50–100 nm, Cubic and Star/ Flower 2–7 nm, Spherical

TeNPs AuNPs

Müller et al. (2016) Ahmed et al. (2018)

Roughly spherical and rods

Degradation of methyl orange dye Reduction of toxic compounds

20–25 nm, Spherical

Degradation of methylene blue

Srinath et al. (2018)

Zonaro et al. (2017)

Bacillus cereus SZT1

AgNPs

18–39 nm, Spherical

control BLB disease in rice plants Antibacterial activity against multi drug resistant bacteria

Ahmed et al. (2020)

Bacillus brevis NCIM 2533

AgNPs

41–68 nm, Spherical

Streptacidiphilus durhamenesis Streptomyces rochei MHM13

AgNPs

8–48 nm, Spherical

Regulate antibacterial and anticancer activity Antimicrobial activity and synergistic impact with antibiotics Application in methylene blue degradation Antimicrobial activity

Buszewski et al. (2016) Abd-Elnaby et al. (2016)

AgNPs

22–85 nm, Spherical

Streptomyces griseoruber Streptomyces parvulus Streptomyces zaomyceticus Oc-5 and Streptomyces pseudogriseolus Acv-11 Streptomyces xinghaiensis OF1

AuNPs AgNPs

5–50 nm, Spherical, triangular and hexagonal 1–40 nm

CuO NPs

78 nm and 80 nm, Spherical

Various biotechnological applications

AgNPs

5–20 nm, Spherical

Antimicrobial activity and synergistic impact with antibiotics

Saravanan et al. (2018)

Actinomycetes

Ranjitha and Rai (2017) Silva-Vinhote et al. (2017) Hassan et al. (2019)

Wypij et al. (2018)

26

CHAPTER 2  Synthesis of metal nanoparticles by microbes

to various mechanisms influencing the synthesis and stabilization of nanoparticles by the yeast cell. The list of different yeast used for the synthesis of various nanoparticles is shown in Table 1.

2.3 ­Algae Different studies claim that biological molecules in the cell wall of various seaweeds serve as a catalyst in which the precursor metal salt is reduced into MNPs (Kumar et  al., 2013), while enormous amphiphilic biomolecules guide and conduct the growth of the nanoparticle (Stalin Dhas et al., 2012). Spirulina platensis, blue - green algae for AuNPs processing, was used by Suganya et al. (2015) to adsorb Au ions and synthesize them into AuNPs. Intracellularly manufactured in vacuoles by involving such biological molecules in fungal cell metabolism, such as 3-glucon binding proteins, 3-phosphate dehydrogenase glyceraldehyde, and ATPase. There is another study stating that Ulvan armoricana sp. It has been investigated that green algae with Ulvan sulfated polysaccharide are recognized as a stabilizing and reducing agent for the development of AgNPs. It can also be used as an advanced material in the field of cosmetics and biomedicine to prepare antimicrobial compounds (Massironi et al., 2019). Subramaniyam et al. (2015) employed micro soil algae, Chloro coccum sp. for the synthesis of spherical FeNPs ranging in size from 20 to 50 nm with salt iron chloride. As confirmed by TEM findings, the microalgae cell surface retained nano iron, not just localized within and outside the cell. Patel et al. (2015) is an AgNPs formed by several microalgae strains, including Botryococcus braunii, Coelastrum sp., spirulina sp., and Limnothrix sp. The diameters demonstrated were 15–67, 19–28, 13.85, and 25.65 nm, respectively. Using Chlorella vulgaris as a reduction agent, AgNPs of sizes between 15 and 47 nm were biosynthesized. (Annamalai and Nallamuthu, 2016). Abdelghany et al. (2018) later assessed the anti-tumor efficacy of different concentrations of biosynthesized AgNPs by the blue - green algae and Anabaena oryzae. Nostoc museum and Calothrix marchic on ascites carcinoma of Ehrlich-Lettre in a test tube. Such techniques provide sufficient proof for cellular internalization. Spirulina platensis (average size 11.5 nm) and Nastoc sp. were used for the bioprocessing of AgNPs in Chlamydomonas reinhardtii, which are extremely functional for embracing execution, and the future of AgNPs in the aquatic environment of AgNPs. At room temperature (average size 20.3 nm), recorded by Abdelghany et al. (2018). The dried unicellular microalgae, Chlorella valgenis, was used by Ferreira et al. (2017) to synthesize AgNPs in a spherical form within a range of 9.81 ± 5.7 nm. As an antimicrobial agent for biomedical applications, synthesized nanoparticles have been discovered. In addition, Arsiya et  al. (2017) investigated the synthesis of PdNPs using Chlorella vulgaris aqueous extract within 10 min. The findings of the TEM study suggest that the nanoparticles are spherical and have a size of 5 to 20 nm. Edison et al. (2016) have been reported, economical green method for synthesis of AgNPs using marine green algae Caulerpa racemosa and applied as a catalyst in Methylene blue degradation. Ramakrishna et al. (2016) have studied the biosynthesis of AuNPs

2 ­ Synthesis by microorganisms

using brown algae Sargassum tenerrimum and Turbinaria conoides, and synthesized particles, showing excellent biocatalytic activity in the degradation of aromatic nitro compounds and organic dyes. Two marine brown seaweeds, such as Padina tetrastromatica and Turbinaria conoides algae, were used by Rajeshkumar (2018) for the biosynthesis of ZnO NPs and assessed their antimicrobial activity against fish pathogens. Likewise, Sanaeimehr et al. (2018) synthesized ZnO NPs and evaluated their antiangiogenic and antiapoptotic ability against liver cancer cell lines using Sargassum muticum extract. In another study, developed an eco-friendly method of stable silver nanoparticles (AgNPs) production using the aqueous extract of Trichodesmium erythraeum. The synthesized AgNPs demonstrated good radical scavenging activity, as well as inhibited clinical bacterial and drug-resistant strains strongly (Sathishkumar et al., 2019). All these reports concluded that marine organisms are appropriate for the biogenic synthesis of nanoparticles because they contain numerous biologically active compounds and secondary metabolites that have allowed them to function as nano-industries. Such marine algae have considerable utilization in the biomedical field. Table 1 highlights results of different reports on algae-based biosynthesis of nanoparticle.

2.4 ­Bacteria Many bacteria are documented to be able to effectively reduce metal ions and accelerate either the reduction, biosorption, or oxidation of metal ions (Wang et al., 2016). As they are simple to handle and can grow in a cost-effective medium, bacteria are one of the appropriate candidates for the synthesis of nanoparticles. Correa- Llanten et al., Geobacillus sp. (Correa-Llanten et al., 2013) synthesized AuNPs. Strain, 1D17, and with Au + 3 ions, a thermophilic bacterium. Enzymes moderated the reaction and NADP as co-factor nanoparticles of cadmium sulfide with a mean size of 12 nm synthesized after the reduction of the Serratia nematodiphila CdSO4 solution obtained from the chemical company’s effluent. Antibacterial activity against Klebsiella planticola and Bacillus subtilis was seen in the generated nanoparticles (Malarkodi et  al., 2013). The extracellular synthesis of AgNPs using the radiation-resistant Deinococcus radiodurans by reducing Ag + ions was evaluated by Kulkarni et  al. (2015). The biosynthesized AgNPs demonstrated Gram-positive and Gram-negative antibacterial and antibiofilm activity (Ahmed et al., 2018). Shewanella loihica PV-4 for elucidated synthesis of Au, Pd and Pt nanoparticles with a mean size of 2–7 nm. A biofilm of loihica was used in this work for the synthesis of small particles, and synthesized nanoparticles showed excellent catalytic applications in the degradation of methyl orange dye. The synthesis of tellurium nanoparticles was reported by Zonaro et al. (2017) using ochrobacterium sp. They revealed that the strain could serve to transform toxic tellurite species into nanoparticles that are useful. For the synthesis of spherical AgNPs with a size range of 41–62 nm, Saravanan et al. (2018) applied Bacillus brevis. Synthesized AgNPs demonstrated exceptional antibacterial activity against Salmonella typhi and Staphylococcus aureus ­multidrug-resistant. Sinha et al.

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CHAPTER 2  Synthesis of metal nanoparticles by microbes

(2011) used Bacillus sp. for synthesizing nanoparticles of MnO2. Monodispersed nanoparticles with a 4.62 nm diameter and orthorhombic morphology were demonstrated by TEM micrographs. Multiple proteins retained by the metal resistant bacterium are effective in reducing and stabilizing the fabricated product. This chapter covers various strains of bacteria such as Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Bacillus brevis, etc., have been applied for the synthesis of nanoparticles in Table 1.

2.5 ­Actinomycetes Actinomycetes are a group of gram-positive bacteria that form branched filamentous hyphae having resemblance with fungal hyphae and produce numerous biomolecules, such as protein, enzymes, antibiotics and vitamins. Actinomycetes facilitate both intracellular and extracellular MNPs synthesis and are efficient for the production of polydisperse, stable and small size MNPs. Secondary metabolites and new chemical entities derived from Actinomycetes have not been extensively studied for the fabrication of metal/metal oxide nanoparticles (Manimaran and Kannabiran, 2017) (Table 1). AgNPs demonstrate that Rhipicephalus microplus and Haemaphysalis bispinosa have good acaricidal or antiparasitic activity. Buszewski et al. (2016) applied actinobacteria, streptacidiphilus durhamenesis for the fabrication of AgNPs. The characterization results reveal the formation of stable spherical silver nanoparticles within a size range of 4–48 nm exhibited antibacterial activity, against Pseudomonas aeruginosa, Staphylococcus aureus, and Proteus mirabilis. Furthermore AgNPs demonstrated good antibacterial activity against various bacteria, such as Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis, Bacillus cereus, Vibrio fluvialis, and concluded that Actinomycetes’ most frequently identified nanoparticles were AgNPs. Ranjitha and Rai (2017); Streptomyces griseoruber and Streptomyces capillispiralis ca-1, respectively, applied for the synthesis of gold and copper nanoparticles by Hassan et al. (2019). Marine bacteria used by Karthik et  al. (2014), Streptomyces sp. LK-3 for the AgNPs synthesis. The study concluded that nanoparticles and NADH-dependent nitrate reductase were extracellularly synthesized, which is responsible for the formation of AgNPs through an electron transfer reaction.

3 ­Synthesis by biocompatible green reagents 3.1 ­Ascorbic acid The research was executed to utilize nontoxic, synthetic biodegradable materials for the synthesis of MNPs (Table 1). In this scenario, Jain et al. (2015) used ascorbic acid for the fabrication of spherical copper nanoparticles as a reducing and stabilizing agent. Synthesized nanoparticles were applied as a catalyst in the oxidation of amino acid (Fig.  3). Gonçalves Martins et  al. (2020) studied the pH effect of the use of ascorbic acid as a reducing and stabilizing agent in the synthesis of CuNPs. Produced CuNPs in non-uniform size with a diameter of 1042–3.34 nm. Malassis et al. (2016)

3 ­ Synthesis by biocompatible green reagents

FIG. 3 Synthesis of copper nanoparticles using ascorbic acid as biocompatible reagent. Data from Jain, S., Jain, A., Kachhawah, P., Devra, V., 2015. Synthesis and size control of copper nanoparticles and their catalytic application. Trans. Nonferrous Met. Soc. China. 25, 3995–4000, with permission from Elsevier.

reported the synthesis of AuNPs (Size-8-80 nm) and AgNPs (Size 20–175 nm) using ascorbic acid as reducing agent. This approach is the simple, fast and versatile nanoparticle surface modification with a large variety of water-soluble surfactants that can be neutral, positively or negatively charged. Moreover, ascorbic acid has been used as functionalizing and capping agent for nanoparticles. Sreeja et al. (2015) using ascorbic acid to synthesize stable particles for medical use, superparamagnetic iron oxide nanoparticles were coated and further functionalized. The TEM analysis findings show that particles with an average particle size of 5 nm were spherical. Fathima et al. (2018) also reported a simple, single-step process for preparing copper nanoparticles (CuNPs) together with photocatalytic dye degradation activity, the use of l-ascorbic acid as a reducing and capping agent. Ascorbic acid Used as an agent reducer along with chitosan as a stabilizing agent. It produced nanoparticles, with uniform size (Shao et al., 2018).water-soluble an antioxidative agent like ascorbic acid seems to be responsible for the reduction in Desmodium triflorum. The plant produces a large number of hydrogen ions, along with NAD during glycolysis, and act as a robust and reducing agent (Ahmad et al., 2011). This is a unique approach in the field of green nanotechnology that suggest the application of natural agents in the advancement of this field.

3.2 ­Biopolymers In the past decades, research has centered on the preparation and characterization of MNPs using biopolymers due to their remarkable characteristics such as non-­ toxicity, biocompatibility biopolymers, such as polysaccharides proteins. As a

29

30

CHAPTER 2  Synthesis of metal nanoparticles by microbes

s­ tabilizer and reduction agent in the green synthesis of MNPs, polyesters and lipids have been reported. In this regard, (El-Sherbiny et al., 2016) used chitosan (Cs) as non-core for the synthesis of core-shell amino terminated hyper-branched CsNPs (HBCS-NH2NPs). The developed nanocomposite (HBCS-NH2NPs) were then characterized. Used because of their consistent spherical morphology and a large number of terminal amino groups for the controlled synthesis of AgNPs on their surface. The results reveal that was AgNPs were tamped on the surface of the nanocomposite. In another study, the innovative model for the synthesis of Ag, Au, and Pt nanoparticles was the use of cellulose nanocrystals (CNC) (Padalkar et al., 2010). Cetyl trimethyl ammonium bromide (CTAB), a cationic surfactant was used to increase the stability of nanoparticles. The result illustrates the concentration and size of the nanoparticle were regulated by changing the concentration of surfactant precursor solutions, reaction time and pH of the solution. Jegan et al. (2011) also reported coprecipitation of iron (III) and iron (II) was used to synthesize well-dispersed magnetite Fe3O4 agar nanocomposite. Hanan et al. (2016) reported AuNPs colloid was prepared using alkali catalyzed pectin biopolymer. Pectin was used as reductant small size spherical AuNPs were produced with the size distribution of 2 to 16 depends on alkali type. Polysaccharides serve as a capping agent in the manufacture of low-cost, hydrophilic, stable and biodegradable nanoparticles. In the presence of water, synthesis is carried out, thereby reducing the use of harmful solvents. (Duan et  al., 2015). They have not only been found to alter TiO2 structure and morphology, but have induced various rutile phases in the presence of chitosan (Bao et al., 2013). Cheng et al. (2013) synthesized AgNPs using amino cellulose as a reduction and capping agent within the size range of 2 to 14 nm. Polysaccharides have, therefore, one of the sustainable green alternatives for nanoparticles synthesis (Table 1). Hossam and Hanan (2015) were firstly applied polysaccharide as a reducer and stabilizer for AgNPs. Polysaccharides are particularly attractive biomedical applications due to their biocompatibility. Additionally, to its eco -friendly effects and easy method into different hydrogel shapes, made polysaccharides used on a large-scale synthesis of AgNPs.

3.3 ­Amino acids and proteins Due to its non-toxic nature and eco-friendly methods, the synthesis of nanoparticles using biomolecules has recently gained interest. Amino acid serves as an effective reduction and capping agent with the unique structure to synthesize MNPs (Table 1). Maruyama et al. (2015) used amino acids, L-histidine for the synthesis of AuNPs with size 4–7 nm. The higher concentration of L- histidine produced smaller size of NPs. Characterization results reveal amino and carboxyl group present in the amino acids is responsible for the reduction and coating of nanoparticle surface. Ramakrishnan et al. (2015) investigating the interaction between specific amino acids and crystallographical aspects of Pt. Their observation shows that the electrostatic interactions were accountable for the binding of amino acid to surface of Pt. The effect of G-12(GLHUMHKVAPPR) binding peptide ZnO and its G-16 derivative (GLHUMHKVAPPRGGGC) on the growth and morphology of crystalline ZnO was

3 ­ Synthesis by biocompatible green reagents

reported by Sola-Rabada et al. (2015). G-12 and G-16 changed the morphology of ZnO by means of adsorption, a growth inhibition mechanism. In order to synthesize iron nanocomposites, Siskova et  al. (2013) used various amino acids, such as L-glutamic acid, l-glutamine, L-arginine and L-cysteine, and studied the pH effect on FeNPs generation. Mandizadeh et al. (2019) reported amino acids assisted hydrothermal synthesis of W-type SrFe18O27 nanoparticles and their use as hydrodesulphurization catalyst. The activity of SrFe18O27 nanoparticles for HDS process was examined in different conditions. Increasing concentration of nanoparticles cause to promote the rate of desulfurization. In addition, the removal of sulfur contents enhances by rise in temperature. Hydrogen partial pressure can also affect the hydrodesulphurization. A protein is a large biomolecule consisting of one or more long chains of amino acids reduces that can be involved in both metallic NP biosynthesis and stabilization. A plethora of biomolecules including proteins and amino acids with exposed disulfide bridges and thiol groups were stabilizing and reducing agents during the biogenesis of NPs (Duran et al., 2015). Chakraborty and Parak (2019) explain the protein-directed shape control process based on recent advancement and emphasis to syntheses, which directly involve proteins for the shape-controlled growth of noble nanoparticles. Dezhi et al. (2019) reported Size and morphology controllable synthesis of AgNPs in trypsin matrix by changing the experimental factors. The protein-assisted synthetic strategy eliminates the requirement of intermediate protecting and linking agents, which is simple, effect, less energy consuming, and closer to the needs of green chemistry. Due to the small size and complex morphologies, synthesized AgNPs demonstrated good antibacterial activity against both Gram-positive and Gram-negative bacteria.

3.4 ­Sugars Yan et al. (2015) applied wood-derived sugar under hydrothermal carbonization conditions to synthesize carbon encapsulated iron nanoparticles. Detailed characterization results revealed that nanospheres with an iron core diameter of 10 to 25 nm were around 100–150 nm in diameter. The study also includes their catalytic effect to convert the Syn gas into liquid hydrocarbons. The synthesis and stability of MNPs can be influenced by plant sugar extracts. The capping properties of sugar extract have been reported to depend on the content of non-soluble carbohydrates such as starch (Sharma et  al., 2009). Glucose and soluble starch are used as a stabilizing agent to synthesize silver and gold nanoparticles. (Shervani and Yamamoto, 2011). The synthesized AuNPs was reported using selected glucose derivatives (Sousa et al., 2016). In reaction to glycosides substituted at carbon center, the sugar C-6 position was oxidized to carboxylic acid with a reduction of auric acid to AuNPs. Hemmati et al. (2019) reported, Silver nanostructures have been synthesized as green reducing agents at low temperatures using various sugar substitutes and artificial sweeteners. Through the addition of sodium hydroxide (NaOH), the pH of the solution was varied to increase the strength of the reducing agents by converting non-reducing sugars to reducing ones and thus increasing the silver nanoparticle formation rate (Table 2).

31

Table 2  Metal/metal oxide nanoparticles biogenic synthesis by biocompatible green reagents. Biochemical agent

Biogenic Nps

Size (nm) and shape

Application

Reference

Ascorbic acid

CuNPs

Oxidative deamination of amino acids

Jain et al. (2015)

Ascorbic acid

CuNPs

Ascorbic acid

FeO NPs

9 nm, Spherical Crystalline 1042 ± 3.24 nm, non-uniform 5 nm, Spherical

Ascorbic acid Ascorbic acid

AgNPs AgNPs

Food packaging material

Nanocomposite biopolymer (HBCS-NH2 NPs) Natural biopolymer

AgNPs

> 50 nm, Spherical and FCC Spherical

AgNPs, CuNPs, AuNPs, Pt NPs

Agar

Fe3O4 NPs

Pectin biopolymer Amino cellulose polysaccharide Nano cellulose Polysaccharides

AuNPs AgNPs

5–20 nm, Polydisperse, 5 nm, Polydisperse 5–20 nm, Polydisperse ~̴5 nm, Polydisperse 50–200 nm, Spherical and Hexagonal 2–16 nm, Spherical 2–14 nm

AgNPs AgNPs

Spherical Different Hydrogel Shapes

l-Arginine

FeNPs

Spherical (pH dependent)

and l-cysteine

As agent for MRI applications

Optical sensor for ammonia detection

Gonçalves Martins et al. (2020) Sreeja et al. (2015) Rathore et al. (2020) Shao et al. (2018) El-Sherbiny et al. (2016)

Padalkar et al. (2010)

Jegan et al. (2011)

Antibacterial agents Antimicrobial agents Medical devices and antimicrobial agents Pollutant removal

Hanan et al. (2016) Cheng et al. (2013) Pawcenisa et al. (2019) Emam and Ahmed (2016) Siskova et al. (2013)

Valine

SrFe18O27

45 nm, Spherical

l-histidine

AuNPs

4–7 nm

Trypsin

AgNPs

10 nm, Spherical

Sugar

FeNPs

Sugar and artificial sweeteners

AgNPs

Nanosphere: 100– 150 nm, Iron Core: 10–25 nm Different Shapes and size

Glucose derivative Sucrose

AuNPs AuNPs-AgNPs

 10 nm, Spherical

Catalyst for the hydrodesulphurization of liquid fuels Biological, medical and environmental application Application in bio-medical field Catalyst

Mandizadeh et al. (2019)

Biological and pharmaceutical application Nano medicine Photocatalytic activity for reduction of 4 nitro-phenol

Hemmati et al. (2019)

Maruyama et al. (2015) Dezhi et al. (2019) Yan et al. (2015)

Sousa et al. (2016) Sun et al. (2018)

34

CHAPTER 2  Synthesis of metal nanoparticles by microbes

4 ­Factors affecting biogenic synthesis of MNPs The physico-chemical properties of nanoparticles are generally known to be highly dependent on their size and morphology. Sadeghi et al. (2012) reported that the nano plate shaped nanoparticles due to the large surface area shows good antibacterial activity than, with nano road shape. In another report is smaller size of ZnO NPs (12 nm) effectively inhibited bacterial growth in comparison to larger size (212 nm) (Raghupathi et al., 2011). Consequently, for fabrication with the effective size distribution morphology of NPs, it is important to optimize the different parameters, such as pH, temperature, concentration of reactants, reaction time, and conditions. The biosynthesis of NPs appears to be better to gain economical recognition, if the NPs are synthesized with high yield in the required size and shape.

4.1 ­Effect of pH In the synthesis of NPs, the pH of the reaction solution plays a major role. PH has the ability to modify the properties of biomolecules responsible for capping and stabilizing NPs (Mohd Yusof et al., 2019). The species of microbes applied in the synthesis can also affect the optimization of pH. For instance, the acidophilic Bactrim, Lactobacillus casei, increases the absorption of the generation of AgNPs at lower pH. This confirms that growth and activity of L. casei are superior in acidic environment (Korbekandi et  al., 2012). Whereas, Gurunathan et  al. (2009) observed that synthesis of AgNPs within 30 min indicating that the protein that acts as a reducing agent was active under alkaline conditions at pH 10. In addition, the characterization result exhibited smaller size of NPs (10–15 nm). These results are in agreement with another study, which reports, increase in absorbance peak of AgNPs as increased the pH value (Ma et al., 2017) The reduction of silver ions by the amino acid (tyrosine) as a reducing agent in the alkaline medium is also highly influenced by pH. The phenyl group of tyrosine at higher pH is ionized and the electron is transferred to silver ions and oxidized into semiquinone (Selvakannan et al., 2004).

4.2 ­Effect of temperature The temperature can strongly affect the rate of formation and size as well as the shape of the NPs. The rate of reaction and capability of some microorganisms, with respect to synthesis of NPs are increases at high temperature (Shah et  al., 2015). For example, using fungi Chrysosporium and Fusarium as reducing agent for the synthesis of AgNPs at 25o -30o degree temperature. The results indicate at lower temperature the smaller size of NPs formed, and at the higher temperature formation of large ones (Soni and Prakash, 2011). Another study states that the optimization of the reaction temperature with NP size from 5 to 25 nm could be achieved by the size selective synthesis of CuNPs. The reaction temperature variation and capping molecules has been demonstrated to synthesize CuNPs, with different shapes such as roads and cubes (Mott et al., 2007). Mohammed Fayaz et al. (2009) observed the

4 ­ Factors affecting biogenic synthesis of MNPs

effect of temperature on size of NPs synthesized by Tricorderma viride at different temperature. The results showed at higher temperature, the spectra of NPs are observed at lower wavelength (405 nm), whereas at lower temperature spectra observed at higher wavelength (451 nm) indicating the increasing size of NPs at higher wavelength regions. In another research at 80 °C with 10–15 mm size range produced maximum AgNPs using Sclerotinia scleroticrum. The postulated that at higher temperature, kinetic energy of reaction increases thus rate of synthesis increases consequently, maximum NPs are obtained with a smaller size (Saxena et al., 2016). The decrease in particle size at higher temperatures is due to a greater reaction at higher temperatures. (Gurunathan et al., 2009).

4.3 ­Effect of reactants concentration Another critical factor is the initial concentration of metal salt in the reaction mixture. With the synthesis of AuNPs by cytosolic extract of Candida albicans, the formation of NPs could be regulated by different cytosolic extract concentrations (Chauhan et al., 2011). The study reports, the synthesized NPs were non- spherical at low concentration of the extract, but spherical when it was high. The effect of different reactant salt concentration on fabrication of AuNPs applying fungus Cladosporium oxysporum reported that optimal concentration of salt at 1.0 × 10− 3 mol/liter gave maximum yield of NPs, whereas at 2.0 × 10− 3 and 5.0 × 10− 3 mol/liter mol/liter NPs were not formed (Bhargava et al., 2016). This conclusion is consistent with that reported by Jain et al. (2017). The study described synthesis of CuNPs using ascorbic acid, as a reducing and stabilizing agent. The average dimension of CuNPs were found to be 28, 16, 12 nm, at varying concentration of ascorbic acid. It is due to the number of Cu+ 2 ions encapsulated in ascorbic acid decreases with increasing concentration of ascorbic acid, leading to the formation of smaller CuNPs (Fig. 4). In addition, the study reports size-dependent catalytic activity of synthesized NPs at different concentration of ascorbic acid. The effect of metal ion concentration on synthesis of AgNPs using Penicillium aculeatum Su1suggested that at higher concentration of salt ions increased aggregation of NPs, resultant formation of larger size NPs. The study reports the highest NPs production observed at UV–Vis spectra absorbance peak at 415 nm whereas, the absorption peak moved to 435 nm at higher salt concentrations, confirming the greater size of the formation of NPs. (Ma et al., 2017). Meanwhile, Gurunathan et al. (2009) reported that synthesis of Ag NPs by E. coli. The results showed that the increase in the concentration of metal ions to a certain point created smaller NPs.

4.4 ­Effect of time Another important factor influencing the size and shape of NPs is reaction time. An rise in the rate of reaction has been observed with reduced dimension of NPs (ElSeedi et al., 2019). Darroudi et al. (2011) studied time-dependent effect in synthesis of AgNPs in natural polymeric media using gelatin and glucose, as a stabilizer, and

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CHAPTER 2  Synthesis of metal nanoparticles by microbes

FIG. 4 TEM images with a histogram of the synthesized copper nanoparticles with various concentrations of l-ascorbic acid: the average particle size is: (i) 0.08 mol L_1, d = 28 nm (ii) 0.09 mol L_1, d = 16 nm (iii) 0.10 mol L_1, d = 12 nm. Data from Jain, S., Jain, A., Devra, V., 2017. Copper nanoparticles catalyzed oxidation of threonine by peroxomonosulphate. J. Saudi Chem. Soc. 21, 803–810, with permission from Elsevier.

­References

reducing agent. The study includes in UV. Vis spectra, the AgNPs can be shown by surface plasma resonance (SPR) peak at 400 nm, but a small shift in the wavelength of the peak could be related to different shapes, size of synthesized AgNPs. Jain et al. (2015) also reports shift of wavelength at different interval of time during synthesis of CuNPs by ascorbic acid. There was an increase in intensity of spectra with the reaction progressing, this was due to the growth of CuNPs. The synthesis of ZnO NPs using Pichia kudriavzevii extends reaction time when exposed to salt ions at 36 h and synthesized NPs are obtained in irregular shapes. Whereas reaction time 12, and 24 h, produced smallest size of NPs (Moghaddam et al., 2015). On the other hand, Selvarajan and Mohanasrinivasan (2013) observed synthesis of ZnO NPs using Lactobacillus sp. yielded NPs with a size of 7 nm within 5–10 min of reaction time.

5 ­Conclusion and future perspectives The chapter highlights the synthesis of MNPs by different microbes and bio- compatible green reagents. The microorganisms secrete biologically active compounds have dual role functional groups in reducing and capping agent. The biosynthesized nanoparticles were produced at ambient conditions, without any additional chemicals, with unique properties and applications. Due to their biocompatibility and stability, it was also proven that biosynthesized NPs are a feasible another possibility to the physical and chemical methods. However, limitation of biosynthesis of MNPs still exist, such as low production, poor product quality contamination from bio cells, and tedious separation of NPs from biological materials Many optimization processes have therefore been carried out to obtain suitable MNPs with high yield through various physico-chemical parameters and various types of micro-organisms. Further research should focus on better understanding of the mechanism involved in the MNP formation and controlling the morphology, size, and dispersing. Further, exploring the microbial diversity to search for novel and sustainable microbes to synthesis of MNPs. In near future, new possibilities may also come with new problem solutions.

­References Abdelghany, T., Al-Rajhi, A.M., Al Abboud, M.A., Alawlaqi, M., Magdah, A.G., Helmy, E.A., Mabrouk, A.S., 2018. Recent advances in green synthesis of silver nanoparticles and their applications: about future directions. A review. BioNanoSci. 8, 5–16. Abd-Elnaby, H.M., Abo-Elala, G.M., Abdel-Raouf, U.M., Hamed, M.M., 2016. Antibacterial and anticancer activity of extracellular synthesized silver nanoparticles from marine Streptomyces rochei MHM13. Egypt. J. Aquat. Res. 42 (3), 301–312. Abdel-Raouf, N., Al-Enazi, N.M., Ibraheem, I.B., 2017. Green biosynthesis of gold nanoparticles using Galaxaura elongata and characterization of their antibacterial activity. Arab. J. Chem. 10, S3029–S3039.

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Sreeja, V., Jayaprabha, K.N., Joy, P.A., 2015. Water-dispersible ascorbic-acid-coated magnetite nanoparticles for contrast enhancement in MRI. Appl. Nanosci. 5, 435–441. Srinath, B., Namratha, K., Byrappa, K., 2018. Eco-friendly synthesis of gold nanoparticles by bacillus subtilis and their environmental applications. Adv. Sci. Lett. 24, 5942–5946. Sriramulu, M., Sumathi, S., 2018. Biosynthesis of palladium nanoparticles using Saccharomyces cerevisiae extract and its photocatalytic degradation behavior. Adv. Nat. Sci. Nanosci. Nanotechnol. 9, 025018. Stalin Dhas, T., Ganesh Kumar, V., Abraham, L.S., Karthick, V., Govindaraju, K., 2012. Sargassum myriocystummediated biosynthesis of gold nanoparticles. Spectrochim. Acta A MolBiomol Spectrosc. 99, 97–101. Subramaniyam, V., Subashchandrabose, S.R., Thavamani, P., Megharaj, M., Chen, Z., Naidu, R., 2015. Chlorococcum sp. MM11-a novel phyco-nanofactory for the synthesis of iron nanoparticles. J. Appl. Phycol. 27, 1861–1869. Suganya, K.S.U., Govindaraju, K., Kumar, V.G., 2015. Blue green alga mediated synthesis of gold nanoparticles and its antibacterial efficacy against gram positive organisms. Mater. Sci. Eng. C47, 351–356. Sun, L., Yin, Y., Wang, F., Su, W., Zhang, L., 2018. Facile one-pot green synthesis of Au–Ag alloy nanoparticles using sucrose and their composition-dependent photocatalytic activity for the reduction of 4-nitrophenol. Dalton Trans. 47, 4315. Suryavanshi, P., Pandit, R., Gade, A., Derita, M., Zachino, S., Rai, M., 2017. Colletotrichum sp.- mediated synthesis of Sulphur and aluminium oxide nanoparticles and it’s in vitro activity against selected food-borne pathogens. LWT–Food Sci. Technol. 81, 188–194. Wang, C., Kim, Y.J., Singh, P., et  al., 2016. Green synthesis of silver nanoparticles by Bacillusmethylotrophicus, and their antimicrobial activity. Artif Cells Nanomed. Biotechnol. 44, 1127–1132. Wypij, M., Czarnecka, J., Swiecimska, M., Dahm, H., Rai, M., Golinska, P., 2018. Synthesis, characterization and evaluation of antimicrobial and cytotoxic activities of biogenic silver nanoparticles synthesized from Streptomyces xinghaiensis OF1 strain. World J. Microbiol. Biotechnol. 34, 23. Yan, Q., Street, J., Yu, F., 2015. Synthesis of carbon-encapsulated iron nanoparticles from wood derived sugars by hydrothermal carbonization (HTC) and their application to convert bio-syngas into liquid hydrocarbons. Biomass Bioenergy 83, 85–95. Yang, Z., Li, Z., Lu, X., He, F., Zhu, X., Ma, Y., He, R., Gao, F., Ni, W., Yi, Y., 2017. Controllable biosynthesis and properties of gold nanoplates using yeast extract. Nano-Micro Lett. 9, 5. Zhang, X., Qu, Y., Shen, W., Wang, J., Li, H., Zhang, Z., Li, S., Zhou, J., 2016. Biogenic synthesis of gold nanoparticles by yeast Magnusio mycesingens LH-F1 for catalytic reduction of nitrophenols. Colloids Surf. A Physicochem. Eng. Asp. 497, 280–285. Zonaro, E., Piacenza, E., Presentato, A., Monti, F., Dell'Anna, R., Lampis, S., Vallini, G., 2017. Ochrobactrum sp. MPV1 from a dump of roasted pyrites can be exploited as bacterial catalyst for the biogenesis of selenium and tellurium nanoparticles. Microb. Cell Factories 16, 215.

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CHAPTER

Plant and agri-wastemediated synthesis of metal nanoparticles

3 Vijay Devra

Department of Chemistry, J.D.B. Govt. P. G. Girls College, Kota, Rajasthan, India

1 ­Introduction In recent years, research interest in metal nanoparticles and their synthesis has increased significantly because of their intensive applications in different industrial sectors (Das and Chatterjee, 2019). Nanoparticles are being investigated to the fundamental building blocks of nanotechnology. Nanotechnology branch is interdisciplinary, which mentioned to the subdivision of science and engineering, with a range of technical characteristics, including manufacture, characterization, nanoscale structure and material handling. Nanoscience is the study of phenomena, at 1–100 nm particle size and nanoparticles are particulate dispersion of solid particles with at least one dimension less than 100 nm (Khan et  al., 2019a). Nanoparticles have opened on various fronts for the design of new materials and assessment of their properties by regulating size, morphology and distribution of particles (Albanese et al., 2012). Metal nanoparticles do not consider in metal–metal chemical bond and determined as isolated particle between 1 and 100 nm sizes. Metal nanoparticles consist different extraordinary characteristics as compared to their bulk metal that generally contains a degenerated density of energy state, and a high ratio of surface to volume, increasing their contact with other molecules (Moghadam et al., 2019; Maghsoodi et al., 2019). Therefore, shows extensive applications in the various emerging fields, such as medicine, pharmacy, food technology, agriculture, and environmental science (Vishwakarma et al., 2017; Tazwar and Devra, 2020). For the synthesis of metal nanoparticles, different protocols have been developed. Two key strategies are commonly used to synthesize particles, referred to top-down, and bottom-up approach (Ahmed et al., 2016). In the top-down approach, the bulk material is broken down into small particles by size reduction using physical and chemical techniques, such as grinding, milling, and chemical reduction, etc. (Shedbalkar et al., 2014). The physical approaches require a high amount of energy, which makes these processes more capital intensive. However, chemical methods are eco-toxic because of the use of various hazardous chemicals, which are responsible for carcinogenicity or genotoxicity and cytotoxicity (Kharisov et al., 2016). Agri-Waste and Microbes for Production of Sustainable Nanomaterials. https://doi.org/10.1016/B978-0-12-823575-1.00030-5 Copyright © 2022 Elsevier Inc. All rights reserved.

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CHAPTER 3  Plant and agri-waste-mediated synthesis

Whereas nanoparticles are synthesized by self-assembly of atoms into nuclei in the bottom-up method, which further develop into nano-sized particles. This approach included a chemical and biological method for the production of nanoparticles. The most successful method for the synthesis of nanoparticles, however, is the bottomup approach, where a nanoparticle is formed from simpler molecules recognized as precursors of reactions. In this way, the size and shape of nanoparticles can be regulated by variations in precursor concentrations and reaction conditions such as pH temperature, etc., depending on the consecutive applications (Virkutyte and Varma, 2013). Researcher, constant efforts to develop a green process for the synthesis of nanoparticles that is simple, efficient and genuine. In order to synthesize stable and well-defined functionalized nanoparticles, several species serve as safe, eco-friendly and green precursors (Singh et al., 2019). Thus, it is important to explore the synthesis of nanoparticles in a more authentic and feasible process. In the production of nanoparticles, topics of concern are economically relevant, ecofriendly, and socially appropriate, as well as the accessibility of local properties. In order to keep the prices of competing nanotechnology-based goods economical for the purchaser, companies must maintain complex system stability and sustainability between environmentally green methods and methods. Without the presence of harmful chemicals, the green technology-based synthesis method works under green conditions. The green synthesis includes biological resources like plant extract and biodegradable waste as a reducing agent. In terms of eco-friendly alternatives, this method is beneficial for toxic chemicals that can be processed in comparatively less time, feasible, and can provide immense applications. Moreover, because plant components act as a stabilizing agent, there is no need to stabilize agents (Makarov et al., 2014). Abundant pharmacological metabolites are available and set up to bind to the synthesized nanoparticles, providing additional benefit through the increased efficacy of the nanoparticles (Singh et al., 2016). Coincidentally, the ever-growing amount of agri-waste resulting from agricultural and horticultural activities has also caused significant concern in recent years (Sharma et al., 2019). Researchers started researching waste valorization techniques for turning agri-waste into value-added goods as an eco-friendly alternative to traditional methods of disposal such as composting, incineration, and landfill to solve this ever-increasing issue. An attractive sustainable source of biomolecules and bioactive compounds that can be used by the chemical and pharmaceutical industries to manufacture high-value products such as metal nanoparticles are produced by plant-based agri-waste. Therefore, the synthesis of biogenic metal nanoparticles is considered a very interesting alternative to greener and more eco-friendly processing due to the use of chemicals lower toxicity and the use of ambient and pressure temperatures in the synthesis (Chhipa, 2019). The next section highlights the different green approaches used to synthesize metal nanoparticles that, as a green chemistry term, are successful and retain their biological properties. This is accompanied by a review of the different factors influencing the metal nanoparticles’ synthesis rate.

2 ­ Synthesis from plant materials

2 ­Synthesis from plant materials In nanotechnology, plant-mediated synthesis of metal nanoparticles has been considered as an eco-friendly process. Biological synthesis, pathways of molecular tolerance, and metabolic processes for the synthesis of nanoparticles (Rai et al., 2018). Plants have a high inclination to synthesize nanoparticles as it is renewable, biodegradable, and it provides a natural stabilizing agent to the nanoparticles immediately. According to Yallappa et  al. (2015), the simplest cost-effective and reproducible method is green synthesis of metallic nanoparticles by various plants, parts. Higher antioxidants found in photochemical constituents in seeds, fruits, leaves, and stems are blocked by various herbs and plant sources. Therefore, in the synthesis and development of nanoparticles, the benefit of plant-based phytochemicals provides a significant symbiosis between natural science and nanotechnology. This relation gives nanotechnology, introduced as green nanotechnology, a characteristically green approach. These manufacturing processes can be carried out without substantial environmental emissions, thereby setting new standards for clean and green technologies that are highly sustainable and economically viable (Zambre et al., 2013). For the synthesis of metal and metal oxide nanoparticles, extracts from various parts of the plants, including leaf, root, latex, fruit, seed, and stem, were used. Bioactive polyphenol proteins, phenolic acids, alkaloids, carbohydrates, terpenoids, etc. are plant extracts that play an important role in reducing and then stabilizing metallic ions (Schrofel et al., 2014). The key factor in the different size and shape of the synthesized nanoparticles is presumed to be the concentration and confirmation of these active molecules among different plants and their parts with metal ion (Njagi et al., 2010). An ambient atmospheric action is the synthesis of nanoparticles by metal salt reduction by plant extract. The plant extract and metal salt solution are well combined at room temperature (Park et al., 2011). The biochemical reduction in salt instants begins and the formation of nanoparticles is demonstrated by a change in the color of the reaction solution (Fig. 1). The synthesis of green nanoparticles supported by plants can be split into three stages: activation, growth and termination (Kim et al., 2010). Metal ions are recovered from their salt solution in the activation step by the reaction of plant metabolites. The metal ions move from the state of mono or divalent oxidation to zero-valent states, then a metal atom is nucleated (Malik et al., 2014). This is followed by the growth stage; nanoparticle collects to form and different morphologies like cubic, spherical, triangle, rods and wires (Akhtar et al., 2013). In the last termination stages, the nanoparticle gets their stable morphology when capped by plant biomolecules (Fig. 2).

2.1 ­Leaf extract The green synthesis of metallic nanoparticles using different plant leaf extracts has been documented by many researchers. Nilavukkarasi et  al. (2020) reported that the biosynthesized silver nanoparticles from C. zeylanica leaf extract have

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50

CHAPTER 3  Plant and agri-waste-mediated synthesis

Milling

Boiling

Filtration

Leaf Fruit, Seed

PLANT

Bark Tuber

NPs precursor Salt addition

Polysaccharides Organic acids Polypeptides

Terpe noids

NP

Flavones Phenolic compounds

NPs stabilization

NPs synthesis

FIG. 1 Graphical representation of synthesis of metal/metal oxide nanoparticles using plant extract.

FIG. 2 Activation, growth and stabilization of plant mediated nanoparticles.

a­ dmirable antimicrobial activity against pathogenic microorganisms and cytotoxicity studies have excellent anti proliferative properties. Biosynthesized AgNPs have Crystalline, The FT-IR spectrum confirmed that uniform, spherical, and monodispersed nanoparticles with a mean size of 23 nm, and the functional groups present in the AgNPs. Machado et al. (2013) analyzed the feasibility of several tree leaves for generating iron nanoparticles. The antioxidant potential of leaf extract was also assessed. The findings indicate that extracts with a higher antioxidant potential than non-dried leaves derive from dried leaves. The richest extracts were

2 ­ Synthesis from plant materials

produced from oak pomegranate and green tea, and the results of TEM analysis verified the iron nanoparticles (diameter 10 to 20 nm) could be synthesized using these plant extracts. The cheapest and greenest process for the synthesis of nanoparticles is known to be water used as a solvent for leaf extract preparation. The maximum absorption peak in UV used a low-cost reductant for the synthesis of AgNPs by Azardirachta indica (Neem) leaf extract in another study by Nagar and Devra (2019). Visible spectroscopy of synthesized AgNPs was found at 433 nm. In the oxidative degradation of acid orange 10 (AO10) and acid orange 52 (AO52) by advanced oxidation in an aqueous medium, synthesized AgNPs showed excellent catalytic activity. Joghee et al. (2019) reported eco-friendly and cost-effective biosynthesis of ZnO and MgO NPs were obtained from the leaf extract of Pisonia grandis R.Br. GCMS analysis reveals 50 phytochemicals were present in the plant extract. In stabilizing details on zinc and magnesium nanoparticles, biological molecules containing phenolic compounds present in an extract play an essential role confirmed by FTIR studies. XRD analysis indicates that ZnO particles were hexagonal phase and MgO particles as face-centered cubic geometry, with a diameter in the range, 30–60 nm, and 60–80 nm, respectively. Patil et al. (2016) examined the use of Limonia acidissima leaves to synthesize ZnO NPs and to test their effectiveness against the growth of Mycobacterium tuberculosis. The UV.Visible data show that the formation of ZnO NPs is confirmed by an absorbance peak at 374 nm, and are spherical with a size between 12 and 53 nm. Agarwal et  al. (2017) reported phyto-assisted synthesis of ZnO NPs using leaf broth of Cassia alata, and Zinc acetate (0.01 M) in another study. The formation of ZnO NPs by UV. Visible spectra, suggested the presence of a strong peak at 320 nm, confirming the nanoparticles synthesis. SEM micrographs illustrate the presence of spherical nanoparticles with size range 60–80 nm. Furthermore, FTIR spectra indicated the peak at 476.42 cm− 1 corresponding to the stretching vibrations of ZnO-Zn, characteristic peak at ZnO NPs. By using Ni(NO3)2.6H2O as a precursor and a leaf extract of Ocimum sanctum as a reducing and stabilizing agent, Pandian et al. (2015) synthesized NiNPs. The NiNPs formation was confirmed by the peak of visible spectra at 395 nm corresponding to NiNPs. XRD results confirm NiNPs have face-cantered cubic structure and average size 30 nm, which are good agreement with SEM and TEM results. To research further, in the biosynthesis of TiO2 NPs,  Thakur et al. (2019) reported characterization results revealed that transmission electron microscopy images showed the synthesized particles were spherical in shape and size ranged from 15 to 50 nm. They also studied the function of TiO2 exhibited broad spectrum antimicrobial activity against vast range of pathogens. In addition, the O. sanctum (Tulsi) leaf extract was used as a reduction agent for the synthesis of PtNPs at a temperature of 100°C.The average size of the PtNPs was 23 nm (Soundarrajan et al., 2012). Some other recent studies are reported for the biosynthesis of metal/metal oxide nanoparticles by plant leaves are includes in Table 1.

51

Table 1  Metal/metal oxide nanoparticles biosynthesized by leaves and fruit extract as plant parts. Biogenic agent

Green NPs

Size (nm) and shape

Applications

References

Capparis zeylanica

AgNPs

23 nm, Spherical

Nilavukkarasi et al. (2020)

Oak, pomegranate, green tea A. indica Pisonia grandis R.Br.

FeNPs

10–20 nm

Antimicrobial and antiproliferation activities Antioxidant

CuNPs ZnO MgO

For degradation of dye Orange G

Nagar and Devra (2018a) Joghee et al. (2019)

C. alata Limonia acidissima

ZnO NPs ZnO NPs

48 nm, Cubical 30–60 nm, Hexagonal 60–80 nm, cubical 60–80 nm, Spherical 12–53 nm, Spherical

Agarwal et al. (2017) Patil et al. (2016)

O. sanctum A. indica

NiNPs TiO2 NPs

30 nm, FCC Crystal 124 nm, Spherical

A. indica O. sanctum Bauhinia purpurea

AgNPs PtNPs AgNPs, AuNPs

15–50 nm, Spherical 9 nm, Spherical 23 nm, Irregular Spherical, hexagonal

Olea europaea Nigella arvensis Piper beetle Tomato

CuNPs AuNPs AgNPs AgNPs

20–50 nm, Spherical 3–37 nm, Spherical 6–14 nm, Spherical  80 nm, Amorphous; PdNPs > 100 nm Cubical 22.3 ± 3 nm, Spherical

AuNPs

15–20 nm

C. maxima

AuNPs

25.7 ± 10 nm

P. longum Dhruva serrulata

AuNPs AgNPs, AuNPs

Chaenomeles sinensis Phyllanthus emblica P. farcta Comus mas

AgNPs, AuNPs

56 nm, Spherical 66 nm Spherical, 65 nm, Hexagonal 5–20 nm, 20–40 nm

Catalytic activity for 4-nitrophenol reduction to 4-aminophenol reduction Antioxidant and catalytic agent Biomedical and environmental applications Biomedical applications

30 nm, Hexagonal 12.68 nm 16 nm, spherical, 19 nm, pseudo spherical

Antimicrobial applications Biomedical applications Mobilized the antioxidant defense mechanisms

Behravan et al. (2019) Lee et al. (2019) Singh et al. (2019) Zangeneh et al. (2019)

Rajeshkumar et al. (2019) Ali et al. (2019) Zhang et al. (2019) Rabiee et al. (2020a,b) Rabiee et al. (2020a,b) Kumar et al. (2020) Chanraker et al. (2020)

Fruit extract

AgNPs AgNPs AgNPs, AuNPs

Antireducing agent Synthesis of biological important 2-arylbenzimidazoles Biomedical application

Mohan Kumar et al. (2013) Kumar et al. (2014a,b) Basavegowda et al. (2014) Yu et al. (2016) Nakkala et al. (2016) Singh et al. (2018) Oh et al. (2018) Renuka et al. (2020) Salari et al. (2019) Filip et al. (2019)

54

CHAPTER 3  Plant and agri-waste-mediated synthesis

2.2 ­Fruit extract In Table  1, some scientists use fruit for the synthesis of metallic nanoparticles. Kumar et al. (2013), using the fruit extract of Terminates chebula, formed palladium and iron nanoparticles. Polyphenolic-rich T. chebula extract displays a redox potential of 0.63 V vs. saturated calomel electrode by cyclic voltammetry, which helps to minimize iron salt to iron nanoparticles. Highly stable FeNPs were developed by T. chebula extract, which requires polyphenol complexation, by reducing the ferrous salt solution. A 5:1 ratio of fruit extract to FeSO4.7H2O solution, then centrifugally separated solid substance, was reacted. Analysis of X-ray diffraction (XRD) and transmission electron microscope (TEM) indicates that amorphous FeNPs were less than 80 nm in scale. Fe3O4 NPs were synthesized by Passiflora tripartita var. mollissima fruit extract and applied as a catalyst at room temperature for the synthesis of 2-arylbenzimideazole. P. tripartita var. aqueous extract Mollissima reacts with iron salt solution, synthesizes spherical FeO NPs with a size of 22.3 ± 3 nm, and synthesizes Nanocatalyst is highly active for the synthesis of critical biological 2-­arylbenzimideazole. It has been used for the production of intermediates in molecular growth for pharmaceutical and biological purposes. Basavegowda et al. (2014) also reported AuNPs of 15–20 nm size with biomedical applications photosynthesized with the help of fruit extract of Hovenia dulcis. The molecules present in the fruit extract reduced the gold metal ions in AuNPs due to a change in solution color within 30 min. In order to generate AuNPs, the Citrus maxima fruit extract underwent green synthesis. At 535 nm, the UV visible spectra showed the highest peak and FTIR analysis showed a peak of 1658 cm− 1, which corresponds to the CC double biomolecular bond vibration modes. The reduction agent is flavonoids, terpenes and vitamins, among which chloroauric acid has shown a peak of 1376 cm− 1, which could be attributed to the axial vibration of the CN bonds in the acid (Yu et al., 2016). In the presence of Prosopis farcta fruit extract as a reducing agent, Salari et al. (2019) stated that the biosynthesis of silver nanoparticles (AgNPs) was achieved. The analysis shows that in plant-AgNPs the total phenolic compounds and total flavonoids were higher than in plant extract alone. Compared to P. farcta fruit extract alone, plant-AgNPs exhibited greater antioxidant and antibacterial activity. Nakkala et al. (2016) documented the synthesis of AuNPs with data on their in-vitro antioxidant and catalytic activity using Piper longum fruit extract. The researchers concluded that these AuNPs are useful in cleaning toxic dyes in industrial effluents with strong catalytic activities.

2.3 ­Seed extract The synthesis of AuNPs using Abelmoschus esculentus aqueous seed extract has been documented. The outcomes described in the AuNPs synthesis played a vital role in the OH functional group present in the extract. The synthesized nanoparticles with a spherical size range of 45–75 nm were found. The antifungal activity of AuNPs was tested using standard diffusion methods against different types of fungi (Jayaseelan et al., 2013). Venkateswarlu et al. (2014) used Syzygium cumini seed extract for the

2 ­ Synthesis from plant materials

synthesis of iron oxide nanoparticles as a reducing agent and sodium acetate as a stabilizing agent. X-ray diffraction findings indicate that spherical magnetic NPs have been synthesized. TEM findings showed that the diameter of the cubic structure was 9–20 nm. Analysis of Bruner-Emmett-Teller (BET) gives a surface area of 3517 m2/g of synthesized FeO NPs and particles have been classified as mesoporous. In the field of water and wastewater remediation, synthesized FeO NPs can be used for the removal of toxic dyes. Azizi et al. (2017) prepared AgNPs in aqueous Citrullus colocynthis seed extract as a reducing and stabilizing agent. Biosynthesized AgNPs presented functional antibacterial activities against Staphylococcus aureus, Methicillin resistant S. aurous, Pseudomonas aeruginosa, and Escherichia coli. A green approach to the synthesis of AgNPs using an aqueous extract of Durio zibethinus seed was developed by another study and its antibacterial, photocatalytic and cytotoxic effects were determined. Surface Plasmon Resonance confirmed the formation of AgNPs with a maximum absorbance (λmax) of 420 nm. SEM and TEM images showed that AgNPs were rod-shaped and spherical, with a size range between 20 and 75 nm. AgNPs demonstrated antibacterial activity against brine shrimp and demonstrated stronger photocatalytic action against blue methylene. In the future, synthesized AgNPs could be used in the fields of water, pharmaceuticals, biomedicine, biosensors and nanotechnology (Sumitha et al., 2018).

2.4 ­Bark extract Bark extract is used for the synthesis of different metallic nanoparticles Table  2. 18.2 nm average spherical AuNPs with face-centered cubic structure synthesized using Eucommia ulmoides bark extract demonstrated excellent photocatalytic activity for the decolonization of an azo dye, cango red, and 179 reactive yellow modal compounds (Guo et al., 2015). Due to the presence of biomolecules surrounding the AuNPs core, the DLS calculation showed a greater scale. In addition, Yallappa et al. (2013) used the plant extract of Terminalia arjuna bark for the synthesis of CuO NPs within 23 nm, the size of particles. It is important to note that the Mimusops elengi bark extract was used at room temperature for the green synthesis of AuNPs. The polyphenols present in the extract of the bark were both a reduction and a stabilizing agent. As an important catalyst for the reduction of 3-nitrophenol and 4-nitrophenol to the corresponding aminophenol, synthesized AuNPs have been used (Majumdar et al., 2016). A facile and green route for the synthesis of PdNPs was carried out from PdCl2 solution (Kora and Rastogi, 2018). The investigator as a reducing and stabilizing agent used gum ghatti, a non-toxic, sustainable plant polymer obtained from the Anogeissus latifolia tree. The fabricated particles show excellent catalytic activity in the dye degradation and environmental remediation. A successful study was carried out that synthesized AgNPs using spruce bark (Picea abies L.) as a bio resource of cost-effective nonhazardous reducing and stabilizing compounds. The effects of different factors like the reactants concentration, ratio extract/salt silver nitrate and time of incubation on the controlled synthesis of AgNPs were explored (Tanase et al., 2020). The synthesis of CuONPs was reported by Vellora et al. (2013), using

55

Table 2  Biogenic synthesis of metal/metal oxide nanoparticles by plant parts of seed, bark, root and flower extract. Biogenic agent

Green NPs

Size (nm) and shape

Applications

References

Abelmoschus esculentus Syzygium cumini

AuNPs

45–75 nm, Spherical

Antifungal agent

Jayaseelan et al. (2013)

FeO Nps

9–20 nm, Cubical

Wastewater remediation

C. colocynthis Pimpinella anisum

AgNPs AgNPs, AuNPs

Biomedical applications Antifungal and antibacterial agent

Cucurbita pepo Durio zibethinus

TiO2 NPs AgNPs

23 ± 2 nm 18–22 nm,16-22 nm, Spherical > 100 nm, Tetragonal 20–75 nm, Spherical and rod

Venkateswarlu et al. (2014) Azizi et al. (2017) Zayed et al. (2020)

Various applications Antibacterial, photocatalytic

Abisharani et al. (2019) Sumitha et al. (2018)

Photocatalyst for environmental remediation Antioxidant Efficient catalyst for 3-nitrophenol and 4-nitrophenol reduction Antioxidant and catalyst

Guo et al. (2015)

Antimicrobial against E. coli Catalytic application

Vellora et al. (2013) Ganapuram et al. (2015) Suganthy et al. (2018)

Seed extract

Bark E. ulmoides

AuNPs

18.2 nm, FCC

T. arjuna M. elengi

CuO NPs AuNPs

23 nm, Spherical 9–14 nm, Spherical

A. latifolia

PdNPs

4.8 ± 1.6 nm, Spherical

Cochlospermum gossypium

AgNPs, AUNPs, PtNPs

Karaya gum S. malabarica

CuO NPs AuNPs

T. arjuna

AuNPs

5.5 ± 2.5 nm, FCC 7.8 ± 2.3 nm, FCC 2.4 ± 0.7 nm, FCC 4.8 nm, Monoclinic 12 ± nm, FCC crystalline 20–50 nm, Spherical

P. abies L.

AgNPs

226 nm, compact blocks

Neuroprotective potential via antioxidant, anticholinesterase, and antiamyloidogenic effects Antibacterial agent

Yallappa et al. (2013) Majumdar et al. (2016) Kora and Rastogi (2018) Vinod et al. (2011)

Tanase et al. (2020)

Erythrina caffra Cinnamomum verum

AgNPs MnNPs

 1 million based on an estimate in 2009 (Resh, 2009). There is a little number of these pesticides, almost (0.1%), that reaches the targeted pests and the remaining pesticides which is (99.9%) are causing contamination to the environment (Carriger et  al., 2006). This could lead to serious consequences on human health and food chain, as well as developing non-target species pesticides. Additionally, the presence of ubiquitin in pesticides has caused the development of pesticide resistance in weeds, pathogens, and insects (Rai and Ingle, 2012). Recently, biopesticides appeared to reduce the hazardous effects that synthetic pesticides are causing them. However, their use is limited due to their slow and ­environment-dependent efficiency against several pests. To overcome such a problem, nano-pesticides are showing great potential regarding such limitations. Effective pest

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control can be obtained by the controlled release and slow degradation of active ingredients in the presence of nanomaterials (Chhipa, 2017). As a result, nano-­pesticides are great tools to produce an effective and sustainable pesticide that could minimize the use of chemically synthesized pesticides. Moreover, the nano-pesticides act differently from known pesticides to increase their efficacy (Kah et al., 2019). Nano-sized particles can be transported in two different states of dissolved and colloidal states, in addition to the fact that the solubility of the active ingredient could increase degradation and mobility by the use of soil inhabiting microorganisms. For instance, the nanoparticle-based pesticides are increasing Al solubility, which could lead to less harmful impact on the environment, in comparison to the chemically synthesized ones (Kah and Hofmann, 2014). Overall, nano-pesticides are enhancing the pesticide efficiency, as well as the crop productivity by the lower input costs and higher yields by the waste and labor reduction. However, these nano-pesticides could cause some health issues according to different factors described by the protection agency (EPA, USA) (Ragaei and Sabry, 2014). The reported health issues could be as: (i) Nano-pesticides dermal absorption because of their very small sizes, so they can pass into the cell membrane, (ii) they can go deep in lungs and shift to the brain with the blood circulation, (iii) nanomaterials reactive potential is raising some environmental concerns, and (iv) lack of information of the consequences of the environmental exposure to the engineered nanomaterials (Usman et al., 2020). Nanoparticles antimicrobial activity is also well-develop to destroy bacterial, viral, and fungal pathogens. The most important inorganic nanoparticles that are having pesticidal properties are copper (Gogos et al., 2012), aluminum (Stadler et al., 2012), and sliver (Kim et al., 2012). Weeds are considered as a huge threat in modern agriculture. Nano-herbicides are depending on the biodegradable polymeric substances that could cause an improvement of the herbicides’ efficiency. Weeds are considered a huge threat to modern agriculture techniques. Most of the nano-herbicides content is biodegradable polymeric compounds. These compounds could improve the herbicides. Efficiency e.g., poly (epsilon-caprolactone) due to its good physio-chemical properties it has been used to encapsulate atrazine, which enhanced the biocompatibility and bioavailability (Abigail and Chidambaram, 2017). These polymeric nanoparticles which are encapsulated with atrazine were effective on target plant such as Brassica spp. Moreover, it enhanced the herbal activity, stability for 3 months, and reduced the soil mobility in comparison to the other types without atrazine (Grillo et al., 2012). Similar results were reported in other studies that the polymer-based encapsulated with different herbicides such as atrazine, paraquat, and ametryn and simazine increased the bioavailability of the herbicide which has similar or slightly glyphosate nanoemulsion efficacy than the commercial formulation (Jiang et al., 2012; Lim et al., 2013).

2.2 ­Nano-fertilizers Climate change has a great effect on the agricultural sector which aggregated by urbanization, global warming, and unbalanced use of resources and environmental

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problems such as eutrophication and runoff which are related to the use of conventional fertilizers. These addressed problems are increasing rapidly because of the population increase that is estimated to reach 9.6 billion in 2050 (DeSA, 2013). Furthermore, the use of conventional fertilizer is considered as one of the reasons behind the huge economic losses due to the leaching issues (40%–70%) that is crucial for developing countries where they are relying heavily on agriculture for their economy (Ditta and Arshad, 2016). As a result, there is a huge need to introduce new fertilizers that could provide the plants with the needed nutrients in slow and small ratios to avoid nutrient loss (Liu and Lal, 2015). Moreover, several types of slowrelease nano-fertilizers have been synthesized and introduced to the market such as encapsulated materials or polymer-coated (Costa et al., 2013; Guo et al., 2005), biochar based (Ding et al., 2016; Xie et al., 2011), and zeolite-based (Bansiwal et al., 2006; Lateef et al., 2016). The most preferred ones are biochar and zeolite-based due to their natural sources which make them environmentally friendly (Colella, 1999; Hunt et al., 2010; Ramesh and Reddy, 2011; Xie et al., 2015). Nano-fertilizers are nano-materials which either could be nutrients themselves, micro or macro-nutrients, or are playing key roles as additives/carriers, for example by composting them with minerals, for the nutrients (Kah et al., 2018). Additionally, nano-fertilizers can improve crop yield and quality by reducing the production cost, as well as using higher nutrient efficiency. As a result, this could contribute to agricultural sustainability. A critical analysis of a nano-fertilizers dataset revealed that there is a median efficacy gain of approximately 18%–29% by nano-fertilizers when comparing them to conventional fertilizers (Kah et al., 2018). The use of phosphatic nano-fertilizers has been linked to the growth rate increase by 32% and seed yield by about 20% of soybeans (Glycine max L.) when comparing it to those prepared with conventional fertilizer (Liu and Lal, 2015). Furthermore, nano-fertilizers can enhance the plant metabolism and the nutrients uptake through nanometric pores which are facilitated by nanostructure cuticle pores of molecular transporters (Rico et al., 2011). The induction of nanotechnology techniques and materials in plant nutrition is enhancing the development of slow/controlled-release fertilizers that consequently could improve the efficiency of the fertilizer itself, as well as reducing the nutrient loss (Liu and Lal, 2014). The fertilizer, that is designed to, use efficiency of the conventional nitrogenous fertilizers is 30%–60%, whereas 8%–90% of conventional phosphatic fertilizers are being lost due to chemical bonding in the soil and become unavailable to the plant use (Giroto et al., 2017). On the other hand, urea and hydroxyapatite nanocomposites are offering the controlled release of nitrogen, lower NH3 volatilization, as well as sustained availability of phosphorus after incubation for 4 weeks (Giroto et al., 2017). Overall, the amount of used fertilizer is reduced when using slow-release products. Ideally, nano-fertilizers could be able to implement the nutrient release with the perfect timing and amount for the plants which could restrict the conversion of extra fertilizers. Moreover, this can be also achieved if the nutrient release is based on the signaling of the targeted plant (DeRosa et al., 2010) and these used fertilizers can explain the communicational signals between the soil microbes and the plant roots (Mastronardi et al., 2015). Additionally, nanomate-

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rials that are containing plant nutrients can respond to several physical and/or chemical stimuli that indicate the importance of the nutrients for the growth of the plants (DeRosa et al., 2010). These stimuli could be responsible for the ethylene production by the plant roots, as well as acidification of rhizosphere (Rop et al., 2019). Finally, the implementation of nanoparticles could enhance the internal root signals as was suggested and reported by Syu et al. (2014) and that affect the production of ethylene by Arabidopsis roots. In addition to, the internal roots stimuli for nutrient release in response to N and/or P deficiency could be a new breakthrough to control the release nano-fertilizers (Usman et al., 2020).

2.3 ­Nano-sensors in plant system Biosensors contributed a lot to the understanding of the physiological processes of several plants. The other traditional methods were lacking basic information regarding the substrates, transporters, and location and dynamics of enzyme receptors. As a result, this information can be easily detected with the use of biosensors (Sarma et al., 2019). The very high-resolution measurements provided by biosensors uncovered the understanding of calcium oscillation process from a deeper perspective, which is required for the symbiosis signaling in root hair cells (Miwa et al., 2006). Nuclear calcium oscillations could be easily observed with the use of Cameleon where is localized in the nucleus. Furthermore, the inner nuclear membrane is releasing calcium that was identified by the imaging of the biosensor. These Cameleon biosensors were able to help in the discovery of the deep understanding of the calcium role in the pollen tube growth, mechano-sensing in root, cell regulation, and root response to aluminum treatment. Moreover, the metabolites of biosensors have aided the understanding of transport and dynamics of metabolites in the roots. Other sensors also have helped in the measurement of the pH, reactive species in plants, and redox state. The identification of components that are missing in processes such as analyte transport, regulation or metabolism was done easily by the help of the biosensors as well. For instance, An FRET sensor for sucrose that is found in proteins and performed a transport step in the phloem loading sucrose efflux from the mesophyll layer (Bermejo et al., 2011a,b). Additionally, the fluorescence-based FRET sugar sensors have successfully indicated the transporters of sugar that act right after the yeast cells are being starved and exposed to glucose. There was a great biosensor that is developed by Diaconu et  al. who developed a Laccase-MWCNT-Chitosan biosensor which is responsible for the detection of phenolic secondary metabolites in plants (Diaconu et al., 2010). Another study that was carried out by Giraldo et al. revealed that SWCNT localizes and transporters are unalterable in the plant chloroplasts, as well as it increases the electron transport rates and photosynthetic activity to a high extent (Giraldo et  al., 2014). Biosensors could also be used in the identification of the genes that are affecting cytosolic or vacuolar pH in the cells of yeast. Finally, these reported results are proving that there could be a great application of biosensors in genetic discovery.

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2.4 ­Nano-additives The nano-delivery systems can be implemented in food applications which could be formulated as nanospheres, nanoemulsions, and nanoparticles by using several well-reported techniques. These techniques are being as precipitation, coacervation, electrospraying, spray drying, and solvent evaporation (Jafarizadeh-Malmiri et al., 2019). Several natural-derived polymers are being fabricated into the nan0-delivery systems by using one of the stated techniques. This nano-delivery system can be used in encapsulating bioactive molecules such as flavors, antimicrobials, antioxidants, and nutraceuticals (Luo and Hu, 2017). One of the applications of these nanoparticles is the introduction of them into a food matrix to function as preservatives, flavor enhancers, and nutrient supplements. There is a unique advantage for the encapsulation in comparison to the micro-sized counterparts of the nanoparticles is that the nanosized particles are safe and do not affect the food organoleptic properties unlike the micron-sized particles. Moreover, the other advantage is that the nanoparticles can offer an increasement for the bioavailability of the encapsulated nutrients and this is because of their increased surface to volume ratio (Sampathkumar et al., 2020). Several bioactive agents that are well-studied for nanoencapsulation could be classified as: minerals (Iron(Fe), Ca); fatty acids (omega-3); polyphenols (curcumin, catechins, resveratrol); vitamins (A, B, C, D); and carotenoids (lycopene, β-carotene, lutein, astaxanthin). Recently, a very important terminology appeared which is nanofood that is considered as food products that the nanoparticles or any nanostructured material are used during any stage of the food development stages (cultivation, production, processing, and packaging) (Sekhon, 2010). Moreover, the nanofood concept is raising daily and could have the potential to replace essential food products. For instance, it can increase nutritional value, reduce cost, and improve food safety and flavor. Nanofood materials are including additives that help in achieving a longer shelf life for the products, as well as improving health or even introducing new flavors. For example, the anti-microbial agents are packed in starch colloid and are coated in a way that to release the antimicrobial agents if there is any microbial infection happened on the packed food (Bouman, 2003). There’s a quicker way to be achieved during the production process which is by the addition of the nano-sensors in food to detect the pathogens present. On the other hand, some food products already have nano-sized transport systems for the supplements and nutrition addition, such as vitamins, flavors, preservatives, color, minerals, and antioxidants (Sekhon, 2010). Furthermore, the addition of the nanocarrier system is for the protection of ingredients and additives during food product processing. However, the Food and Drug Administration (FDA) issued a nanofood products warning stating that these products have some modifications in their chemical and physical properties. Additionally, nano food products are different from the macroparticles especially in their properties of the same elements and they may cause toxicity on the biological system interaction (Sharma et al., 2019). Probiotics are referring to a mixture of live bacterial species into fruit-based drinks, cheese and pudding, yoghurts and yoghurt-type fermented milk which have

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a direct beneficial effect on human consummation. After consuming these products, they are balancing the beneficial bacterial of human gut, enhancing the immune system, lowering blood cholesterol levels, and improving gut health. Moreover, encapsulation of these products increases the food shelf life. Nanoencapsulation enhances the development of specific types of bacterial probiotic and this latter could be delivered to the gastro-intestinal tract and finally, it can have an interaction with specific receptors (Sekhon, 2010). In addition to that, Vidhyalakshmi et al. (2009) studied the encapsulation effect on the healthy ingredients to achieve higher efficiency of the ingredients by using different encapsulated techniques (Vidhyalakshmi et al., 2009). They also stated that there is an improvement was achieved in the viability with the acidic food product and survival growth rates in extremely tough environmental conditions by using the encapsulated probiotic material (Vidhyalakshmi et al., 2009).

2.5 ­Food packaging The nanotechnology development in the food industry sector has resulted in an improvement of edible nano-coatings of approximately 5 nm thickness. These thin edible nano-coatings are created first on the outer layer of raw meat, cheese, vegetables and fresh fruits, bakery goods, and ready-to-eat foods. Specifically, it acts as an obstruction to the gases and moisture exchange which releases enzymes, antimicrobial agents, antioxidants, color, and flavor (Sharma et  al., 2019). This coating process has an essential rule regarding the protection of food from spoilage and, as a result, this increases the food shelf life. There are many edible coatings that have been developed and improved for vegetables, raw meat, and fresh fruits. Development of an edible coating on “Chandler” strawberries was achieved to increase their shelf life by Dhital and his colleagues (Dhital et al., 2017). Additionally, antibacterial edible nanocoating can be implemented in bakery goods directly without any extra processes. An edible smart gelatin film based was developed on gelatin and curcumin by Musso et al. (2017). The film was containing a high antioxidant property with the ability of color change as an indication for the contact with a different pH media (Sharma et al., 2019). Furthermore, nanomaterial that is being coated on food surfaces is revealing high-performance abilities in the resistance of biofilm development. Nanoparticles are being used for the reduction of the colonization of the microorganisms, inhibiting their propagation, as well as functionalization and controlled antimicrobial agents release from surfaces. These nanostructured materials are effective in preventing pathogenic bacterial growth and inhibiting food spoilage for a longer duration. Several types of nanoparticles, such as silver, titanium oxide, zinc oxide, gold, and many more, have been well-studied as coating agents for various food contact materials. A nanocoating of TiO2 was developed by Yemmireddy and Hung (2017) for the surface of chopping boards and they reported that they found a significant microbial reduction on these surfaces. Intelligent packaging or “smart and active packing systems” are referring to the same thing which is the technique that is used to pack food and products to obtain the desired attributes such as increasing the shelf life of food, monitoring

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transport and storage, and scrutinizing freshness and releasing the antimicrobial agents to reduce the contamination and spoilage of food. The bioengineered food packaging materials are associated with active and smart packing, as well as intelligent packaging (Ghoshal, 2018). Small packets of metal and their oxides, such as silver, gold, zinc oxide, iron oxide, aluminum oxide, silica, etc., are incorporated into the packaging process. Several packaging systems are using zinc oxide, silver, and magnesium oxide as antimicrobial agents. They are claiming that as they are active agents, they inhibit microbial growth for longer durations (Sharma et al., 2019). Pathogens and variations of temperatures are being detected by the use of nanostructured porous silicon food packaging. Furthermore, the improvement of the next-generation packaging reveals that the implementation of radio frequency identification display (RFID) as smart labels could assist in obtaining a quicker and more accurate distribution of foodstuffs that have a short shelf life. Nano-sensors can be also implemented in smart packaging due to their tiny sensor sizes that are being attached to food or food packaging (Sharma et al., 2019). Additionally, they can also detect viruses, chemical contaminants, and pathogenic bacteria in different food systems. For instance, one sensor can identify a wide range of pathogens which reveals their high efficiency. Research on nano-sensor is focused on the rapid detection of contaminants in food, as well as the tracking of food by incorporating a nano-sensor in the material of the food packaging. The packaging technology has a very high impact on the safety and quality of meat (Fang et al., 2017). More importantly, intelligent packaging enables a regular check on the product condition and exchanges information, while active packaging influences the packaging internal environment. A biodegradable film was formed from natural extracts and starch by Medina-Jaramillo et al. (2017). They found that this film has high antioxidant properties, as well as its color changes with any change that occurs in the pH level (Sharma et al., 2019).

2.6 ­Nano-carriers for gene delivery into plants Nanomaterials are very attractive for the intracellular biomolecules delivery such as, small interfering RNA (siRNA), proteins, or DNA) as they can inter the biological membranes and overcoming several chemical and physiological barriers (Donahue et  al., 2019; Rani et  al., 2018). Nanocarriers are already studied and explored for their unique properties for drug delivery in mammals due to their small size and surface which reveals an excellent control of the exogenous interactions with living organisms (Manuja et al., 2016). On the other hand, the use of nanocarriers in plants has not been studied sufficiently yet. This could be due to the challenging anatomic hurdle of the multilayers of plants, especially the cell wall, in comparison to the animal cell wall. In addition to that, several plant species are present compared to animal species. Plant physiology must be taken into consideration when interacting with nanocarriers in the host environment (Pérez-de-Luque, 2017). However, we can overcome these challenges by controlling the size of the used nanoparticle to fit with the diameter of the cell wall, which is ranging from 5 to 20 nm, and by tuning

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the surface properties of the nanoparticle to be able to carry different cargos (Nair et al., 2010). Now, nanoparticles with these properties can pass through the different chemical and physiological barriers to reach the plasma membrane (Chang et  al., 2013; Kwak et  al., 2019). Nanoparticles enter plant tissues in two ways either by root tissues, such as ruptures, rhizo-dermis, and root tips, or by aboveground tissues such as stigma, cuticles, hydathodes, and stomata. After the introduction into plants, the nanoparticles movement through tissues can be occurred in the simplest by sieve plates and plasmodesmata (Eichert and Goldbach, 2008; Kwak et  al., 2019; Ma et al., 2010) or in the apoplast by cell walls, xylem vessels, and extracellular spaces (Albanese et al., 2012). Nanoparticles can move through the apoplast pathway which allows the radial movement within plant tissues. However, for reaching the nucleus then nanoparticles have to pass through several chemical and physiological barriers, and this is controlled by size exclusion limits. For instance, Casparian strips (