Nanopesticides, Nanoherbicides, and Nanofertilizers: Formulations and Applications [1 ed.] 1032428120, 9781032428123

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Nanopesticides, Nanoherbicides, and Nanofertilizers Nanopesticides, Nanoherbicides, and Nanofertilizers: Formulations and Applications demonstrates the potential for nanomaterials to revolutionize modern agriculture to become more sustainable. A team of expert scientists explain how the nanoformulation of traditionally used herbicides, fertilizers, and pesticides can protect large-scale crops from unwanted weeds and pests as well as from the environmental side effects that are caused by the bulk application of chemicals. This book demonstrates how nanomaterials, such as hydroxyapatite, clay minerals, zeolites, and polyacrylic acid, have been successfully used to develop fertilizers that promote a slower release of chemicals due to the unique properties of nanomaterials. Their use in lower concentrations helps in decreasing the toxicity to non-targeted organisms as well as lowering the risk of environmental degradation.

FEATURES: • Categorically discusses the formulations and applications of nanopesticides, nanoherbicides, and nanofertilizers, as well as their impact on the environment. • Presents chapters on patent landscape, environmental acceptability, and environmental risks. • Addresses degradation of nanoparticles as well as expected toxicity and drawbacks of nanomaterial-based pesticides, herbicides, and fertilizers. This book is essential reading for researchers and professionals working in the fields of biotechnology, nanomaterials, and agricultural chemistry. Dr. Anjali Gupta is Professor and Researcher in the Division of Chemistry, Galgotias University, Uttar Pradesh, India. Dr. Divya Bajpai Tripathy is Professor and Researcher in the Division of Chemistry, Galgotias University, Uttar Pradesh, India. Dr. Gaurav Kumar is Associate Professor in the Clinical Research Division and Institution’s Innovation Council In-Charge at Galgotias University, Uttar Pradesh, India. Dr. Pooja Agarwal is Professor in the Division of Chemistry, Galgotias University, Uttar Pradesh, India. Dr. Anujit Ghosal is Researcher at the Richardson Centre for Food Technology and Research, Department of Food and Human Nutritional Sciences, The University of Manitoba, Canada.

Nanopesticides, Nanoherbicides, and Nanofertilizers Formulations and Applications

Edited by Anjali Gupta, Divya Bajpai Tripathy, Gaurav Kumar, Pooja Agarwal, and Anujit Ghosal

Designed cover image: Shutterstock_2048834960 First edition published 2024 by CRC Press 6000 Broken Sound Parkway NW, Suite 300, Boca Raton, FL 33487–2742 and by CRC Press 4 Park Square, Milton Park, Abingdon, Oxon, OX14 4RN CRC Press is an imprint of Taylor & Francis Group, LLC © 2024 selection and editorial matter, Anjali Gupta, Divya Bajpai Tripathy, Gaurav Kumar, Pooja Agarwal, and Anujit Ghosal; individual chapters, the contributors Reasonable efforts have been made to publish reliable data and information, but the editors and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The editors and publisher have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, access www.copyright.com or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978–750–8400. For works that are not available on CCC please contact [email protected] Trademark notice: Product or corporate names may be trademarks or registered trademarks and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging‑in‑Publication Data Names: Gupta, Anjali (Bioorganic chemist), editor. | Tripathy, Divya Bajpai, editor. | Kumar, Gaurav (Biomedical engineer), editor. | Agarwal, Pooja (Professor of chemistry), editor. | Ghosal, Anujit, editor. Title: Nanopesticides, nanoherbicides, and nanofertilizers : formulations and applications / edited by Anjali Gupta, Divya Bajpai Tripathy, Gaurav Kumar, Pooja Agarwal and Anujit Ghosal. Description: First edition. | Boca Raton, FL : CRC Press, 2024. | Includes bibliographical references and index. Identifiers: LCCN 2023024002 Subjects: LCSH: Nanobiotechnology. | Agricultural innovations. | Pesticides— Technological innovations. | Herbicides—Technological innovations. | Fertilizers— Technological innovations. Classification: LCC TP248.25.N35 N3582 2024 | DDC 660.6—dc23/eng/20230630 LC record available at https://lccn.loc.gov/2023024002 ISBN: 978-1-032-42812-3 (hbk) ISBN: 978-1-032-42814-7 (pbk) ISBN: 978-1-003-36442-9 (ebk) DOI: 10.1201/9781003364429 Typeset in Times by Apex CoVantage, LLC

Contents Preface�����������������������������������������������������������������������������������������������������������������������������������������������xi List of Contributors�������������������������������������������������������������������������������������������������������������������������xiii Chapter 1 Introduction to Nanopesticides, Nanoherbicides, and Nanofertilizers������������������������� 1 Priyanka Singh, Dania Khan, and Ashok Kumar 1.1 Introduction������������������������������������������������������������������������������������������������������� 1 1.2 Overview of Pesticides, Herbicides, and Their Nanoparticles�������������������������� 2 1.2.1 Pesticides and Their Classification�������������������������������������������������������2 1.2.2 Effects and Regulation of Pesticides����������������������������������������������������3 1.2.3 Biopesticides�����������������������������������������������������������������������������������������4 1.2.4 Nanopesticides�������������������������������������������������������������������������������������5 1.2.5 Nanoherbicides�������������������������������������������������������������������������������������6 1.2.6 Major Challenges of Nanopesticide and Nanoherbicides Uses������������������������������������������������������������������������������������������������������8 1.3 Overview of Fertilizers and Their Nanoparticles���������������������������������������������� 9 1.3.1 Biofertilizers�����������������������������������������������������������������������������������������9 1.3.2 Nanofertilizers������������������������������������������������������������������������������������ 11 1.4 Different Synthetic Approaches for Synthesis of Nanomaterials�������������������� 12 1.4.1 Silicon Nanoparticles (SiNPs)������������������������������������������������������������ 12 1.4.2 Zinc Nanoparticles (ZnNPs)�������������������������������������������������������������� 13 1.4.3 Copper Nanoparticles (CuNPs)���������������������������������������������������������� 13 1.4.4 Iron Nanoparticles (FeNPs)���������������������������������������������������������������� 14 1.4.5 Silver Nanoparticles (AgNPs)������������������������������������������������������������ 14 1.4.6 Other Types of Nanoparticles������������������������������������������������������������� 14 1.5 Conclusion������������������������������������������������������������������������������������������������������� 15 References������������������������������������������������������������������������������������������������������������������ 15 Chapter 2 Sustainable Nanotechnology in Agriculture��������������������������������������������������������������� 26 Bhavna Kumari and Anupam Prakash 2.1 Introduction�����������������������������������������������������������������������������������������������������26 2.2 Nanotechnology in Agriculture – A Sustainable Approach���������������������������� 27 2.3 Nanotechnological Intervention to Improve Crop Productivity���������������������� 27 2.3.1 Nanobiosensors���������������������������������������������������������������������������������� 29 2.3.2 Nanofertilizers������������������������������������������������������������������������������������ 30 2.3.3 Nanopesticides����������������������������������������������������������������������������������� 31 2.3.4 Nanoherbicides����������������������������������������������������������������������������������� 32 2.3.5 Nanofiltration in Agriculture�������������������������������������������������������������� 32 2.3.6 Application of Nanotechnology in Seed Science������������������������������� 33 2.3.7 Nanomaterials to Control Plant Diseases�������������������������������������������34 2.4 Nano-Bio-Farming: The Future of Agriculture����������������������������������������������34 2.5 Conclusion of Sustainable Development���������������������������������������������������������34 References������������������������������������������������������������������������������������������������������������������ 35

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Chapter 3 Nanopesticides: Formulation and Applications���������������������������������������������������������� 38 Anurag Chaudhary, Neha Krishnarth, and Prabhash Nath Tripathi 3.1 Introduction����������������������������������������������������������������������������������������������������� 38 3.2 Nanopesticides������������������������������������������������������������������������������������������������� 39 3.2.1 Merits of Nanopesticides�������������������������������������������������������������������� 41 3.2.2 Demerits of Nanopesticides��������������������������������������������������������������� 41 3.3 Conventional Pesticides vs. Nanopesticides (Yadav et al. 2022)��������������������� 42 3.4 Formulation����������������������������������������������������������������������������������������������������� 42 3.4.1 Nanoemulsions����������������������������������������������������������������������������������� 43 3.4.2 Nanosuspensions/Nanodispersions���������������������������������������������������� 43 3.4.3 Polymer-Based Nanopesticide Formulations������������������������������������� 43 3.4.4 Polymer Nanoencapsulations�������������������������������������������������������������46 3.4.5 Nanospheres (Nalini et al. 2022)��������������������������������������������������������46 3.4.6 Mycelium��������������������������������������������������������������������������������������������46 3.4.7 Nanogels��������������������������������������������������������������������������������������������� 49 3.4.8 Nanofibers������������������������������������������������������������������������������������������ 49 3.4.9 Chitosan Nanoparticle-Based Formulations�������������������������������������� 50 3.4.10 Lipid-Based Nanopesticide Formulations������������������������������������������ 50 3.4.11 Nanoliposomes����������������������������������������������������������������������������������� 50 3.4.12 Solid Lipid Nanoparticles������������������������������������������������������������������� 51 3.4.13 Clay-Based Nanopesticide Formulations������������������������������������������� 52 3.4.14 Porous Silica-Based Nanopesticide Formulations����������������������������� 52 3.5 Nanotechnology Applications (Kumari et al. 2020)��������������������������������������� 55 3.5.1 In Different Fields of Science������������������������������������������������������������� 55 3.5.2 Applications of Nanotechnology in Agriculture�������������������������������� 55 3.5.3 Other Applications����������������������������������������������������������������������������� 57 References������������������������������������������������������������������������������������������������������������������ 59 Chapter 4 Nanofertilizers: Formulations and Applications��������������������������������������������������������� 64 Prabhash Nath Tripathi, Ankit Lodhi, Mohd Talib, Anurag Chaudhary, Nazia Siddiqui, and Lavdeep Singh 4.1 Introduction�����������������������������������������������������������������������������������������������������64 4.2 Types of Nanofertilizers���������������������������������������������������������������������������������� 65 4.2.1 Nitrogen-Based Nanofertilizers��������������������������������������������������������� 65 4.2.2 Zinc-Based Nanofertilizers���������������������������������������������������������������� 67 4.2.3 Phosphorus-Based Nanofertilizers����������������������������������������������������� 67 4.2.4 Potassium-Based Nanofertilizers������������������������������������������������������� 67 4.2.5 Calcium-Based Nanofertilizers���������������������������������������������������������� 68 4.2.6 Magnesium-Based Nanofertilizers����������������������������������������������������� 68 4.2.7 Sulfur-Based Nanofertilizers�������������������������������������������������������������� 68 4.2.8 Iron-Based Nanofertilizers����������������������������������������������������������������� 69 4.2.9 Copper-Based Nanofertilizers������������������������������������������������������������ 69 4.2.10 Boron-Based Nanofertilizers�������������������������������������������������������������� 70 4.2.11 Nanofertilizers Composed of Biofertilizers��������������������������������������� 70 4.3 Nanofertilizer Uptake Mechanisms���������������������������������������������������������������� 70 4.4 Manufacturing of Nanofertilizers�������������������������������������������������������������������� 71

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4.5

Applications of Nanofertilizers����������������������������������������������������������������������� 72 4.5.1 Fertilizers Coated or Encapsulated with Nanoparticles��������������������� 72 4.5.2 Hydroxyapatite-Based Nanoparticles������������������������������������������������� 73 4.6 Mode of Application���������������������������������������������������������������������������������������� 73 4.6.1 In Vivo Methods��������������������������������������������������������������������������������� 73 4.6.2 In Vitro Methods�������������������������������������������������������������������������������� 73 4.7 Future Prospects���������������������������������������������������������������������������������������������� 74 4.8 Conclusion������������������������������������������������������������������������������������������������������� 76 References������������������������������������������������������������������������������������������������������������������ 77 Chapter 5 Nanoherbicides: Formulations and Applications������������������������������������������������������� 83 Neha Sharma, Bharti Choudhary, and Nidhi Puri 5.1 Introduction����������������������������������������������������������������������������������������������������� 83 5.1.1 Competitive Nature of Herbs and Weeds������������������������������������������� 83 5.1.2 Behavioral Changes in the Main Produce������������������������������������������ 83 5.1.3 Allergy-Causing and Toxic Nature of Herbs�������������������������������������� 83 5.2 Era of Nanoherbicides�������������������������������������������������������������������������������������84 5.2.1 Mode of Action of Nanoherbicides����������������������������������������������������84 5.2.2 Metabolism of Nanoherbicides����������������������������������������������������������� 85 5.3 Formulations of Nanoherbicides��������������������������������������������������������������������� 85 5.4 Applications����������������������������������������������������������������������������������������������������� 87 5.4.1 Nanoparticles Commonly Used for Herbicides���������������������������������� 87 5.4.2 Plant Protection via Nanoscale Carriers of Herbicide����������������������� 88 5.4.3 Nanoherbicidal Approach for Weed Control�������������������������������������� 89 5.5 Future Prospects and Aspects of Nanoherbicides�������������������������������������������90 5.6 Conclusion������������������������������������������������������������������������������������������������������� 91 References������������������������������������������������������������������������������������������������������������������ 91 Chapter 6 Nanopesticides, Nanoherbicides, and Nanofertilizers: Risks and Environmental Acceptability������������������������������������������������������������������������������ 94 Javed Khan, Awaneet Kaur, Md. Aftab Alam, Agrima Yadav, Debaashish Paramanick, and Shikha Chaudhary 6.1 Introduction�����������������������������������������������������������������������������������������������������94 6.2 Nanotechnology����������������������������������������������������������������������������������������������� 95 6.3 Current Status on Agriculture Nanotechnology����������������������������������������������96 6.4 Nanopesticides�������������������������������������������������������������������������������������������������97 6.5 Current Approaches to Environmental Risk Assessment of Nanopesticides��������������������������������������������������������������������������������������������99 6.6 Nanoherbicides���������������������������������������������������������������������������������������������� 101 6.7 Nanofertilizers����������������������������������������������������������������������������������������������� 102 6.8 Impact of Nanopesticides and Nanofertilizers on the Environment������������� 104 6.9 Risks of Nanoparticles���������������������������������������������������������������������������������� 104 6.10 Smart Target Delivery System����������������������������������������������������������������������� 106 6.11 Future Needs and Recommendation������������������������������������������������������������� 107 6.12 Conclusion����������������������������������������������������������������������������������������������������� 108 References���������������������������������������������������������������������������������������������������������������� 108

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Chapter 7 The Future of Nanopesticides, Nanoherbicides, and Nanofertilizers����������������������� 114 Shivang Dhoundiyal, Awaneet Kaur, Md. Aftab Alam, and Aditya Sharma 7.1 Introduction��������������������������������������������������������������������������������������������������� 114 7.1.1 Impact of Nanotechnology on Agriculture�������������������������������������� 114 7.1.2 Uptake, Translocation, Accumulation, Release, and Delivery of Nanoformulations���������������������������������������������������������� 116 7.1.3 Agriculture’s Future with Nanotechnology�������������������������������������� 116 7.2 Implementing Nanotechnology in Research in Agriculture and Allied Sciences���������������������������������������������������������������������������������������������� 117 7.2.1 Nanofood������������������������������������������������������������������������������������������ 118 7.2.2 Agricultural Seed Technology��������������������������������������������������������� 118 7.2.3 Precision Farming���������������������������������������������������������������������������� 118 7.2.4 Biosensors in Precision Farming������������������������������������������������������ 119 7.3 Nano-Enabled Agriculture���������������������������������������������������������������������������� 119 7.3.1 Nanopesticides��������������������������������������������������������������������������������� 120 7.3.2 Nanoherbicides��������������������������������������������������������������������������������� 121 7.3.3 Nanofertilizers���������������������������������������������������������������������������������� 122 7.4 Agriculture Employing Nanosized Particles: Definitions, Concepts, and Points of View����������������������������������������������������������������������������������������� 123 7.5 Conventional Pesticides vs. Nanobiopesticides��������������������������������������������� 124 7.6 Conventional Fertilizers vs. Nanofertilizers������������������������������������������������� 124 7.7 Nanotechnology in Agriculture��������������������������������������������������������������������� 124 7.7.1 Nanotechnology and Sustainable Agricultural Development���������� 125 7.7.2 Application of Nano-Based Formulation in Improving Crop Yield���������������������������������������������������������������������������������������� 127 7.7.3 Effect of Nanopesticides and Nanofertilizers on the Environment������������������������������������������������������������������������������������� 127 7.7.4 Current Status����������������������������������������������������������������������������������� 128 7.7.5 Benefits and Future Studies�������������������������������������������������������������� 128 7.8 Future Perspectives���������������������������������������������������������������������������������������� 129 7.8.1 The Future of Nanopesticides���������������������������������������������������������� 129 7.8.2 The Future of Nanofertilizers����������������������������������������������������������� 130 7.8.3 The Future of Nanoherbicides���������������������������������������������������������� 130 7.9 Conclusion����������������������������������������������������������������������������������������������������� 130 References���������������������������������������������������������������������������������������������������������������� 131 Chapter 8 Patent Landscape of Nanopesticides, Nanoherbicides, and Nanofertilizers������������ 137 Omji Porwal, Amit Singh, Sachin Kumar Singh, Neeraj Kumar Fuloria, Dinesh Kumar Patel, Nitin Chitranshi, Saurabh Gupta, and Prachi Varshney 8.1 Introduction��������������������������������������������������������������������������������������������������� 137 8.2 Agriculture Nanotechnology������������������������������������������������������������������������� 139 8.3 Nanoparticle as Nanofertilizers��������������������������������������������������������������������� 141 8.4 Nanoparticle in Plant Protection������������������������������������������������������������������� 142 8.4.1 Nanoinsecticides������������������������������������������������������������������������������� 142 8.4.2 Nanofungicides��������������������������������������������������������������������������������� 143 8.4.3 Nanoherbicides��������������������������������������������������������������������������������� 144 8.4.4 Nanobactericides������������������������������������������������������������������������������ 145

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8.5

Nanotechnology’s Toxicological Effects on Agriculture������������������������������� 145 8.5.1 Agricultural Nanotechnology in Regulations���������������������������������� 146 8.5.2 Mechanism of Action����������������������������������������������������������������������� 151 8.6 Conclusion and Future Perspectives�������������������������������������������������������������� 151 8.7 Recent Patents����������������������������������������������������������������������������������������������� 156 References���������������������������������������������������������������������������������������������������������������� 156 Index............................................................................................................................................... 163

Preface The incredible properties of nanosized materials have fascinated researchers as they study the applications in sectors such as food and agriculture. The revolution in modern agriculture helps to detect various plant diseases, increase crop production, and reduce waste to promote sustainable agriculture. This innovation specifically focuses on the drug delivery, diagnostics, and controlled delivery of nanoherbicides, nanopesticides, and nanofertilizers along with genetically modified crops. Nanoformulation of herbicides, fertilizers, and pesticides has been designed to protect crops from unwanted weeds as well as prevent the side effects caused by the bulk application of chemicals. Nanomaterials like hydroxyapatite, clay minerals, zeolites, and polyacrylic acid have been used to develop fertilizers that can then be used in agriculture. This enables slower and controlled release of the chemical due to properties of nanomaterials like large surface area and the interaction of chemicals with different coatings used to encapsulate them. Their use in lower concentrations helps in decreasing the toxicity to nontargeted organisms as well as in lowering the risk of environmental degradation. For example, it has been observed that nitrogen release for urea-upgraded hydroxyapatite nanoparticles is found to be double, that is, 60 days of plant growth as compared with conventional fertilizers (release of nitrogen till 30 days). In addition, increased content of chlorophyll has been found in soybean with the use of superparamagnetic iron oxide as well as cowpea when Fe nanoparticles were applied on foliage. Several studies also proved the efficacy of nanopesticides against a variety of pests. Nanoformulation of imidacloprid, which is an effective pesticide, was found to be more successful with LC50 9.86 mg/L against Martianus dermestoides as compared with conventional formulation (LC50 13.45 mg/L). Nano-imidacloprid was also found to be photodegradable, which proves its sustainability. Nanopesticides also increase the pesticide uptake and decrease the harmful effects on plants as well as on soil bacteria. Herbicides are used in agriculture to control the growth of unwanted plants, but their intensive use in agriculture is posing serious consequences on the environment, thereby resulting in enhanced herbicide levels in soil, water, and other food material. Polymeric materials that are biodegradable have been used to encapsulate herbicides, which result in improved efficiency and stability with less mobility in soil. For example, atrazine encapsulated in poly(epsilon caprolactone) has been used as a potential nanoformulation herbicide with enhanced biocompatibility, stability, and higher herbicidal activity against Brassica species. Atrazine otherwise would contaminate ground and surface water; hence these nanoherbicides are effective against weeds with less toxic impact. Despite many applications of nanomaterials in agriculture to improve yield and sustainability, more investigation and research need to be optimized regarding environmental hazards, genetic mutation, and legal perspectives for large-scale execution of nano-based strategies. This book will illustrate the synthesis, properties, and applications of nanoformulations for the effective and controlled delivery of fertilizers, pesticides, and herbicides. Dr. Anjali Gupta Dr. Divya Bajpai Tripathy

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Contributors Md. Aftab Alam Department of Pharmacy, School of Medical and Allied Sciences Galgotias University, Greater Noida Uttar Pradesh, India

Awaneet Kaur Department of Pharmacy, School of Medical and Allied Sciences Galgotias University, Greater Noida Uttar Pradesh, India

Anurag Chaudhary Department of Pharmaceutical Technology, Meerut Institute of Engineering and Technology Meerut, India

Dania Khan NIMS Institute of Allied Medical Sciences & Technology NIMS University, Rajasthan, India

Shikha Chaudhary Department of Pharmacy, School of Medical and Allied Sciences Galgotias University, Greater Noida Uttar Pradesh, India

Javed Khan Department of Pharmacy School of Medical and Allied Sciences Galgotias University Greater Noida, Uttar Pradesh, India

Nitin Chitranshi Faculty of Medicine and Health Sciences Macquarie University, North Ryde, NSW, Australia

Neha Krishnarth Raj Kumar Goel Institute of Technology (College of Pharmacy), Ghaziabad, Uttar Pradesh, India

Bharti Choudhary Department of Biotechnology, IILM University, Greater Noida Uttar Pradesh, India

Ashok Kumar NIMS Institute of Allied Medical Sciences & Technology NIMS University, Rajasthan, India

Shivang Dhoundiyal Department of Pharmacy, School of Medical and Allied Sciences Galgotias University, Greater Noida Uttar Pradesh, India

Bhavna Kumari School of Biological and Life Sciences, Galgotias University, Greater Noida Uttar Pradesh, India

Neeraj Kumar Fuloria Faculty of Pharmacy and Centre of Excellence for Biomaterials Engineering, AIMST University, Bedong, Kedah, Malaysia

Ankit Lodhi Department of Pharmaceutical Technology, Meerut Institute of Engineering and Technology Meerut, India

Saurabh Gupta Department of Pharmacology, Chitkara College of Pharmacy Chitkara University, Rajpura Punjab, India

Debaashish Paramanick Department of Pharmacy, School of Medical and Allied Sciences K.R. Mangalam University, Greater Gurgaon Uttar Pradesh, India

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Dinesh Kumar Patel Faculty of Health Science, Shalom Institute of Health and Allied Sciences Sam Higginbottom University of Agriculture, Technology and Sciences (SHUATS)-State University (formerly Allahabad Agriculture Institute), Naini, Prayagraj, India Omji Porwal Department of Pharmacognosy, Faculty of Pharmacy, Tishk International University, Erbil, Iraq Anupam Prakash School of Biological and Life Sciences, Galgotias University, Greater Noida, Uttar Pradesh, India Nidhi Puri Department of Applied Science & Humanities, Lloyd Institute of Engineering & Technology, Greater Noida, Uttar Pradesh, India Aditya Sharma Department of Pharmacy, School of Medical and Allied Sciences, Galgotias University, Greater Noida, Uttar Pradesh, India Neha Sharma Department of Biotechnology, IILM University, Greater Noida, Uttar Pradesh, India Nazia Siddiqui Department of Pharmaceutical Technology, Meerut Institute of Engineering and Technology, Meerut, India Amit Singh Department of Pharmacy, School of Medical and Allied Sciences, Galgotias University, Greater Noida, Uttar Pradesh, India

Contributors

Lavdeep Singh Kharvel Subharti College of Pharmacy, Swami Vivekanand Subharti University, Meerut, India Priyanka Singh NIMS Institute of Allied Medical Sciences & Technology, NIMS University, Rajasthan, India Sachin Kumar Singh School of Pharmaceutical Sciences, Lovely Professional University, Phagwara, India; and Faculty of Health, Australian Research Centre in Complementary and Integrative Medicine, University of Technology Sydney, Ultimo, NSW, Australia Mohd Talib Department of Pharmaceutical Technology, Meerut Institute of Engineering and Technology, Meerut, India Prabhash Nath Tripathi Department of Pharmaceutical Technology, Meerut Institute of Engineering and Technology, Meerut, India Prachi Varshney Department of Pharmacy, School of Medical and Allied Sciences, Galgotias University, Greater Noida, Uttar Pradesh, India Agrima Yadav Department of Pharmacy, School of Medical and Allied Sciences, Galgotias University, Greater Noida, Uttar Pradesh, India

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Introduction to Nanopesticides, Nanoherbicides, and Nanofertilizers Priyanka Singh, Dania Khan, and Ashok Kumar

1.1 INTRODUCTION The production and nutritional quality of varieties of crops are affected with different levels of biotic and abiotic stresses. Abiotic stresses mainly apply negative effects on cell division, differentiation, and photosynthesis process (Hasan et  al. 2021). The industrial waste effluents, sewage sludge discharge, and continuous use of chemical fertilizers and pesticides will cause a high degree of soil salinity and heavy metal contamination (Mason et  al. 2012; Khan et  al. 2020). The uncontrolled use of agrochemicals has negatively affected soil fertility and human health. These factors are major causes for soil erosion, decreased soil fertility, nutrient imbalance, and low water h­ olding capacity (Ostadi et al. 2020). The release of unused synthetic pesticides and fertilizers heavily affected the water quality and, hence, the food chain. Researchers have designed biofertilizers and biopesticides from biological sources to replace synthetic chemical ingredients for crop productivity. Plants undergo different physiological, morphological, and biochemical changes during abiotic stress conditions. Under these conditions, the higher rates of formation of reactive oxygen species (ROS) that cause oxidative stress reduced the stability of cell membranes, which affects the structure and functions of cell organelles (Senapati et al. 2021). Eco-friendly approaches are being required to ameliorate stresses and to increase the yield of crops. The consumption of biofertilizers and biopesticides by plants has released various primary metabolites, plant hormones, and polysaccharides for improving soil quality and plant growth. These components have inhibitory effects on the growth and proliferation of different plant pathogens, which have developed tolerance or resistance in plants against biotic stress (Gao et al. 2020). P ­ lant-growth-promoting rhizobacteria (PGPR) have been used as common biofertilizers for improving crop yield. They stimulate plant growth by nitrogen fixation, production of phytohormone, and solubilization of phosphorus and potassium. Their inoculation in the rhizosphere makes the plants stress-tolerant or stress-resistant and their uses also minimized the dependency on chemical fertilizers (Kalia 2019). Use of Azospirillum sp. Supplemented biofertilizer will improve the germination and morphological characteristics of Triticum aestivum L. under abiotic stresses (Alen’Kina and Nikitina 2021). Inoculation with PGPR will decrease electrolyte leakage and increases the relative water content and proline synthesis in wheat (Khan et al. 2021) and soybeans (Jabborova et al. 2021). Nanotechnology has been used to improve the efficacy of these biofertilizers and biopesticides in agricultural sectors. Nanoparticles synthetic approach has stimulated various defense systems in plants under unfavorable conditions. These nanobiofertilizers and nanopesticides are considered superior because of their high surface area, high solubility, and high ability. Nanobiofertilizers/ biopesticides are produced with the combination of nanoparticles and biofertilizers/biopesticides. It is a technique in which biofertilizers are nanoencapsulated within a suitable nanomaterial. They

DOI: 10.1201/9781003364429-1

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Nanopesticides, Nanoherbicides, and Nanofertilizers

slowly released the nutrients into the soil in a controlled manner and reduced the side effects of environmental stresses. They have decreased the use of synthetic fertilizer and improved the availability of micronutrients (Eliaspour et al. 2020; Pudake et al. 2019). These nanoparticles have direct and indirect effects on plant–microbe interaction. They directly affected the availability of nutrients in the rhizosphere and indirectly stimulated the metabolic activity within bacterial strains (Timmusk et al. 2018). Nanobiofertilizers and nanopesticides have been significantly used as bioinoculant and enhancer for crop productivity. They help in the distribution of plant-promoting agents at target sites. Nanobiofertilizers have not been widely suggested due to the lack of information on the interaction of biofertilizers with nanoparticles and plant (Elnahal et al. 2022). It is essential to explore some more suitable nanofertilizers and nanopesticides, which could be commercialized and easily available to farmers. This book chapter will give detailed information for significant nanobiofertilizers/biopesticides and their primary mechanism of action on plant productivity. The different parameters for evaluation of different nanobiofertilizers/biopesticides on the metabolism of plants under biotic and abiotic stresses will also be discussed.

1.2  OVERVIEW OF PESTICIDES, HERBICIDES, AND THEIR NANOPARTICLES 1.2.1  Pesticides and Their Classification Pesticides as toxic agents adversely affect the population density of weeds, insects, microbes, and animals. They have caused harmful effects on the physiological systems of plants and animals. Some pests become mutant due to continuous exposure with specific pesticides and developed a great degree of genetic resistance to pesticides. The integrated pest management has been developed for managing biological predators or parasites for controlling pests. IPM management program has reduced the population density of pests up to a lower extent, but they are not being considered an alternative for chemical pesticides. The international team, Stockholm Convention, has completely banned the use of 12 persistent organic pollutants (POPs) including DDT in 2001. Later in 2013, the European Union (EU) has also supported the restriction for commercial use of these pesticides along with neonicotinoid pesticides. The classification of these chemical pesticides has been carried on the basis of their properties for repelling, mitigation, and destruction. Insects and pests have developed genetic resistance to these chemical pesticides due to longer exposure (Speck-Planche et al. 2012). The effects of pesticides depend on the toxicity level, morphology of insects, exposure time, and the pests’ population density (Schmolke et  al. 2010). These pesticides are commonly divided into different categories such as insecticides, fungicides, rodenticides, molluscicides, herbicides, and plant growth regulators as shown in Figure 1.1. Pesticides have physiological characteristics of water solubility and thermal stability, and therefore, it is difficult to reduce their lethal nature. Pesticides cause toxicity among people working in the agriculture field and disrupt the food chain cycle (Rashid et al. 2010). These pesticides provide primary societal benefits by killing pests and insects to save crops and plants in the agricultural field. They are being used for longer periods under the scheme of Benefits of Pesticides and Crop Protection Chemicals. They have also prevented disease outbreaks by controlling the population density of pests, insects, rodents, and vectors. They protect wildlife habitats from attacks of invasive species of insects and other pests and improve agricultural yields for food crops. They may drastically affect nontarget species, animal system, plant biodiversity, and aquatic as well as terrestrial food chain ecosystems (Straathoff 1986). Pesticides have entered the biological system by two different modes depending on their solubility nature. The water-soluble pesticides could be dissolved in water and cause harm to untargeted species through groundwater and freshwater contamination process. Pesticides with fat-soluble components could enter the animal system through the process of bioamplification. A greater concentration of pesticides has been reported in

Introduction to Nanopesticides and Nanofertilizers

3

FIGURE 1.1  Different Classes of Pesticides Based On Their Uses.

FIGURE 1.2  Disadvantages of Continuous Use of Pesticides in the Agricultural Field.

higher levels of the trophic system. The continuous use of pesticides will damage the crop productivity in agricultural sectors as shown in Figure 1.2.

1.2.2 Effects and Regulation of Pesticides The continuous exposure to pesticides in the agricultural field severely affects human health with symptoms such as headache, diarrhea, dizziness, nausea, vomiting, abdominal pain, throat infection, skin rashes, blisters, blurred vision, and blindness. Some people have been reported with neurological disorder, weak immune system, hypersensitivity, asthma, and allergies. Organochlorinated derivatives in pesticide caused hypersensitivity, dizziness, vomiting, nausea, confusion, seizures, and nervousness. The ingestion of organophosphates and carbamates has caused nervous disorder by increasing secretion of acetylcholine neurotransmitter. Exposure to pyrethroids has caused symptoms such as aggressiveness, hyperexcitation, allergic skin response, reproductive issues, tremors, and seizures (Casida and Durkin 2013; Mahmood et al. 2016).

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Nanopesticides, Nanoherbicides, and Nanofertilizers

The Green Revolution program has made India self-sufficient in terms of production of food grains, but continuous use of chemical pesticides has contaminated the food chain and environment (Rahman and Debnath 2015). The commercial use of pesticides in Indian agriculture has been in great demand after the Green Revolution. This has helped our country to fight major issues of food crisis. India has been reported as Asia’s largest producer of pesticides and has ranked 12th worldwide (Tomer et al. 2015). The average consumption of pesticides in India is far lower than other developed countries, but its environmental and health issues are very high (Abhilash and Singh 2008). DDT has been used as a common pesticide to help farmers reduce the population density of pests and insects to a greater extent. Because of its adverse effects on human health, including cancer, reproductive organ failure, nervous disorder, lung damage, and dysfunction of the immune and digestive system, the nation decided to ban it (Thuy 2015).

1.2.3  Biopesticides Altosid (S)-Methoprene has been formulated with insect juvenile hormone as the first biopesticide inspired by a natural compound. Ribonucleic acid (RNA) interference technology has played a major role in pest management for developing biopesticides with a molecular approach. The US Environmental Protection Agency (EPA) has approved three categories of biopesticides: (1) biochemical biopesticides with natural agents used for pest management, (2) plant-incorporated protectants (PIPs) with transgenes imparting synthesis of natural pesticides for crop improvement, and (3) biocontrol agents with fungi. Biopesticides are now derived from natural components from animals, plants, bacteria, and certain minerals. These biopesticides have reduced toxicity level for nontarget organisms and reduced persistence in the environment. They are commonly used in organic agriculture and highly safe for people working in the agricultural field. Bt toxins are commonly used biopesticides for introduction of transgenic corn, soybeans, and cotton to protect from insects. Microbial biopesticides have been formulated using commercial pesticides such as bialaphos, spinosyn, validamycin, streptomycin, blasticidin, abamectin, and milbemectin (Copping et al. 2007). The semisynthetic modification of microbial products has been employed for generation of biological products like lepimectin from milbemectin, emamectin from avermectin, and spinetoram from spinosyns. Natural product-inspired pesticides have been formulated as azoxystrobin-based fungicides, and glufosinate containing natural herbicide phosphinothricin. Biocontrol agents in the third category biopesticides include Bacillus thuringiensis, Bacillus subtilis, and Thichoderma spp. Thaxtomin and mevalocidin have been introduced as new biopesticide products from microbes. Chromobacterium subtsugae has been formulated as a microbial bioinsecticide product with high sustainability. It also showed repellency, oral toxicity, and deterioration of the egg hatching process. Neem derivatives are used as natural pest management plant products for controlling insects and pests (Seiber et al. 2014). Lignocellulosic materials are also consumed by some microorganisms for the production of biopesticides active substances. Saccharopolyspora has also produced spinosyns through the fermentation of carbohydrates (Lewer et al. 2009). Biopesticides have been synthesized commonly by three approaches: (1) using crude extract like microbial suspension or lignocellulosic materials, (2) using a biochemical process under standard condition, and (3) opting for a computational chemistry-aided pesticide design. The synthetic approaches of biochemical process and computational-based designing are mixed solutions for synthesis of biopesticides after their identification. These biological integrated processes and rational design have involved many indirect biological and toxicological studies. These studies are possibly justified with the proper scientific method and research protocols for allowing feasible results. Synthesis of pesticides is mainly based on a specific basic structure with physiochemical function for regulating the growth of plants. The demand for biopesticides has increased globally during the last few decades. A total of 175 biopesticide active ingredients with 700 derived products are being registered worldwide. The active ingredients of biopesticides are encapsulated with Trichoderma viride, Metarhizium spp., Beauveria bassiana, Bacillus thuringiensis (Bt), and polyhedrosis virus,

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Introduction to Nanopesticides and Nanofertilizers

TABLE 1.1 Difference in Pesticides and Biopesticides in Terms of Their Physiological Parameters. Chemical Pesticides

Biopesticides

Chemical pesticides decrease the population density of nontarget flora and fauna. Chemical pesticides enter the food chain by direct application or biomagnification process causing health issues like abdominal pain, skin problems, irritation of eyes, and cancer.

They are nontoxic and nonpathogenic to nontarget organisms. They do not directly affect predators and parasitoids. Their residues are safe and nonhazardous and accumulate in food, fodder, and fibers. They decompose quickly due to short shelf life and low degree of biodegradability.

The chemical components of these pesticides may cause contamination of underground water bodies. Continuous exposure to pesticides causes poisoning hazards for pesticide operators.

These biopesticides are generally naturally derived products from plants, animals, and microorganisms and therefore could not cause water contamination.

Pests develop genetic resistance property due to prolonged exposure to chemical pesticides.

They are effective in very low concentration and therefore, pests will not develop any genetic resistance to these pesticides.

which are popularly used in plant protection. Among the insect viruses, Baculoviruses, Granulosis virus, and Nuclear polyhedrosis virus are preferred as the best candidates for controlling insects like Lepidoptera and Diptera. The Nuclear polyhedrosis virus has been used for management of Heliothis spp. pests and Spodoptera spp. to protect fruit, cotton, and vegetable crops in many countries. Entomopathogenic fungi (Beauveria spp., Lecanicillium spp., Metarhizium spp., and Isaria spp.) have been used for the formulation of mycoinsecticides to regulate various groups of insect pests. Microbial pesticides are also considered biological control agents due to encapsulation of microbial extract as an active ingredient of bacterium, virus, fungus, protozoan, alga, mycoplasma, rickettsia, and nematodes. They have offered the advantages of higher selectivity and lower toxicity than traditional chemical pesticides. These pesticides generally include Bioherbicides (Phytophthora), bioinsecticides (Bt), Biofungicides (Trichoderma, Pseudomonas, Bacillus). They generally inhibit the population of pests by secreting toxic metabolites (Kachhawa 2017). Microbial fungicides are used to control weeds in agricultural sectors without showing any effect on the growth of crops in that area. Microbial Bt pesticide has specifically killed the larvae of insects like flies, mosquitoes, and moths by affecting their digestive tract (Essiedu et  al. 2020). The biological control of insect pests in agricultural land and forest has been carried out by using pesticides synthesized with crude extract of bacteria, fungi, and viruses. The global demand for biopesticides will likely increase up to 10–15% per annum in the next ten years compared with 2–3% chemical pesticides. Table 1.1 shows the difference between pesticides and biopesticides.

1.2.4 Nanopesticides The commercial application of biopesticides is in great demand for management of pests like pathogens, harmful insects, and parasitic weeds in the agricultural field without comprising productivity, food chain, and human health. Genetic resistance among pathogens and insects also develops from continuous exposure to biopesticides. Therefore, scientists are more focused on exploring eco-friendly approaches for preventing the growth of pests without affecting the natural habitat of ecosystems (Chaud et al. 2021). Nanotechnology has revolutionized agricultural practices during the last ten years. The advancement of techniques like nanosensors, nanofibers, and nanocapsules has effectively solved these agricultural problems. Nanopesticides are synthesized by encapsulating active ingredients in nanometer

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Nanopesticides, Nanoherbicides, and Nanofertilizers

size range to increase their effectivity rate. These nanostructures have improved the solubility and bioavailability of active components. They also provide protection to agrochemical components against environmental degradation and have revolutionized the control of pathogenicity and infection in the crops (Chaud et al. 2021). Nanoentities are generally dispersed as ‘colloidal dispersion’ in a specific solvent according to their surface property. These nanoparticles should not affect the biochemical properties of biopesticides. Some pesticides will turn into gas faster and could be lost before reaching the target site. Therefore, nanotechnology has provided nano-safety aspects to these biopesticides with a lower degree of volatility and good solubility in water (Yadav et al. 2020). Nanopesticides should be formulated in terms of emulsion, and granular or pellets, which have contributed less drift and volatile losses during application. Nanopesticides with liquid formulations have been controlled by colloidal principles in terms of electrostatic forces, van der Waals forces, and surface tension. The unstable colloidal dispersion may form nano agglomerates with reduced functional efficiency rate. The nanotechnology has contributed to the control system with the release of small-sized molecules at the target site. These molecules enhanced the target specificity, optimized the action of the active ingredients, minimized the residual impacts, and improved the physicochemical stability of biopesticides. These nanopesticides have showed an improved degree of biocompatibility, biodegradation, and efficient delivery of active ingredients. The most common pesticide formulation for hydrophobic components is in terms of emulsification concentrates (ECs) and oil-in-water emulsions (Knowles 2009). These ECs are dissolved in an organic solvent (xylene), and blend of surfactant emulsifiers are added to ensure spontaneous emulsification into the water in the spray tank. The main disadvantages of ECs are relatively poor stability after dilution up to 10 μm droplet’s size, increased costs with the use of specific organic solvents, and inflammability of these EC-based nanopesticides with the possibility of dermal toxicity for the handlers. The nanotechnology has controlled the slow release of active ingredients and enhanced crop productivity by improving their target-specific binding sites against pathogens (Chaud et al. 2021). The different approaches of nanobiopesticides are shown in Figure 1.3.

1.2.5 Nanoherbicides In the current scenario, nanoherbicides have demonstrated their potential use for weed control in sustainable agriculture practices. There are many types of nanoherbicides reported based on using inorganic and organic nanocarriers. Their morphological and physiological properties are varying with size >100 nm according to the nature of nanocarrier specific agents (Chen and Wang 2019; Takeshita et al. 2021). Several studies have been carried out on developing varieties of nano-enabled herbicides due to their greater efficiency and environmental advantages (Mariana et al. 2022; Pontes et al. 2021). These nanoherbicides have shown better efficacy with a higher rate of diffusion, adhesion, and longer contact time on the leaves. They are being effectively used to control the movement of ions/biomolecules across the plant cell (Grillo et  al. 2021; Peixoto et  al. 2021). The effect of nanoherbicides on plants has been studied with respect to their physicochemical properties, including size, morphology, surface chemistry, and concentration. A specific design has been applied for ensuring optimal properties of nanoherbicides on target organisms. Organic nanomaterials are excellent materials for uniformly assembling nanoherbicides. These organic materials may be specific polymers, proteins, lipids, or lignocellulosic materials (Chen and Wang 2019; Takeshita et  al. 2021; Heydari et  al. 2021; Maes et  al. 2021; Lima et  al. 2021). Nanoemulsion has been used as an effective methodology for the production of nanoherbicides (Lim et  al. 2012; Lim et  al. 2013; Guo et  al. 2014; Zainuddin et  al. 2019). Polymers are extensively used in nanoherbicide formulations because of their higher degree of biodegradability and biocompatibility. Poly(ε-caprolactone) nanoparticles were developed primarily for herbicides like atrazine (ATZ) (Takeshita et al. 2021; Zhai et al. 2020; Bombo et al. 2019; Kah et al. 2014; Grillo et al. 2012); metribuzin (MTZ) (Boyandin and Kazantseva 2021), and ametryn (Clemente

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FIGURE 1.3  Efficacy of Different Nanoparticle Synthetic Approaches for Improving Crop Yield and Soil Fertility.

et al. 2014). Chitosan-based nanoherbicides have been developed by adding chemical crosslinking agents like tripolyphosphate (TPP) (Grillo et al. 2014; Paulraj et al. 2017). They can also be developed by functionalizing of chitosan polymers with 11-mercapto undecanoic acid (MUA) or N-octyl derivatives (Yu et al. 2015; Kamari and Yusoff 2019). The nanoherbicides formulated with bioconjugated chitosan have excellent functionalization processes for suitable nano-enabled herbicides. Therefore, chitosan nanoparticles have been developed for herbicides like imazapic and imazapyr (Maruyama et al. 2016), glyphosate (Rychter 2019), paraquat (PQ) (Silva et al. 2011; Grillo et al. 2015; Moreno et al. 2018; Rashidipour et al. 2019; Dong et al. 2021; Pontes et al. 2021), and clomazone (de Oliveira et al. 2016). The effective nanoherbicides have been developed using copolymers like poly (lactic-co-glycolic acid) (PLGA) with higher efficacy in the agriculture field (Tong et al. 2017; Schnoor et al. 2018). Lignin and cellulose have also been preferred as other efficient biopolymers for the nanoencapsulation of herbicides (Yin et al. 2021; Lima et al. 2021; Kumar et al. 2014). Pectin has been used as lignocellulosic material and as a potential acceptor for metsulfuron methyl herbicide (Kumar et al. 2017). These pectin molecules can also form blends with essential oils and have herbicidal activity (Taban et al. 2021). These essential oils have been nanoemulsified by blending with gums/gelatin in an oil/water solution (Hazrati et al. 2017; Taban et al. 2020). Proteins are currently preferred for the formulation of organic nano-enabled herbicides. Zein protein has been commercially used as a nanocarrier for the binding of tribenuron-methyl (TM) herbicides (Heydari et al. 2021). Polydopamine, phytantriol, perylene-3-ylmethanol, and rice husk derivatives are also being used as organic nanocarriers for nanoencapsulation of herbicides (Shen et al. 2019; Atta et al. 2015). These organic nanoherbicides have been characterized by different types of morphology and physiochemical properties. Inorganic nanomaterials are generally used for improving crop yield and herbicidal performance (Mariana et al. 2022). These inorganic herbicides are based on silica (Ghazali et al. 2021a), silver

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metal (Ke et al. 2018), and mesoporous silica nanoparticles (MSNs) (Cao et al. 2018). These nanoherbicides can efficiently release ions, while other metal-based nanoherbicides can encapsulate organic molecules with an efficient release of ions in a controlled manner. Inorganic nanoformulations have been designed as nanoherbicides using zinc/aluminum hydroxides (Hussein et al. 2005; Sharif et  al. 2020) or magnesium-aluminum associated with sepiolite clay (Mariana et  al. 2022; Ghazali et al. 2021b; Rebitski et al. 2019; Sarijo et al. 2015; Hussein et al. 2005). They are generally used to improve the transport of active ingredients for the metabolic activity of plant cells (Rebitski et al. 2019). These systems can efficiently encapsulate hydrophobic herbicides between their layers and be used to combat Chlamydomonas reinhardtii Dang algae (Touloupakis et al. 2011). On the other hand, clay minerals can potentially form nanoherbicides due to their high biocompatibility, good scalability, and low-cost effectiveness (Lima et  al. 2022). Nanoherbicides based on hydrotalcite nanosheets have shown better physicochemical stability and herbicidal activity than conventional ones (Gao et al. 2021). MSNs are also being used as herbicide carriers due to their response to pH and strong electrostatic interactions (Cao et al. 2018; Shan et al. 2019). Hybrid materials have the potential to combine organic and inorganic properties into a single structure (Gao et al. 2020) with different morphology, chemical compositions, and physiochemical properties (Aich et al. 2014; Ananikov 2019). These hybrid nanoherbicides have improved the properties of targetability, traceability, and stimuli-responsiveness (Chen et al. 2018; Zhao et al. 2020; Li et al. 2021). Biomass-based hybrids associated with xylan, lignin, starch, and cellulose have been used for targeted delivery of herbicides due to their biocompatibility, biodegradability, and easy functionalization characteristics (Mahajan et al. 2021). These hybrid nanoparticles have formed a core-shell structure with amphiphilic properties (Jiang et al. 2020). The lignin-based derivatives can be formulated using copper sulfate as an inorganic substance with antimicrobial properties (Mariana et al. 2022; Sinisi et al. 2019; Almasi et al. 2018) for weed control. Inorganic mineral materials can also serve as hybrid nanoherbicide. Natural clay and biopolymers have a great affinity for a wide range of pesticides, and a chemical modification process has been employed to improve their physiochemical properties (Granetto et al. 2022). Iron metals are also associated with montmorillonite (Mt) clay to design hybrid nanoherbicides (Marco-Brown et  al. 2012) with excellent sorption capacity (Marco-Brown et al. 2017; Xiang et al. 2017). Therefore, iron oxide nanoparticles have superparamagnetic properties for improving the transportation of ions/biomolecules from soils to plant cells (Chi et al. 2021; Forini et al. 2020; Grillo et al. 2016). In addition, metal-organic frameworks (MOFs) act as suitable carriers for the controlled release of herbicides with different properties like versatile hybrid compositions, large surface areas, and good stability (Lee et  al. 2022; Rojas et al. 2022). These MOF frameworks have improved the encapsulation efficiency of herbicides by facilitating their transport mechanism for plant cells (Mejías et al. 2021). Chemical interactions among different compounds can turn materials into excellent nano-enabled herbicide carriers for hydrophobic pesticides and herbicides (Hao et  al. 2020a). These have improved the efficacy of nanoherbicides with better spreadability, better leaf adhesion, and less UV irradiation degradation (Zhao et al. 2020; Hao et al. 2020b). Nanoherbicides with a size of 1% of the plant’s dry biomass, whereas non-accumulator plants have Si content from rice husk (Jabeen et al. 2017; Ghorbani et al. 2015). It has been validated that silicon nanoparticles (SiNPs) have shown better results for exogenous application compared with Si salt. These nanoparticles have increased the activities of glutathione reductase, dehydro-ascorbate reductase, ascorbate peroxidase, superoxide dismutase, and ascorbic acid in Zea mays L. under heavy metal stress (Tripathi et  al. 2016). They have effectively alleviated ultraviolet stress in Triticum aestivum by stimulating activities of antioxidant enzymes like ascorbate peroxidase, catalase, guaiacol peroxidase, and superoxide dismutase. They have also enhanced the content of proline, flavonoids, phenolics, and ascorbate as antioxidative agents. These improved synthetic approaches for antioxidants have helped in scavenging of reactive oxygen species and maintaining the rate of photosynthesis in plants (Tripathi et al. 2017). The relative water content, anthocyanin, ascorbic acid, and total phenolic compounds have been also improved under drought stress after foliar spray of Si and selenium nanoparticles on Fragaria vesca L. (Zahedi et  al. 2020). These nanoparticles subsequently decreased the bioavailability of SiNPs and accumulation of heavy metals in food crops. They immobilized the metals in the soil and competed with the heavy metals for absorption and translocation in the plant. They also enhanced the plant growth by translocation of sulfur, phosphorus, manganese, and potassium from soil to aerial parts of plants. They also increased chlorophyll content fresh weight and dry weight in Ocimum basilicum L. plant by osmotic regulation under salinity stress (Khan et al. 2020; Kalteh et al. 2014).

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1.4.2 Zinc Nanoparticles (ZnNPs) Zinc (Zn) as a micronutrient has been used for activation of different enzymes for carbohydrate metabolism. It played a significant role during transcription process and acted as cofactor of most cellular enzymes. It has regulated the biochemical pathways in terms of photosynthesis, hormone synthesis, protein metabolism, and carbohydrate metabolism. It also maintained the cellular structure, functions of cellular membranes, and stomata behavior (Snehal and Lohani 2018). Zn deficiency has inhibited the growth process of crops and caused chlorosis. It also inhibited the production of pollen by affecting their tube growth, and therefore reduced the fertilization rate. It has caused the structural and biochemical changes in the extracellular matrix of pollen grains and downregulated the secretion of esterase (Jabeen et al. 2017; Ghorbani et al. 2015). These Zn metals have decreased the photo-oxidative damage and activated antioxidant enzymes. The application of zinc fertilizer has significantly increased root surface area, dry weight of shoot, dry weight of root, and root length in case of Triticum Aestivum, Zea mays (Tripathi et al. 2017; Danish et al. 2020; Liu et al. 2019)). The foliar application of Zn fertilizer has improved the quality and quantity of crops, but excessive use of chemical fertilizers has decreased the growth and yield of crops (Ma et al. 2017). These zinc nanofertilizers have slowly released the nutrients in a controlled way with a higher rate of translocation in plants (Siddiqi et al. 2018). Leaf extract of Camellia sinensis (L.) O. Kuntze has been used as green synthetic approach for the development of zinc nanoparticles (ZnNPs) by encapsulating zinc acetate (Shah et al. 2015; Lawre et al. 2014). These ZnNP-based nanobiofertilizers have reduced the adverse effects of biotic and abiotic stresses. They have detoxified heavy metals, increased water uptake efficiency, maintained membrane stability, and balanced the uptake of nutrients. Different levels of ZnNP application have increased the productivity of Sorghum bicolor (L.) Moench. under drought stress condition (Dimkpa et al. 2019). They have also enhanced the DPPH (2, 2-diphenyl1-picryl-hydrazyl-hydrate) radical scavenging activity in the root and shoot of Camelina sativa L. under salinity stress (Akhavan Hezaveh et  al. 2020). The combinatorial approach for the use of Zn and Fe nanofertilizers as foliar spray has improved anatomical structures of leaf and stem and significantly enhanced the rate of photosynthesis with increased yield of crops (Talebi et al. 2016). They increased the yield of Solanum melongena L. from 50% to 66% under salinity and drought stress conditions (Semida et al. 2021). The effect of zinc and silicon nanofertilizers on the fruiting process in terms of the number of fruits, their weight, and size has been also studied in Mangifera indica L. under salinity stress.

1.4.3 Copper Nanoparticles (CuNPs) Copper (Cu) as an essential micronutrient has been used for the regulation of mitochondria and chloroplast, and its content in the plant depends on its transportation and bioavailability in the soil. It is involved in biological functions like protein trafficking, iron mobilization, hormone signaling, mitochondrial respiration, and cell metabolism (Elsheery et al. 2020; Lopez-Lima et al. 2021). It is the structural component of plastocyanin, which enhances the production of hydrogen peroxide and develops stress tolerance or resistance in plants. Its exogenous application has enhanced the release of plant biomass and improved yield and quality in plant derivatives (Priyanka et al. 2019; Lafmejani et al. 2018). Copper deficiency may cause leaf curling, stunted growth, and chlorosis, as well as a decrease in photosynthesis. This deficiency may stimulate the production of reactive oxygen species by affecting photosystems. It also affects the flow of electrons during the electron transport chain, decreasing the metabolism for nitrogen and carbohydrate (Shabbir et al. 2020). The synthesis of CuNPs has been performed with leaf extract of A. indica by using cupric chloride solution (Nagar and Devra 2018), fruit extract of citrus limon (L.) (Akl et al. 2021), leaf extract of Tinospora cordifolia (Willd.) Miers. (Sharma et al. 2019), Eclipta prostrate (L.) (Chung et al. 2017), and Plantago asiatica L. (Nasrollahzadeh et al. 2017). The applications of Cu and ZnNPs nanoparticles have also improved

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the morphological and physiological parameters in Ocimum basilicum L. (Abbasifar et al. 2020). These nanoparticles have improved rate of photosynthesis and enhanced the activities of antioxidants under drought stress condition in crops. Foliar application of CuNPs has also improved the fruiting process in S. lycopersicum with stimulation of synthesis of activity of catalase and superoxide dismutase activity (Lopez-Vargas et al. 2018).

1.4.4 Iron Nanoparticles (FeNPs) As an essential micronutrient for plant growth, iron is in great demand in the regulation of the metabolic process. It acts as a cofactor of various plant enzymes and behaves as a catalytic agent in various biochemical reactions. It is required in the synthesis of different cellular enzymes for regulating photosynthesis and respiration activity. Iron deficiency reduces the synthesis of chlorophyll, causing necrosis and chlorosis in the leaves. The application of iron as a fertilizer improves plant growth and reduces the damaging effects of environmental stresses (Rjamshid 2021; Vaghar et al. 2020; Mohamadipoor et  al. 2013). Green synthesis of FeNPs has been carried out using plant extracts of C. sinensis, A. indica, and Eucalyptus tereticornis (Herlekar et  al. 2014). The phytochemical components of these plant extracts have reduced the size of Fe salt (iron oxide hydroxide, ferric oxide, ferrous ferric oxide, and iron mineral complex) and increased their bioavailability for the plant (Mohamadipoor et al. 2013; Ebrahiminezhad et al. 2017). These FeNPs have also increased the content of vitamin C, phenol, and glutathione in S. lycopersicum (El-Desouky et al. 2021). Iron nanoparticles (FeNPs) have induced the selective uptake of mineral ions through the root membrane. They reduced the absorption of sodium ions and enhanced the availability of potassium content in shoots against salinity stress condition. The synthesis of FeNPs using salicylic acid has induced drought tolerance ability in F. vesca (Mozafari et al. 2018). These nanoparticles stimulated the germination, root length, and shoot length in T. aestivum (Yasmeen et al. 2015). The application of FeNPs has minimized the uptake of cadmium (Cd) in plant cells and enhanced the availability of Fe content in plant tissue.

1.4.5 Silver Nanoparticles (AgNPs) Silver ions have a significant role in plant metabolic processes like somatic embryogenesis, genetic transformation, shoot formation, and root formation. These silver ions have decreased the biosynthetic approach for ethylene, which is involved in the production of secondary metabolites in the plant’s cellular metabolism. They have downregulated the process of aging and have improved growth and grain yield in crops (Yasmeen et al. 2015). Their specific role depends on the phytochemical components, and surface reactivity and application rate (Oktem and Kele 2018; Kumari et al. 2017). Phytochemical constituents in leaf extract have been used for the green synthesis of silver nanoparticles (AgNPs) in some plants like Ocimum tanuiflorum L., Centella asiatica (L.) Urban., Citrus sinensis (L.) Osbeck. (peel), and Syzygium cumini (L.). The synthesized AgNPs have also improved germination process and antioxidant activity in the Allium cepa L., Z. mays, Dianthus chinensis L., and Trigonella foenum-graecum L. (Soliman et al. 2020; Sreelekshmi et al. 2021). These silver nanoparticles have also increased the content of chlorophyll, carotenoid, polyphenol oxidase, and fresh weight in S. lycopersicum (Mahawar et  al. 2020). They also showed enhancement in rate of seed germination, root length, shoot length, and biomass in Satureja horten‑ sis L. under salinity stress (Nejatzadeh 2021; Bastami et al. 2021).

1.4.6 Other Types of Nanoparticles Natural polymers including sodium alginate, albumin, chitosan, and starch are used for the development of green synthesized nanoparticles. Synthetic polymers like PLGA, polycaprolactone, and polyvinyl alcohol (PVA) are also being used for formulation of nanoparticles (Diyanat et al. 2019;

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Yadav et al. 2022; Calzoni et al. 2019). These nanoparticles have incorporated nanosized active substances coated with polymers on the surface. Polymeric carriers are mixed with lipids and trapped with vector polymeric carrier (Shekhar et al. 2021). Polymeric nanocapsules with hydrophilic or hydrophobic internal cavity are surrounded by a polymer coating (Yadav et al. 2022). These active substances are generally dissolved in the internal liquid core and encapsulated by polymers spontaneously during the formation of nanocapsules (Zielinska et al. 2020). Polymeric nanospheres are spherical structures with dense polymeric network entrapping pesticide inside or adsorbed on their surface (Zielinska et  al. 2020). Nanogels (hydrogel nanoparticles) are water-swollen nanosized polymeric networks with physiochemically cross-linked polymer chains (Catalin Balaure et al. 2017). Nanofibers have cross-sectional diameters with high surface area and surface-area-to-volume ratio. These nanofibers are formed from highly porous mesh with considerable interconnectivity between their pores. They are usually synthesized by electrospinning methodology (Kenry et al. 2017). These nanofibers have supported plant crops and have been used for environmental protection, financial stability, and biological sustainability (Tiwari et al. 2012). They will introduce stress tolerance gene against abiotic and biotic stress whereas nanofertilizers will improve the overall plant growth. The specific biosensors have also been associated with nanofertilizers for managing bioavailability of nutrients based on plant growth stage and agroclimatic zones (Mahmoud et al. 2020; Leon-Silva et al. 2018; Verma et al. 2022)

1.5 CONCLUSION Nanotechnology has contributed greatly to agriculture by improving plant productivity in an ecofriendly approach. The biological approach of biofertilizers and biopesticides has increased the nutritional quality, crop productivity, and resistance against biotic and abiotic stress factors. The synthesis of nanofertilizers and nanopesticides has increased the solubility of agrochemicals in soil for plant development. It is efficient in enhancing soil fertility with unique positive interactions. Researchers have worked on the development of biofertilizers, biopesticides, and nanoparticles, but not much study has been done on the formulation, molecular level analysis, and application of nanobiofertilizers. The combinatorial approaches for the development of nanobiofertilizers and nanobiopesticides should be optimized to control delivery and release at the target site. The large-scale production of these nanofertilizers and nanopesticides should be formulated and commercialized for availability to farmers. This chapter has summarized studies on biofertilizers and biopesticides and their different approaches for synthesis of nanoparticles, with commercial applications in current scenarios. Their effectiveness in terms of innovative approaches and detailed experimentations has been discussed in detail.

REFERENCES Abbasifar, A.; Shahrabadi, F.; ValizadehKaji, B. Effects of green synthesized zinc and copper nano-fertilizers on the morphological and biochemical attributes of basil plant. J. Plant Nutr. 2020, 1104–1118. https:// doi.org/10.1080/01904167.2020.1724305. Abhilash, P.C.; Singh, N. Pesticide use and application: An Indian scenario.  J. Hazard. Mater. 2009, 1–12. https://doi.org/10.1016/j.jhazmat.2008.10.061. Ahmed, S.; Choudhury, A.R.; Roy, S.K.; Choi, J.; Sayyed, R.Z.; Sa, T. Biomolecular painstaking utilization and assimilation of phosphorus under indigent stage in agricultural crops. In Antioxidants in Plant-Microbe Interaction. Springer: Singapore, 2021; pp. 565–588. Aich, N.; Plazas-Tuttle, J.; Lead, J.; Saleh, N. A critical review of nanohybrids: Synthesis, applications, and environmental implications. Environ. Chem. 2014, 11. https://doi.org/10.1071/EN14127. Akhavan Hezaveh, T.; Rahmani, F.; Alipour, H.; Pourakbar, L. Effects of foliar application of ZnO nanoparticles on secondary metabolite and micro-elements of camelina (Camelina sativa L.) under salinity stress. J. Stress Physiol. Biochem. 2020, 16, 54–69.

16

Nanopesticides, Nanoherbicides, and Nanofertilizers

Akl, M.A.; Amer, M.W. Green synthesis of copper nanoparticles by Citrus limon fruits extract, characterization and antibacterial activity. Chem. Int. 2021, 7, 1–8. Alen’Kina, S.A.; Nikitina, V.E. Stimulating effect from lectins of associative bacteria of the genus Azospirillum on the germination and morphometric characteristics of spring wheat sprouts in simulated abiotic stress. Russ. J. Plant Physiol. 2021, 68, 315–321. Almasi, H.; Jafarzadeh, P.; Mehryar, L. Fabrication of novel nanohybrids by impregnation of CuO nanoparticles into bacterial cellulose and chitosan nanofibers: Characterization, antimicrobial and release properties. Carbohydr. Polym. 2018, 186, 273–281. https://doi.org/10.1016/j.carbpol.2018.01.067. Ananikov, V.P. Organic-inorganic hybrid nanomaterials. Nanomaterials. 2019, 9, 1197. https://doi.org/10.3390/ nano9091197. Atta, S.; Bera, M.; Chattopadhyay, T.; Paul, A.; Ikbal, M.; Maiti, M.K.; Singh, N.D.P. Nano-pesticide formulation based on fluorescent organic photoresponsive nanoparticles: For controlled release of 2,4-D and real time monitoring of morphological changes induced by 2,4-D in plant systems. RSC Adv. 2015, 5, 86990–86996. https://doi.org/10.1039/C5RA17121K. Ayala, S.; Rao, E.V.S.P. Perspective of soil fertility management with a focus on fertilizer use for crop productivity. Curr. Sci. 2002, 82, 797–807. Baba, Z.A.; Hamid, B.; Sheikh, T.A.; Alotaibi, S.H.; El Enshasy, H.A.; Ansari, M.J.; Zuan, A.T.K.; Sayyed, R.Z. Psychrotolerant Mesorhizobium sp. isolated from temperate and cold desert regions solubilizes potassium and produces multiple plant growth promoting metabolites. Molecules. 2021, 26, 5758. Bastami, A.; Amirnia, R.; Sayyed, R.; Enshasy, H. The effect of mycorrhizal fungi and organic fertilizers on quantitative and qualitative traits of two important Satureja species. Agronomy. 2021, 11, 1285. Belal, E.-S.; El-Ramady, H. Nanoparticles in water, soils and agriculture. Nanosci. Food Agric. 2016, 2, 311–358. Bombo, A.B.; Pereira, A.E.S.; Lusa, M.G.; de Medeiros Oliveira, E.; de Oliveira, J.L.; Campos, E.V.R.; de Jesus, M.B.; Oliveira, H.C.; Fraceto, L.F.; Mayer, J.L.S. A mechanistic view of interactions of a nanoherbicide with target organism. J. Agric. Food Chem. 2019, 67, 4453–4462. https://doi.org/10.1021/acs.jafc.9b00806. Boyandin, A.N.; Kazantseva, E.A.; Varygina, D.E.; Volova, T.G. Constructing slow-release formulations of ammonium nitrate fertilizer based on degradable poly(3-hydroxybutyrate). Journal of Agricultural and Food Chemistry, 2017, 65(2), 6745–6752. Calzoni E.; Cesaretti, A.; Polchi, A.; Di Michele, A.; Tancini, B.; Emiliani, C. Biocompatible polymer nanoparticles for drug delivery applications in cancer and neurodegenerative disorder therapies. J. Funct. Biomater. 2019, 10(1), 1–15. Cao, L.; Zhou, Z.; Niu, S.; Cao, C.; Li, X.; Shan, Y.; Huang, Q. Positive-charge functionalized mesoporous silica nanoparticles as nanocarriers for controlled 2,4- dichlorophenoxy acetic acid sodium salt release. J. Agric. Food Chem. 2018, 66, 6594–6603. https://doi.org/10.1021/acs.jafc.7b01957. Casida, J.E.; Durkin, K.A. Neuroactive insecticides: Targets, selectivity, resistance, and secondary effects. Annu. Rev. Entomol. 2013, 58, 99–117. Catalin Balaure, P.; Gudovan, D.; Gudovan, I. Nanopesticides: A  New Paradigm in Crop Protection, New Pesticides and Soil Sensors. Elsevier: Bucharest, 2017, pp. 129–192. Caubet, M.; Cornu, S.; Saby, N.P.A.; Meunier, J.-D. Agriculture increases the bioavailability of silicon, a beneficial element for crop, in temperate soils. Sci. Rep. 2020, 10, 19999. Chaud, M.; Souto, E.B.; Zielinska, A.; Severino, P.; Batain, F.; Oliveira-Junior, J.; Alves, T. Nanopesticides in agriculture: Benefits and challenge in agricultural productivity, toxicological risks to human health and environment. Toxics. 2021, 9(6), 131. Chen, C.; Zhang, G.; Dai, Z.; Xiang, Y.; Liu, B.; Bian, P.; Zheng, K.; Wu, Z.; Cai, D. Fabrication of lightresponsively controlled-release herbicide using a nanocomposite. Chem. Eng. J. 2018, 349, 101–110. https://doi.org/10.1016/j.cej.2018.05.079. Chen, X.-t.; Wang, T. Preparation and characterization of atrazine-loaded biodegradable PLGA nanospheres. J. Integr. Agric. 2019, 18, 1035–1041. https://doi.org/10. 1016/S2095-3119(19)62613-4. Chi, Y.; Chen, C.; Zhang, G.; Ye, Z.; Su, X.; Ren, X.; Wu, Z. Fabrication of magneticresponsive controlledrelease herbicide by a palygorskite-based nanocomposite. Colloids Surf. B: Biointerfaces. 2021, 208, 112115. https://doi.org/10.1016/j.colsurfb.2021. 112115. Chung, I.; Rahuman, A.A.; Marimuthu, S.; Kirthi, A.V.; Anbarasan, K.; Padmini, P.; Rajakumar, G. Green synthesis of copper nanoparticles using Eclipta prostrata leaves extract and their antioxidant and cytotoxic activities. Exp. Ther. Med. 2017, 14, 18–24. Clemente, Z.; Grillo, R.; Jonsson, M.; Santos, N.Z.; Feitosa, L.O.; Lima, R.; Fraceto, L.F.; Ecotoxicological evaluation of poly(epsilon-caprolactone) nanocapsules containing triazine herbicides. J. Nanosci. Nanotechnol. 2014, 14(7), 4911–7. doi: 10.1166/jnn.2014.8681.

Introduction to Nanopesticides and Nanofertilizers

17

Copping, L.G.; Duke, S.O. Natural products that have been used commercially as crop protection agents – a review. Pest Manage. Sci. 2007, 63, 524 − 554. Danish Toor, M.; Adnan, M.; Javed, M.S.; Habibah, U.E.; Arshad, A.; Mughees, M.; Ahmad, R.; Danish, M. Foliar application of Zn: Best way to mitigate drought stress in plants. A review. Int. J. Appl. Res. 2020, 6, 16–20. Das, K.; Dang, R.; Shivananda, T.N.; Sekeroglu, N. Influence of bio-fertilizers on the biomass yield and nutrient content in Stevia rebaudiana Bert. grown in Indian subtropics. J. Med. Plant Res. 2007, 1, 5–8. de Oliveira, C.R.; Fraceto, L.F.; Rizzi, G.M.; Salla, R.F.; Abdalla, F.C.; Costa, M.J.; Silva-Zacarin, E.C.; Hepatic effects of the clomazone herbicide in both its free form and associated with chitosan-alginate nanoparticles in bullfrog tadpoles. Chemosphere. 2016, 149, 304−313. doi: 10.1016/j.chemosphere.2016.01.076. Dimkpa, C.O.; Singh, U.; Bindraban, P.S.; Elmer, W.H.; Gardea-Torresdey, J.L.; White, J.C. Zinc oxide nanoparticles alleviate drought-induced alterations in sorghum performance, nutrient acquisition, and grain fortification. Sci. Total Environ. 2019, 688, 926–934. Diyanat, M.; Saeidian, H.; Baziar, S.; Mirjafary, Z. Preparation and characterization of polycaprolactone nanocapsules containing pretilachlor as a herbicide nanocarrier. Environ. Sci. Pollut. Res. 2019, 26(21), 21579–21588. Dong, J.; Liu, X.; Chen, Y.; Yang, W.; Du, X. User-safe and efficient chitosan-gated porous carbon nanopesticides and nanoherbicides. J. Colloid Interface Sci. 2021, 594, 20–34. https://doi.org/10.1016/j. jcis.2021.03.001. Ebrahiminezhad, A.; Zare-Hoseinabadi, A.; Sarmah, A.K.; Taghizadeh, S.; Ghasemi, Y.; Berenjian, A. Plantmediated synthesis and applications of iron nanoparticles. Mol. Biotechnol. 2017, 60, 154–168. El-Desouky, H.S.; Islam, K.R.; Bergefurd, B.; Gao, G.; Harker, T.; Abd-El-Dayem, H.; Ismail, F.; Mady, M.; Zewail, R.M.Y. Nano iron fertilization significantly increases tomato yield by increasing plants’ vegetable growth and photosynthetic efficiency. J. Plant Nutr. 2021, 44, 1649–1663. Eliaspour, S.; Sharifi, R.S.; Shirkhani, A.; Farzaneh, S. Effects of biofertilizers and iron nano-oxide on maize yield and physiological properties under optimal irrigation and drought stress conditions. Food Sci. Nutr. 2020, 8, 5985–5998. Elnahal, A.S.M.; El-Saadony, M.T.; Saad, A.M.; Desoky, E.-S.M.; El-Tahan, A.M.; Rady, M.M.; AbuQamar, S.F.; El-Tarabily, K.A. The use of microbial inoculants for biological control, plant growth promotion, and sustainable agriculture: A review. Eur. J. Plant Pathol. 2022, 1–34. Elsheery, N.I.; Helaly, M.N.; El-Hoseiny, H.M.; Alam-Eldein, S.M. Zinc oxide and silicone nanoparticles to improve the resistance mechanism and annual productivity of salt-stressed mango trees. Agronomy. 2020, 10, 558. Enrico, J.M.; Piccinetti, C.F.; Barraco, M.R.; Agosti, M.B.; Eclesia, R.P.; Salvagiotti, F. Biological nitrogen fixation in field pea and vetch: Response to inoculation and residual effect on maize in the Pampean region. Eur. J. Agron. 2020, 115, 126016. Essiedu, J.A.; Adepoju, F.O.; Ivantsova, M.N. Benefits and limitations in using biopesticides: A review. In AIP Conference Proceedings. AIP Publishing LLC, 2020, December, Vol. 2313, No. 1, p. 080002. Fasusi, O.; Cruz, C.; Babalola, O. Agricultural sustainability: Microbial biofertilizers in rhizosphere management. Agriculture. 2021, 11, 163. Fatima, A.; Singh, S.; Prasad, S.M. Interaction between copper oxide nanoparticles and plants: Uptake, accumulation and phytotoxicity. In: Sustainable Agriculture Reviews. Springer: Cham, Switzerland, 2020, pp. 143–161. Forini, M.M.L.; Antunes, D.R.; Cavalcante, L.A.F.; Pontes, M.S.; Biscalchim, E.R.; Sanches, A.O.; Santiago, E.F.; Fraceto, L.F.; Grillo, R. Fabrication and characterization of a novel herbicide delivery system with magnetic collectability and its phytotoxic effect on photosystem II of aquatic macrophyte. J. Agric. Food Chem. 2020, 68, 11105–11113. https://doi.org/10.1021/acs.jafc.0c03645. Franche, C.; Lindstrom, K.; Elmerich, C. Nitrogen-fixing bacteria associated with leguminous and non-leguminous plants, Plant and Soil. 2009, 321(1–2), 35–59. Gao, Y.; Xiao, Y.; Mao, K.; Qin, X.; Zhang, Y.; Li, D.; Zhang, Y.; Li, J.; Wan, H.; He, S. Thermoresponsive polymer-encapsulated hollow mesoporous silica nanoparticles and their application in insecticide delivery. Chem. Eng. J. 2020, 383, 123169. https://doi.org/10.1016/j.cej.2019.123169. Gao, Y.; Zhou, Z.; Chen, X.; Tian, Y.; Li, Y.; Wang, H.; Li, X.; Yu, X. Controlled release of herbicides by 2,4D-, MCPA-, and bromoxynil-intercalated hydrotalcite nanosheets. Green Chem. 2021, 23. https://doi. org/10.1039/D1GC01349A. Garrigue, P.; Delville, M.-H.; Labrugère, C.; Cloutet, E.; Kulesza, P.J.; Morand, J.P.; Kuhn, A. Top-down approach for the preparation of colloidal carbon nanoparticles. Chem. Mater. 2004, 16, 2984–2986.

18

Nanopesticides, Nanoherbicides, and Nanofertilizers

Ghazali, S.A.I.S.M.; Fatimah, I.; Bohari, F.L. Synthesis of hybrid organic-inorganic hydrotalcite-like materials intercalated with duplex herbicides: The characterization and simultaneous release properties. Molecules. 2021a, 26, 5086. https://doi.org/10.3390/molecules26165086. Ghazali, S.A.I.S.M.; Sarijo, S.H.; Hussein, M.Z. New synthesis of binate herbicideinterleaved anionic clay material: Synthesis, characterization and simultaneous controlled-release properties. J. Porous Mater. 2021b, 28, 495–505. https://doi.org/10.1007/s10934-020-01011-x. Ghorbani, F.; Sanati, A.M.; Maleki, M. Production of silica nanoparticles from rice husk as agricultural waste by environmental friendly technique. Environ. Stud. Persian Gulf. 2015, 2, 56–65. Glick, B.R. Plant growth-promoting bacteria: Mechanisms and applications. Scientifica. 2012, 963401. doi:10.6064/2012/963401 Granetto, M.; Serpella, L.; Fogliatto, S.; Re, L.; Bianco, C.; Vidotto, F.; Tosco, T. Natural clay and biopolymerbased nanopesticides to control the environmental spread of a soluble herbicide. Sci. Total Environ. 2022, 806, 151199. https://doi.org/10.1016/j.scitotenv.2021.151199. Grillo, R.; Abhilash, P.C.; Fraceto, L.F. Nanotechnology applied to bio-encapsulation of pesticides. J. Nanosci. Nanotechnol. 2016, 16(1), 1231–1234. https://doi.org/10.1166/jnn.2016.12332. Grillo, R.; Clemente, Z.; Oliveira, J.Ld, Campos, E.V.R.; Chalupe, V.C.; Jonsson, C.M.; Lima, Rd, Sanches, G.; Nishisaka, C.S.; Rosa, A.H.; Oehlke, K.; Greiner, R.; Fraceto, L.F. Chitosan nanoparticles loaded the herbicide paraquat: The influence of the aquatic humic substances on the colloidal stability and toxicity. J. Hazard. Mater. 2015, 286, 562–572. https://doi.org/10.1016/j.jhazmat.2014.12.021. Grillo, R.; dos Santos, N.Z.P.; Maruyama, C.R.; Rosa, A.H.; de Lima, R.; Fraceto, L.F. Poly(ɛ-caprolactone) nanocapsules as carrier systems for herbicides: Physicochemical characterization and genotoxicity evaluation. J. Hazard. Mater. 2012, 231–232, 1–9. https://doi.org/10.1016/j.jhazmat.2012.06.019. Grillo, R.; Mattos, B.D.; Antunes, D.R.; Forini, M.M.L.; Monikh, F.A.; Rojas, O.J. Foliage adhesion and interactions with particulate delivery systems for plant nanobionics and intelligent agriculture. Nano Today. 2021, 37, 101078. https://doi.org/10.1016/j.nantod.2021.101078. Grillo, R.; Pereira, A.E.S.; Nishisaka, C.S.; de Lima, R.; Oehlke, K.; Greiner, R.; Fraceto, L.F. Chitosan/tripolyphosphate nanoparticles loaded with paraquat herbicide: An environmentally safer alternative for weed control. J. Hazard. Mater. 2014, 278, 163–171. https://doi.org/10.1016/j.jhazmat.2014.05.079. Guo, Y.; Yang, Q.; Yan, W.; Li, B.; Qian, K.; Li, T.; Xiao, W.; He, L. Controlled release of acetochlor from poly (butyl methacrylate-diacetone acrylamide) based formulation prepared by nanoemulsion polymerisation method and evaluation of the efficacy. Int. J. Environ. Anal. Chem. 2014, 94, 1001–1012. Hamid, B.; Zaman, M.; Farooq, S.; Fatima, S.; Sayyed, R.; Baba, Z.; Sheikh, T.; Reddy, M.; El Enshasy, H.; Gafur, A.; et al. Bacterial plant biostimulants: A sustainable way towards improving growth, productivity, and health of crops. Sustainability. 2021, 13, 2856. Hao, L.; Gong, L.; Chen, L.; Guan, M.; Zhou, H.; Qiu, S.; Wen, H.; Chen, H.; Zhou, X.; Akbulut, M. Composite pesticide nanocarriers involving functionalized boron nitride nanoplatelets for pH-responsive release and enhanced UV stability. Chem. Eng. J. 2020a, 396, 125233. https://doi.org/10.1016/j.cej.2020.125233. Hao, L.; Lin, G.; Lian, J.; Chen, L.; Zhou, H.; Chen, H.; Xu, H.; Zhou, X. Carboxymethyl cellulose capsulated zein as pesticide nano-delivery system for improving adhesion and anti-UV properties. Carbohydr. Polym. 2020b, 231, 115725. https://doi.org/10.1016/j.carbpol.2019.115725. Hasan, M.; Alireza, S.; Georgios, T.; Zohreh, E.; Dimitrios, F.; Silvana, N. Pheno-morphological and essential oil composition responses to UVA radiation and protectants: A case study in three thymus species. 2021, 31–31. https://doi.org/10.3390/horticulturae8010031. Hazrati, H.; Saharkhiz, M.J.; Niakousari, M.; Moein, M. Natural herbicide activity of Satureja hortensis L. essential oil nanoemulsion on the seed germination and morphophysiological features of two important weed species. Ecotoxicol. Environ. Saf. 2017, 142, 423−430. doi: 10.1016/j.ecoenv.2017.04.041. Herlekar, M.; Barve, S.; Kumar, R. Plant-mediated green synthesis of iron nanoparticles. J. Nanoparticles. 2014, 140614. Heydari, M.; Yousefi, A.R.; Nikfarjam, N.; Rahdar, A.; Kyzas, G.Z.; Bilal, M. Plantbased nanoparticles prepared from protein containing tribenuron-methyl: Fabrication, characterization, and application. Chem. Biol. Technol. Agric. 2021, 8, 53. https://doi.org/10.1186/s40538-021-00254-3. Hussein, M.Z., Yahaya, A.H.; Zainal, Z.; Kian, L.H. Nanocomposite-based controlled release formulation of an herbicide, 2,4-dichlorophenoxyacetate incapsulated in zinc–aluminium-layered double hydroxide. Sci. Technol. Adv. Mater. 2005, 6, 956–962. https://doi.org/10.1016/j.stam.2005.09.004. Jabborova, D.; Kannepalli, A.; Davranov, K.; Narimanov, A.; Enakiev, Y.; Syed, A.; Elgorban, A.M.; Bahkali, A.H.; Wirth, S.; Sayyed, R.Z.; et al. Co-inoculation of rhizobacteria promotes growth, yield, and nutrient contents in soybean and improves soil enzymes and nutrients under drought conditions. Sci. Rep. 2021, 11, 22081.

Introduction to Nanopesticides and Nanofertilizers

19

Jabeen, N.; Maqbool, Q.; Sajjad, S.; Minhas, A.; Younas, U.; Anwaar, S.; Nazar, M.; Kausar, R.; Hussain, S.Z. Biosynthesis and characterisation of nano-silica as potential system for carrying streptomycin at nanoscale drug delivery. IET Nanobiotechnol. 2017, 11, 557–561. Jeffries, P.; Gianinazzi, S.; Perotto, S.; Turnau, K.; Barea, J.M. The contribution of arbuscular mycorrhizal fungi in sustainable maintenance of plant health and soil fertility. Biology and Fertility of Soils. 2003, 37(1), 1–16. Jiang, Y.; Chen, Y.; Tian, D.; Shen, F.; Wan, X.; Xu, L.; Chen, Y.; Zhang, H.; Hu, J.; Shen, F. Fabrication and characterization of lignin–xylan hybrid nanospheres as pesticide carriers with enzyme-mediated release property. Soft Matter. 2020, 16, 9083–9093. https://doi.org/10.1039/D0SM01402H. Kachhawa, D. Microorganisms as a biopesticides. J. Entomol. Zool. Stud. 2017, 5(3), 468–473. Kah, M.; Machinski, P.; Koerner, P.; Tiede, K.; Grillo, R.; Fraceto, L.F.; Hofmann, T. Analysing the fate of nanopesticides in soil and the applicability of regulatory protocols using a polymer-based nanoformulation of atrazine. Environ. Sci. Pollut. Res. Int. 2014, 21(20), 11699−707. doi: 10.1007/s11356-014-2523-6. Kalia, A.; Kaur, H. Nano-biofertilizers: Harnessing dual benefits of nano-nutrient and bio-fertilizers for enhanced nutrient use efficiency and sustainable productivity. In Nanoscience for Sustainable Agriculture. Springer: Cham, Switzerland, 2019; pp. 51–73. ISBN 9783319978529. Kalteh, M.; Taj Alipour, Z.; Ashraf, S.; Aliabadi, M.M.; Nosratabadi, A.F. Effect of silica nano-particles on basil (Ocimum basili-cum) under salinity stress. J. Chem. Health Risks. 2014, 4, 49–55. Kamari, A.; Yusoff, S. N-octyl chitosan derivatives as amphiphilic carrier agents for herbicide formulations. Open Chem. 2019, 17, 365–380. https://doi.org/10.1515/chem2019-0043. Ke, M.; Qu, Q.; Peijnenburg, W.J.G.M.; Li, X.; Zhang, M.; Zhang, Z.; Lu, T.; Pan, X.; Qian, H. Phytotoxic effects of silver nanoparticles and silver ions to Arabidopsis thaliana as revealed by analysis of molecular responses and of metabolic pathways. Sci. Total Environ. 2018, 644, 1070–1079. https://doi. org/10.1016/j.scitotenv.2018.07.061. Kenry, L.C.T.; Lim C.T. Nanofiber technology: Current status and emerging developments. Prog. Polym. Sci. 2017, 70, 1–17. Khan, I.; Awan, S.A.; Ikram, R.; Rizwan, M.; Akhtar, N.; Yasmin, H.; Sayyed, R.Z.; Ali, S.; Ilyas, N. Effects of 24-epibrassinolide on plant growth, antioxidants defense system, and endogenous hormones in two wheat varieties under drought stress. Physiol. Plant. 2021, 172, 696–706. Khan, W.; Rayirath, U.P.; Subramanian, S.; et al. Seaweed extracts as biostimulants of plant growth and development. J. Plant Growth Regul. 2009, 28(4), 386–399. Khan, Z.S.; Rizwan, M.; Hafeez, M.; Ali, S.; Adrees, M.; Qayyum, M.F.; Khalid, S.; Rehman, M.Z.U.; Sarwar, M.A. Effects of silicon nanoparticles on growth and physiology of wheat in cadmium contaminated soil under different soil moisture levels. Environ. Sci. Pollut. Res. 2020, 27, 4958–4968. Knowles, A. Global trends in pesticide formulation technology: The development of safer formulations in China. Outlooks on Pest Management. 2009, 20, 5. Konrad, A.; Herr, U.; Tidecks, R.; Kummer, F.; Samwer, K. Luminescence of bulk and nanocrystalline cubic yttria. J. Appl. Phys. 2001, 90, 3516–3523. Kumar, S.; Bhanjana, G.; Sharma, A.; Dilbaghi, N.; Sidhu, M.C.; Kim, K.-H. Development of nanoformulation approaches for the control of weeds. Sci. Total Environ. 2017, 586, 1272–1278. https://doi.org/10.1016/j. scitotenv.2017.02.138. Kumari, M.; Pandey, S.; Bhattacharya, A.; Mishra, A.; Nautiyal, C. Protective role of biosynthesized silver nanoparticles against early blight disease in Solanum lycopersicum. Plant Physiol. Biochem. 2017, 121, 216–225. Kusale, S.; Attar, Y.; Sayyed, R.; Malek, R.; Ilyas, N.; Suriani, N.; Khan, N.; El Enshasy, H. Production of plant beneficial and antioxidants metabolites by Klebsiella variicola under salinity stress. Molecules. 2021, 26, 1894. Lafmejani, Z.N.; Jafari, A.A.; Moradi, P.; Moghadam, A.L. Impact of foliar application of copper sulphate and copper nanoparticles on some morpho-physiological traits and essential oil composition of peppermint (Mentha piperita L.). Herba Pol. 2018, 64, 13–24. Larue, C.; Castillo-Michel, H.; Sobanska, S.; Trcera, N.; Sorieul, S.; Cécillon, L.; Ouerdane, L.; Legros, S.; Sarret, G. Fate of pristine TiO2 nanoparticles and aged paintcontaining TiO2 nanoparticles in lettuce crop after foliar exposure. J. Hazard. Mater. 2014, 273, 17–26. https://doi.org/10.1016/j.jhazmat.2014.03.014. Lawre, S.; Laware, S.L.; Raskar, S. Influence of zinc oxide nanoparticles on growth, flowering and seed productivity in onion. Int. J. Curr. Microbiol. Sci. 2014, 3, 874–881. Lee, S.; Wang, G.; Ji, N.; Zhang, M.; Wang, D.; Sun, L.; Meng, W.; Zheng, Y.; Li, Y.; Wu, Y. Synthesis, characterizations and kinetics of MOF-5 as herbicide vehicle and its controlled release in PVA/ST biodegradable composite membranes. Z. für Anorg. und Allg. Chem. 2022, 648, e202100252. https://doi. org/10.1002/zaac.202100252.

20

Nanopesticides, Nanoherbicides, and Nanofertilizers

Leon-Silva, S.; Arrieta-Cortes, R.; Fernández-Luqueño, F.; Lopez-Valdez, F. Design and production of nanofertilizers. In Agricultural Nanobiotechnology. Springer Science and Business Media LLC: Cham, Switzerland, 2018, pp. 17–31. Lewer, P.; Hahn, D.R.; Karr, L.L.; Duebelbeis, D.O.; Gilbert, J.R.; Crouse, G.D.; Worden, T.; Sparks, T.C.; Edwards, P.M.; Graupner, P.R. Discovery of the butenyl-spinosyn insecticides: Novel macrolides from the new bacterial strain Saccharopolyspora pogona. Bioorg. Med. Chem. 2009, 17(12), 4185–4196. https://doi.org/10.1016/j.bmc.2009.02.035. Li, P.; Huang, Y.; Fu, C.; Jiang, S.X.; Peng, W.; Jia, Y.; Peng, H.; Zhang, P.; Manzie, N.; Mitter, N.; Xu, Z.P. Eco-friendly biomolecule-nanomaterial hybrids as nextgeneration agrochemicals for topical delivery. EcoMat. 2021, 3, e12132. https://doi.org/10.1002/eom2.12132. Lim, C.J.; Basri, M.F.; Omar, D.; Abdul Rahman, M.B.; Salleh, A.B.; Raja Abdul Rahman, R.N.Z. Physicochemical characterization and formation of glyphosate-laden nano-emulsion for herbicide formulation. Ind. Crop. Prod. 2012, 36, 607–613. https://doi.org/10.1016/j.indcrop.2011.11.005. Lim, C.J.; Basri, M.; Omar, D.; Abdul Rahman, M.B.; Salleh, A.B.; Raja Abdul Rahman, R.N. Green nanoemulsion-laden glyphosate isopropylamine formulation in suppressing creeping foxglove (A. gangetica), slender button weed (D. ocimifolia) and buffalo grass (P. conjugatum). Pest Manag Sci. 2013, Jan;69(1), 104−11. doi: 10.1002/ps.3371. Lima, P.H.C.; Antunes, D.R.; Forini, M.Md.L.; Pontes, Md.S.; Mattos, B.D.; Grillo, R. Recent advances on lignocellulosic-based nanopesticides for agricultural applications. Front. Nanotechnol. 2021, 3. Lima, P.H.C.; Tavares, A.A.; de Lima Silva, S.M.; de Moura, M.R.; Aouada, F.A.; Grillo, R. Recent advances on nanohybrid systems constituting clay–chitosan with organic molecules–a review. Appl. Clay Sci. 2022, 226, 10654. Liu, D.-Y.; Liu, Y.-M.; Zhang, W.; Chen, X.-P.; Zou, C.-Q. Zinc uptake, translocation, and remobilization in winter wheat as affected by soil application of Zn fertilizer. Front. Plant Sci. 2019, 10, 426. Lopez-Lima, D.; Mtz-Enriquez, A.; Carrión, G.; Basurto-Cereceda, S.; Pariona, N. The bifunctional role of copper nano-particles in tomato: Effective treatment for Fusarium wilt and plant growth promoter. Sci. Hortic. 2021, 277, 109810. Lopez-Vargas, E.R.; Ortega-Ortíz, H.; Cadenas-Pliego, G.; de Alba Romenus, K.; Cabrera de la Fuente, M.; Benavides-Mendoza, A.; Juárez-Maldonado, A. Foliar application of copper nanoparticles increases the fruit quality and the content of bioactive compounds in tomatoes. Appl. Sci. 2018, 8, 1020. Lugtenberg, B.J.J.; Chin-A-Woeng, T.F.C.; Bloemberg, G.V. Microbe-plant interactions: Principles and mechanisms, Antonie Van Leeuwenhoek. 2002, 81(1–4), 373–383. Ma, D.; Sun, D.; Wang, C.; Ding, H.; Qin, H.; Hou, J.; Huang, X.; Xie, Y.; Guo, T. Physiological responses and yield of wheat plants in zinc-mediated alleviation of drought stress. Front. Plant Sci. 2017, 8, 860. Maes, C.A.-O.X.; Brostaux, Y.A.-O.; Bouquillon, S.; Fauconnier, M.A.-O. Use of New Glycerol-Based Dendrimers for Essential Oils Encapsulation: Optimization of Stirring Time and Rate Using a PlackettBurman Design and a Surface Response Methodology. 2021, 207. https://doi.org/10.3390/foods10020207. Mahajan, R.A.-O.; Selim, A.A.-O.X.; Neethu, K.A.-O.; Sharma, S.A.-O.; Shanmugam, V.A.- O.; Jayamurugan, G.A.-O. A  systematic study to unravel the potential of using polysaccharides based organicnanoparticles versus hybrid-nanoparticles for pesticide delivery. Nanotechnology. 2021. https://doi. org/10.1088/1361–6528/ac1bdc. Mahawar, H.; Prasanna, R.; Gogoi, R.; Singh, S.B.; Chawla, G.; Kumar, A. Synergistic effects of silver nanoparticles augmented Calothrix elenkinii for enhanced biocontrol efficacy against Alternaria blight challenged tomato plants. 3 Biotech. 2020, 10, 102. Mahmood, I.; Imadi, S.R.; Shazadi, K.; Gul, A.; Hakeem, K.R. Effects of Pesticides on Environment. In: Hakeem, K.; Akhtar, M.; Abdullah, S. (Eds.), Plant, Soil and Microbes. Springer: Cham, 2016. https:// doi.org/10.1007/978-3-319-27455-3_13. Mahmoud, F.; Khalid, F.; Majed, A.; Ashwag, S.; Bushra, A.; Martin, L. Nano-fertilization as an emerging fertilization technique: Why can modern agriculture benefit from its use? 2020, 2. https://doi.org/10.3390/ plants10010002. Maissel, L.I.; Glang, R. Handbook of Thin Film Technology. McGraw-Hill, New York, 1970. Makarov, V.V.; Love, A.J.; Sinitsyna, O.V.; Makarova, S.S.; Yaminsky, I.V.; Taliansky, M.E.; Kalinina, N.O. “Green” nanotechnologies: Synthesis of metal nanoparticles using plants. Acta Naturae. 2014, 35–35. Retrieved December 11, 2022, from https://paperity.org/p/209184018. Malusa, E.; Sas-Paszt, L.; Ciesielska, J. Technologies for beneficial microorganisms inocula used as biofertilizers. Sci. World J. 2012, 2012, 491206. https://doi.org/10.1100/2012/491206. Manke, A.; Wang, L.; Rojanasakul, Y. Mechanisms of nanoparticle-induced oxidative stress and toxicity. Biomed. Res. Int. 2013, 2013, 942916. doi: 10.1155/2013/942916.

Introduction to Nanopesticides and Nanofertilizers

21

Marco-Brown, J.L.; Barbosa-Lema, C.M.; Torres Sánchez, R.M.; Mercader, R.C.; dos Santos Afonso, M. Adsorption of picloram herbicide on iron oxide pillared montmorillonite. Appl. Clay Sci. 2012, 58, 25–33. https://doi.org/10.1016/j.clay.2012.01.004. Marco-Brown, J.L.; Undabeytia, T.; Torres Sánchez, R.M.; Dos Santos Afonso, M. Slow-release formulations of the herbicide picloram by using Fe-Al pillared montmorillonite. Environ. Sci. Pollut. Res. Int. 2017, 24(11), 10410−10420. doi: 10.1007/s11356-017-8699-9. Mariana, M.L.; Forini, Montcharles S.; Pontes, Débora R.; Antunes, Pedro H.C.; de Lima, Jaqueline S.; Santos, Etenaldo F.; Santiago, Renato Grillo. Nano-enabled weedmanagement in agriculture: From strategic design to enhanced herbicidal activity. Plant Nano Biology. 2022, 1. https://doi.org/10.1016/j.plana.2022.100008. Maruyama, C.R.; Guilger, M.; Pascoli, M.; Bileshy-José, N.; Abhilash, P.C.; Fraceto, L.F.; de Lima, R. Nanoparticles based on chitosan as carriers for the combined herbicides imazapic and imazapyr. Sci. Rep. 2016, 6, 19768. https://doi.org/10.1038/srep19768. Mason, O.U.; Hazen, T.; Borglin, S.; Chain, P.; Dubinsky, E.; Fortney, J.L.; Han, J.; Holman, H.-Y.N.; Hultman, J.; Lamendella, R.; et al. Metagenome, metatranscriptome and single-cell sequencing reveal microbial response to Deepwater Horizon oil spill. ISME J. 2012, 6, 1715–1727. Mejías, F.J.R.; Trasobares, S.; Varela, R.M.; Molinillo, J.M.G.; Calvino, J.J.; Macías, F.A. One-step encapsulation of ortho-disulfides in functionalized zinc MOF. Enabling metal–organic frameworks in agriculture. ACS Appl. Mater. Interfaces. 2021, 13, 7997–8005. https://doi.org/10.1021/acsami.0c21488. Mittal, D.; Kaur, G.; Singh, P.; Yadav, K.; Ali, S.A. Nanoparticle-based sustainable agriculture and food science: Recent advances and future outlook. Front. Nanotechnol. 2020, 2. Mohamadipoor, R.; Sedaghathoor, S.; Mahboub Khomami, A. Effect of application of iron fertilizers in two methods ‘foliar and soil application’ on growth characteristics of Spathyphyllum illusion. Eur. J. Exp. Biol. 2013, 3. Moreno, A.; Jordana, A.; Grillo, R.; Fraceto, L.; Jaime, C. A study on the molecular existing interactions in nanoherbicides: A chitooligosaccharide/tripolyphosphate loaded with paraquat case. Colloids Surf. A: Physicochem. Eng. Asp. 2018, 562. https://doi.org/10.1016/j.colsurfa.2018.11.033. Mozafari, A.A.; Havas, F.; Ghaderi, N. Application of iron nanoparticles and salicylic acid in in vitro culture of strawberries (Fragaria _ ananassa Duch.) to cope with drought stress. Plant Cell Tissue Organ Cult. (PCTOC). 2018, 132, 511–523. Nadiminti, P.P.; Rookes, J.E.; Dong, Y.D.; Sayer, C.; Boyd, B.J.; Cahill, D.M. Nanostructured liquid crystalline particle assisted delivery of 2,4-dichlorophenoxyacetic acid to weeds, crops and model plants. Crop Prot. 2016, 82, 17–29. https://doi.org/10.1016/j.cropro.2015.12.018. Nagar, N.; Devra, V. Green synthesis and characterization of copper nano-particles using Azadirachta indica leaves. Mater. Chem. Phys. 2018, 213, 44–51. Nasrollahzadeh, M.; Momeni, S.S.; Sajadi, S.M. Green synthesis of copper nanoparticles using Plantago asiatica leaf extract and their application for the cyanation of aldehydes using K4Fe(CN)6. J. Colloid Interface Sci. 2017, 506, 471–477. Nejatzadeh, F. Effect of silver nanoparticles on salt tolerance of Satureja hortensis l. during in vitro and in vivo germination tests. Heliyon. 2021, 7, e05981. Nieman, G.W.; Weertman, J.R.; Siegel, R.W. Microhardness of nanocrystalline palladium and copper produced by inert-gas condensation. Scr. Metall. 1989, 23, 2013–2018. Nisar, S.; Sadique, S.; Kazerooni, G.; Majeed, U.; Shehzad, M. Physical and chemical techniques to produce nano fertilizers. Int. J. Chem. Biochem. Sci. 2019, 15, 50–57. Nithyapriya, S.; Lalitha, S.; Sayyed, R.Z.; Reddy, M.; Dailin, D.; El Enshasy, H.; Suriani, N.L.; Herlambang, S. Production, purification, and characterization of bacillibactin siderophore of Bacillus subtilis and its application for improvement in plant growth and oil content in sesame. Sustainability. 2021, 13, 5394. Oktem, M.; Kele¸s, Y. The role of silver ions in the regulation of the senescence process in Triticum aestivum. Turk. J. Biol. 2018, 42, 517–526. Oliveira-Pinto, P.R.; Mariz-Ponte, N.; Torres, A.; Tavares, F.; Fernandes-Ferreira, M.; Sousa, R.M.; Santos, C. Satureja montana L. essential oil, montmorillonite and nanoformulation reduce Xanthomonas euvesicatoria infection, modulating redox and hormonal pathways of tomato plants. Sci. Hortic. 2022, 295, 110861. https://doi.org/10.1016/j.scienta.2021.110861. Ostadi, A.; Javanmard, A.; Amani Machiani, M.; Morshedloo, M.R.; Nouraein, M.; Rasouli, F.; Maggi, F. Effect of different fertilizer sources and harvesting time on the growth characteristics, nutrient uptakes, essential oil productivity and composition of Mentha x piperita L. Ind. Crops Prod. 2020, 148, 112290. Paulraj, G.M.; Ignacimuthu, S.; Rajiv, G.M.; Shajahan, A.; Ganesan, P.; Packiam, S.M.; AlDhabi, N.A. Comparative studies of Tripolyphosphate and Glutaraldehyde cross-linked chitosan-botanical pesticide nanoparticles and their agricultural applications. Int. J. Biol. Macromol. 2017, 104. https://doi. org/10.1016/j.ijbiomac.2017.06.043.

22

Nanopesticides, Nanoherbicides, and Nanofertilizers

Peixoto, S.; Henriques, I.; Loureiro, S. Long-term effects of Cu(OH)2 nanopesticide exposure on soil microbial communities. Environ. Pollut. 2021, 269, 116113. https://doi.org/10.1016/j.envpol.2020.116113. Pontes, M.S.; Antunes, D.R.; Oliveira, I.P.; Forini, M.M.L.; Santos, J.S.; Arruda, G.J.; Caires, A.R.L.; Santiago, E.F.; Grillo, R. Chitosan/tripolyphosphate nanoformulation carrying paraquat: Insights on its enhanced herbicidal activity. Environ. Sci. 2021, Nano 8, 1336–1351. https://doi.org/10.1039/D0EN01128B. Priyanka, N.; Geetha, N.; Ghorbanpour, M.; Venkatachalam, P. Role of engineered zinc and copper oxide nanoparticles in promoting plant growth and yield: Present status and future prospects. In Advances in Phytonanotechnology. Academic Press: Cambridge, MA, 2019, pp. 183–201. Pudake, R.N.; Chauhan, N.; Kole, C.  Nanoscience for Sustainable Agriculture. Springer, 2019. https://doi. org/10.1007/978-3-319-97852-9. Qureshi, A.; Singh, D.K.; Dwivedi, S. Nano-fertilizers: A novel way for enhancing nutrient use efficiency and crop productivity. Int. J. Curr. Microbiol. Appl. Sci. 2018, 7, 3325–3335. Rahman, K.M.; Debnath, S.C. Agrochemical use, environmental and health hazards in Bangladesh. Int. Multidiscip. Res. J. 2015, 1, 75–79. Rashid, B.; Husnain, T.; Riazuddin, S. Herbicides and Pesticides as Potential Pollutants: A Global Problem. Plant Adaptation Phytoremediation. Springer: Dordrecht, 2010, pp. 427–447. Rashidipour, M.; Maleki, A.; Kordi, S.; Birjandi, M.; Pajouhi, N.; Mohammadi, E.; Heydari, R.; Rezaee, R.; Rasoulian, B.; Davari, B. Pectin/chitosan/tripolyphosphate nanoparticles: Efficient carriers for reducing soil sorption, cytotoxicity, and mutagenicity of paraquat and enhancing its herbicide activity. J. Agric. Food Chem. 2019, 67, 5736–5745. https://doi.org/10.1021/acs.jafc.9b01106. Rebitski, E.P.; Darder, M.; Aranda, P. Layered double hydroxide/sepiolite hybrid nanoarchitectures for the controlled release of herbicides. Beilstein J. Nanotechnol. 2019, 10, 1679–1690. doi: 10.3762/bjnano.10.163. Reddy, S.S.; Chhabra, V. Nanotechnology: Its scope in agriculture. J. Physics: Conf. Series. 2022, 2267(1), 012112. Rico, C.M.; Majumdar, S.; Duarte-Gardea, M.; Peralta-Videa, J.R.; Gardea-Torresdey, J.L. Interaction of nanoparticles with edible plants and their possible implications in the food chain. J. Agric. Food Chem. 2011, 59, 3485–3498. Rjamshid, S.A. Study the effect of iron, zinc and manganese foliar application on morphological and agronomic traits of bread wheat (Chamran cultivar) under different irrigation regimes. Environ. Stress. Crop Sci. 2021, 14, 109–118. Rojas, S.; Rodríguez-Diéguez, A.; Horcajada, P. Metal–organic frameworks in agriculture. ACS Appl. Mater. Interfaces. 2022, 14, 16983–17007. https://doi.org/10.1021/acsami.2c00615. Rychter, P. Chitosan/glyphosate formulation as a potential, environmental friendly herbicide with prolonged activity. J. Environ. Sci. Health, Part B. 2019, 54, 681–692. https://doi.org/10.1080/03601234.2019.16 32644. Sagar, A.; Rai, S.; Ilyas, N.; Sayyed, R.Z.; Al-Turki, A.I.; El Enshasy, H.A.; Simarmata, T. Halotolerant rhizobacteria for salinity-stress mitigation: Diversity, mechanisms and molecular approaches. Sustainability. 2022, 14, 490. Sarijo, S.H.; Ghazali, S.A.I.S.M.; Hussein, M.Z. Synthesis of dual herbicides-intercalated hydrotalcite-like nanohybrid compound with simultaneous controlled release property. J. Porous Mater. 2015, 22, 473– 480. https://doi.org/10.1007/s10934-015-9916-x. Savci, S. An agricultural pollutant: Chemical fertilizer. Int. J. Environ. Sci. Dev. 2012a, 7, 3–80. Schmolke, A.; Thorbek, P.; Chapman, P.; Grimm, V. Ecological models and pesticide risk assessment: Current modeling practice. Environ Toxicol Chem. 2010, 29(4), 1006–1012. Schnoor, B.; Elhendawy, A.; Joseph, S.; Putman, M.; Chacón-Cerdas, R.; Flores-Mora, D.; Bravo-Moraga, F.; Gonzalez-Nilo, F.; Salvador-Morales, C. Engineering atrazine loaded poly (lactic-co-glycolic acid) nanoparticles to ameliorate environmental challenges. J. Agric. Food Chem. 2018, 66, 7889–7898. https://doi.org/10.1021/acs.jafc.8b01911. Seiber, J.N.; Coats, J.; Duke, S.O.; Gross, A.D. Biopesticides: State of the art and future opportunities. J. Agric. Food Chem. 2014, 62(48), 11613–11619. Semida, W.; Abdelkhalik, A.; Mohamed, G.; El-Mageed, T.A.; El-Mageed, S.A.; Rady, M.; Ali, E. Foliar application of zinc oxide nanoparticles promotes drought stress tolerance in eggplant (Solanum melongena L.). Plants. 2021, 10, 421. Senapati, N.; Halford, N.G.; Semenov, M.A. Vulnerability of European wheat to extreme heat and drought around flowering under future climate. Environ. Res. Lett. 2021, 16, 024052. Shabbir, Z.; Sardar, A.; Shabbir, A.; Abbas, G.; Shamshad, S.; Khalid, S.; Natasha; Murtaza, G.; Dumat, C.; Shahid, M. Copper uptake, essentiality, toxicity, detoxification and risk assessment in soil-plant environment. Chemosphere. 2020, 259, 127436.

Introduction to Nanopesticides and Nanofertilizers

23

Shah, R.K.; Boruah, F.; Parween, N. Synthesis and characterization of ZnO nano-particles using leaf extract of Camellia sinesis and evaluation of their antimicrobial efficacy. Int. J. Curr. Microbiol. Appl. Sci. 2015, 4, 444–450. Shan, Y.; Cao, L.; Xu, C.; Zhao, P.; Cao, C.; Li, F.; Xu, B.; Huang, Q. Sulfonatefunctionalized mesoporous silica nanoparticles as carriers for controlled herbicide diquat dibromide release through electrostatic interaction. Int J. Mol. Sci. 2019, 20, 1330. https://doi.org/10.3390/ijms20061330. Sharif, S.N.M.; Hashim, N.; md isa, I.; Mamat, M.; Mohd Ali, N.; Suriani, A.B.; Hussein, M.; Mustafar, S. The intercalation behaviour and physico-chemical characterisation of novel intercalated nanocomposite from zinc/aluminium layered double hydroxides and broadleaf herbicide clopyralid. Chem. Chem. Technol. 2020, 14, 38–46. https://doi.org/10.23939/chcht14.01.038. Sharma, P.; Pant, S.; Dave, V.; Tak, K.; Sadhu, V.; Reddy, K.R. Green synthesis and characterization of copper nano-particles by Tinospora cardifolia to produce nature-friendly copper nano-coated fabric and their antimicrobial evaluation. J. Microbiol. Methods. 2019, 160, 107–116. Sharma, S.B.; Sayyed, R.Z.; Trivedi, M.H.; Gobi, T.A. Phosphate solubilizing microbes: Sustainable approach for managing phosphorus deficiency in agricultural soils. SpringerPlus. 2013, 2, 587. Shekhar, S.; Sharma, S.; Kumar, A.; Taneja, A.; Sharma, B. The framework of nanopesticides: A paradigm in biodiversity. Mater. Adv. 2021, 2(20), 6569–6588. https://doi.org/10.1039/D1MA00329A. Shen, Z.; Zhou, X.; Sun, X.; Xu, H.; Chen, H.; Zhou, H. Preparation of 2,4-dichlorophenoxyacetic acid loaded on cysteamine-modified polydopamine and its release behaviors. J. Appl. Polym. Sci. 2019, 136, 47469. https://doi.org/10.1002/app.47469. Siddiqi, K.S.; Rahman, A.U.; Tajuddin; Husen, A. Properties of zinc oxide nanoparticles and their activity against microbes. Nanoscale Res. Lett. 2018, 13, 141. Silva, Md.S.; Cocenza, D.S.; Grillo, R.; Melo, N.F.Sd, Tonello, P.S.; Oliveira, L.Cd, Cassimiro, D.L.; Rosa, A.H.; Fraceto, L.F. Paraquat-loaded alginate/chitosan nanoparticles: Preparation, characterization and soil sorption studies. J. Hazard. Mater. 2011. 190, 366–374. https://doi.org/10.1016/j.jhazmat.2011.03.057. Singh, N.; Manshian, B.; Jenkins, G.J.S.; Griffiths, S.M.; Williams, P.M.; Maffeis, T.G.G.; Wright, C.J.; Doak, S.H. NanoGenotoxicology: The DNA damaging potential of engineered nanomaterials. Biomaterials. 2009, 30, 3891–3914. https://doi.org/10.1016/j.biomaterials.2009.04.009. Singh, P.; Kim, Y.-J.; Zhang, D.; Yang, D.-C. Biological synthesis of nanoparticles from plants and microorganisms. Trends Biotechnol. 2016, 34, 588–599. Sinisi, V.; Pelagatti, P.; Carcelli, M.; Migliori, A.; Mantovani, L.; Righi, L.; Leonardi, G.; Pietarinen, S.; Hubsch, C.; Rogolino, D. A green approach to copper-containing pesticides: Antimicrobial and antifungal activity of brochantite supported on lignin for the development of biobased plant protection products. ACS Sustain. Chem. Eng. 2019, 7, 3213–3221. https://doi.org/10.1021/acssuschemeng.8b05135. Snehal, S.; Lohani, P. Silica nano-particles: Its green synthesis and importance in agriculture. J. Pharmacogn. Phytochem. 2018, 7, 3383–3393. Soliman, M.; Qari, S.H.; Abu-Elsaoud, A.; El-Esawi, M.; Alhaithloul, H.; Elkelish, A. Rapid green synthesis of silver nanoparticles from blue gum augment growth and performance of maize, fenugreek, and onion by modulating plants cellular antioxidant machinery and genes expression. Acta Physiol. Plant. 2020, 42, 148. Speck-Planche, A.; Kleandrova, V.V.; Scotti, M.T. Fragment-based approach for the in silico discovery of multi-target insecticides. Chemom Intell Lab Syst. 2012, 111, 39–45. Sreelekshmi, R.; Siril, E.A.; Muthukrishnan, S. Role of biogenic silver nanoparticles on hyperhydricity reversion in Dianthus chinensis L. an in vitro model culture. J. Plant Growth Regul. 2021, 41, 23–39. Straathoff, H. Investigations on the phytotoxic relevance of volatilization of herbicides. Mededelingen. 1986, 51(2A), 433–438. Subramanian, K.S.; Thirunavukkarasu, M. Nano-fertilizers and nutrient transformations in soil. Nanosci. Plant – Soil Syst. 2017, 30, 5–319. Suhag, M. Potential of biofertilizers to replace chemical fertilizers. Int Adv Res J Sci Technol. 2016, 3(5), 163–167. Sumbul, A.; Ansari, R.A.; Rizvi, R.; Mahmood, I. Azotobacter: A  potential bio-fertilizer for soil and plant health management. Saudi J. Biol. Sci. 2020, 27, 3634–3640. Taban, A.; Saharkhiz, M.J.; Kavoosi, G. Development of pre-emergence herbicide based on arabic gum-gelatin, apple pectin and savory essential oil nano-particles: A potential green alternative to metribuzin. Int. J. Biol. Macromol. 2021, 167, 756–765. https://doi.org/10.1016/j.ijbiomac.2020.12.007. Taban, A.; Saharkhiz, M.J.; Khorram, M. Formulation and assessment of nanoencapsulated bioherbicides based on biopolymers and essential oil. Ind. Crop. Prod. 2020, 149, 112348. https://doi.org/10.1016/j. indcrop.2020.112348.

24

Nanopesticides, Nanoherbicides, and Nanofertilizers

Takeshita, V.; de Sousa, B.T.; Preisler, A.C.; Carvalho, L.B.; Pereira, Ad.E.S.; Tornisielo, V.L.; Dalazen, G.; Oliveira, H.C.; Fraceto, L.F. Foliar absorption and field herbicidal studies of atrazine-loaded polymeric nanoparticles. J. Hazard. Mater. 2021, 418, 126350. https://doi.org/10.1016/j.jhazmat.2021.126350. Talebi, R.; Drostkar, E.; Kanouni, H. Foliar application of Fe, Zn and NPK nano-fertilizers on seed yield and morphological traits in chickpea under rainfed condition article citation: Foliar application of Fe, Zn and NPK nano-fertilizers on seed yield and morphological traits in chickpea under rainfed condition. J. Resour. Ecol. 2016, 4, 221–228. Tarafder, C.; Daizy, M.; Alam, Md.M.; Ali, Md.R.; Islam, Md.J.; Islam, R.; Ahommed, Md.S.; Aly Saad Aly, M.; Khan, Md.Z.H. Formulation of a hybrid nanofertilizer for slow and sustainable release of micronutrients. ACS Omega. 2020, 5, 23960–23966. Thuy, T.T. Effects of DDT on Environment and Human Health. J. Educ. Soc. Sci. 2015, 2, 108–114. Timmusk, S.; Muthoni, J.; Muraya, A.; Behers, L.; Aronsson, A.-C. Perspectives and challenges of microbial application for crop improvement. Front. Plant Sci. 2017. https://doi.org/10.3389/fpls.2017.00049. Timmusk, S.; Seisenbaeva, G.; Behers, L. Titania (TiO2) nano-particles enhance the performance of growthpromoting rhizobacteria. Sci. Rep. 2018, 8, 617. Tiwari, J.N.; Tiwari, R.N.; Kim, K.S. Zero-dimensional, one-dimensional, two-dimensional and three-­ dimensional nanostructured materials for advanced electrochemical energy devices. Prog. Mater. Sci. 2012, 57, 724–803. Toksha, B.; Sonawale, V.A.M.; Vanarase, A.; Bornare, D.; Tonde, S.; Hazra, C.; Kundu, D.; Satdive, A.; Tayde, S.; Chatterjee, A. Nanofertilizers: A review on synthesis and impact of their use on crop yield and environment. Environ. Technol. Innov. N.d. https://doi.org/10.1016/j.eti.2021.101986. Tomer, V.; Sangha, J.K.; Ramya, H.G. Pesticide: An appraisal on human health implications. Proc Natl Acad Sci India Sect B Biol Sci. 2015, 85(2), 451–463. Tong, Y.; Wu, Y.; Zhao, C.; Xu, Y.; Lu, J.; Xiang, S.; Zong, F.; Wu, X. Polymeric nanoparticles as a metolachlor carrier: Water-based formulation for hydrophobic pesticides and absorption by plants. J. Agric. Food Chem. 2017, 65, 7371–7378. https://doi.org/10.1021/acs.jafc.7b02197. Touloupakis, E.; Margelou, A.; Ghanotakis, D. Intercalation of the herbicide atrazine in layered double hydroxides for controlled-release applications. Pest Manag. Sci. 2011, 67, 837–841. https://doi.org/10.1002/ ps.2121. Tripathi, D.K.; Singh, S.; Singh, V.P.; Prasad, S.M.; Chauhan, D.K.; Dubey, N.K. Silicon nanoparticles more efficiently alleviate arsenate toxicity than silicon in maize cultiver and hybrid differing in arsenate tolerance. Front. Environ. Sci. 2016, 4, 46. Tripathi, D.K.; Singh, S.; Singh, V.P.; Prasad, S.M.; Dubey, N.; Chauhan, D.K. Silicon nanoparticles more effectively alleviated UV-B stress than silicon in wheat (Triticum aestivum) seedlings. Plant Physiol. Biochem. 2017, 110, 70–81. Uhm, Y.R.; Han, B.S.; Lee, M.K.; Hong, S.J.; Rhee, C.K. Synthesis and characterization of nanoparticles of ZnO by levitational gas condensation. In: Mater. Sci. Eng. A, Proceedings of the 12th International Conference on Rapidly Quenched & Metastable Materials 449–451, 2007, pp. 813–816. Vafa, Z.; Sohrabi, Y.; Sayyed, R.; Suriani, N.L.; Datta, R. Effects of the combinations of rhizobacteria, mycorrhizae, and seaweed, and supplementary irrigation on growth and yield in wheat cultivars. Plants. 2021, 10, 811. Vaghar, M.S.; Sayfzadeh, S.; Zakerin, H.R.; Kobraee, S.; Valadabadi, S.A. Foliar application of iron, zinc, and manganese nanochelates improves physiological indicators and soybean yield under water deficit stress. J. Plant Nutr. 2020, 43, 2740–2756. Verma, K.K.; Song, X.P.; Joshi, A.; Tian, D.D.; Rajput, V.D.; Singh, M.; Arora, J.; Minkina, T.; Li, Y.R.; Canesi, L. Recent trends in nano-fertilizers for sustainable agriculture under climate change for global food security. Nanomaterials. 2022 https://doi.org/10.3390/nano12010173. Vessey, J.K. Plant growth promoting rhizobacteria as biofertilizers. Plant and Soil. 2003, 255(2), 571–586. Wang, J.; Xie, H.; Han, J.; Li, J.; Lin, X.; Wang, X. Effect of graphene oxideglyphosate nanocomposite on wheat and rape seedlings: Growth, photosynthesis performance, and oxidative stress response. Environ. Technol. Innov. 2022, 27, 102527. https://doi.org/10.1016/j.eti.2022.102527. Wang, X.; Qin, Y.; Li, X.; Yan, B.; Martyniuk, C.J. Comprehensive Interrogation of Metabolic and Bioenergetic Responses of Early-Staged Zebrafish (Danio rerio) to a Commercial Copper Hydroxide Nanopesticide. Environ. Sci. Technol. 2021, Oct 5;55(19):13033–13044. doi: 10.1021/acs.est.1c04431. Wu, J.; Zhai, Y.; Monikh, F.A.; Arenas-Lago, D.; Grillo, R.; Vijver, M.G.; Peijnenburg, W.J.G.M. The differences between the effects of a nanoformulation and a conventional form of atrazine to lettuce: Physiological responses, defense mechanisms, and nutrient displacement. J. Agric. Food Chem. 2021, 69, 12527–12540. https://doi.org/10.1021/acs.jafc.1c01382.

Introduction to Nanopesticides and Nanofertilizers

25

Xiang, Y.; Zhang, G.; Chi, Y.; Cai, D.; Wu, Z. Fabrication of a controllable nanopesticide system with magnetic collectability. Chemical Engineering Journal, 2017, 328, 320–330. https://doi.org/10.1016/j.cej.2017.07.046. Yadav, J.; Jasrotia, P.; Kashyap, P.L.; Bhardwaj, A.K.; Kumar, S.; Singh, M.; Singh, G.P. Nanopesticides: Current status and scope for their application in agriculture. Plant Protect. Sci. 2022, 58, 1–17. Yadav, R.K.; Singh, N.B.; Singh, A.; Yadav, V.; Bano, C.; Khare, S.; Niharika. Expanding the horizons of nanotechnology in agriculture: Recent advances, challenges and future perspectives. Vegetos. 2020, 33, 203–221. Yasmeen, F.; Razzaq, A.; Iqbal, M.N.; Jhanzab, H.M. Effect of silver, copper and iron nanoparticles on wheat germination. Int. J. Biosci. 2015, 6, 112–117. Yin, R.; Gao, L.; Qin, D.; Chen, L.; Niu, N. Preparation of porous carbon-based molecularly imprinted polymers for separation of triazine herbicides in corn. Microchim. Acta. 2021, 189, 23. https://doi.org/10.1007/ s00604-021-05100-9. Yu, Z.; Sun, X.; Song, H.; Wang, W.; ye, Z.; Shi, L.; Ding, K. Glutathione-responsive carboxymethyl chitosan nanoparticles for controlled release of herbicides. Mater. Sci. Appl. 2015, 06, 591–604. https://doi. org/10.4236/msa.2015.66062. Zahedi, S.M.; Moharrami, F.; Sarikhani, S.; Padervand, M. Selenium and silica nanostructure-based recovery of strawberry plants subjected to drought stress. Sci. Rep. 2020, 10, 17672. Zainuddin, N.J.; Ashari, S.E.; Salim, N.; Asib, N.; Omar, D.; Lian, G.E.C. Optimization and Characterization of Palm Oil-based Nanoemulsion Loaded with Parthenium hysterophorus Crude Extract for Natural Herbicide Formulation. J. Oleo Sci. 2019, 68(8), 747–757. doi: 10.5650/jos.ess18209. Zhai, Y.J.; Monikh, F.A.; Wu, J.; Grillo, R.; Arenas-Lago, D.; Darbha, G.K.; Vijver, M.G.; Peijnenburg, W.J.G.M. Interaction between a nano-formulation of atrazine and rhizosphere bacterial communities: Atrazine degradation and bacterial community alterations. Environ. Sci. -Nano. 2020, 7, 3372–3384. https://doi.org/10.1039/d. Zhang, L.; Borror, C.M.; Sandrin, T.R.; Heimesaat, M.M. A designed experiments approach to optimization of automated data acquisition during characterization of bacteria with MALDI-TOF mass spectrometry. PLoS One. 2014. https://doi.org/10.1371/journal.pone.0092720. Zhang, X.; Xu, Z.; Wu, M.; Qian, X.; Lin, D.; Zhang, H.; Tang, J.; Zeng, T.; Yao, W.; Filser, J.; Li, L.; Sharma, V.K. Potential environmental risks of nanopesticides: Application of Cu(OH)2 nanopesticides to soil mitigates the degradation of neonicotinoid thiacloprid. Environ. Int. 2019, 129, 42–50. https://doi. org/10.1016/j.envint.2019.05.022. Zhao, L.; Huang, Y.; Hannah-Bick, C.; Fulton, A.N.; Keller, A.A. Application of metabolomics to assess the impact of Cu(OH)2 nanopesticide on the nutritional value of lettuce (Lactuca sativa): Enhanced Cu intake and reduced antioxidants. NanoImpact. 2016, 3–4, 58–66. https://doi.org/10.1016/j.impact.2016.08.005. Zhao, M.; Zhou, H.; Chen, L.; Hao, L.; Chen, H.; Zhou, X. Carboxymethyl chitosan grafted trisiloxane surfactant nanoparticles with pH sensitivity for sustained release of pesticide. Carbohydr. Polym. 2020, 243, 116433. https://doi.org/10.1016/j.carbpol.2020.116433. Zielinska, A.; Carreiro, F.; Oliveira, A.M.; Neves, A.; Pires, B.; Venkatesh, D.N.; Durazzo, A.; Lucarini, M.; Eder, P.; Silva, A.M.; Santini, A.; Souto, E.B. Polymeric nanoparticles: Production, characterization, toxicology and ecotoxicology. Molecules. 2020, 25(16), 3731. doi:10.3390/molecules25163731. Zulfiqar, F.; Navarro, M.; Ashraf, M.; Akram, N.A.; Munne-Bosch, S. Nanofertilizer use for sustainable agriculture: Advantages and limitations. Plant Sci. 2019, 289, 110270.

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Sustainable Nanotechnology in Agriculture Bhavna Kumari and Anupam Prakash

2.1 INTRODUCTION One of life’s necessities, food, is largely provided by agriculture, which is also an enterprise. By 2050, the world’s population is expected to increase to over 9 billion people from its current level of fewer than 7 billion, according to a UN projection. By 2050, there must be a supplemental billion tonnes of cereals and 200 million tonnes of animal protein needed each year for a total global food consumption of 3,130 kcal per person per day. It will take a mix of increased crop yields and cropping intensity to meet these aims (FAO 2009). The rise in the production of first-generation biofuels from grains and oilseeds in recent years significantly increases the demand for agricultural products on a worldwide scale (Hervé et al. 2011). Farming has always been the most valuable and stable sector, but the scarcity of natural resources and the growing population require its development to be ecologically and economically sustainable. Adequate crop plant production as well as disease preservation necessitate adequate soil fertility and phytopathogen destruction. There are numerous effective approaches available to increase and diversify agricultural production and mitigate infectious agent burdens in various regions of the world, including synthetic fertilizers to increase the fertility of the soil and pesticides to counteract yield-limiting pathogens, but these methods also result in environmental instability in the region in addition to financial costs. Most of the farmland is losing its fertility as a result of intensive agricultural methods such as increased synthetic fertilizer use, which has a detrimental impact, for instance, traditional fertilizer loses 50–70% of the nitrogen to the atmosphere volatilization, soil acidification, and changes in soil microbiome on crop yield (DeRosa 2010). According to the Food and Agriculture Organization (), the worldwide application of fertilizer in agriculture presently reaches 186 million tonnes, with a forecast growth of 1.5 to 2.4% by 2020 (FAO 2021). The widespread use of such chemicals in agriculture has jeopardized our environment by causing a variety of pollution, in addition to the high economic expenses that farmers face in developing countries. Without the use of agrochemicals like pesticides, fertilizers, etc., sustainable output and efficiency in current farming are unthinkable. To address the concerns of environmental sustainability, as well as the expenses associated with fertilizers, emerging agricultural technologies must be used that can also cope with climate change. The use of nano-enabled techniques is one approach to overcome all these issues. Aside from this, eco-friendly replacements can be used, but they require a large dosage for optimum outcomes in a specific region, and their performance is poor under varied and unexpected environmental changes. The application of nanotechnology in agriculture is not recent. Nanotechnology’s application in agriculture is not a recent development; discussions of it can be found in works that were published as early as 1999 (Roco 1999). Nanotechnology is a discipline of science that utilizes nanostructures, which are particles with sizes varying from 1 to 100 nm (Mansoori & Soelaiman 2005). When used in agriculture, nanotechnology can produce particles smaller than conventional materials, which have several advantages over their nonbiodegradable inorganic counterparts, including elevated affectivity, minimal environmental threats, and minimal financial consequences. Through nanotechnology plants, specific nanofertilizers can be prepared. This analysis focuses on nanomaterials to get beyond the drawbacks of using chemical fertilizers and pesticides, as well as the possibility of nanotechnology for managing sustainable farming in the future. 26

DOI: 10.1201/9781003364429-2

Sustainable Nanotechnology in Agriculture

27

2.2  NANOTECHNOLOGY IN AGRICULTURE – A SUSTAINABLE APPROACH The usage of fertilizers has increased dramatically during the past 50 years. The agricultural industry is struggling with a wide range of issues, including nutritional and organic matter deficiency, climate changes like fluctuating rainfall, temperature rise, drought, stagnant crop production, a decrease in the amount of arable land and water accessible, disease in crops, opposition to GMOs, a labor shortage, and cost of seed manure. Many of these problems are just the result of agrochemical use that is excessive and inappropriate. Insecticide use grew by 4.1 million tonnes globally between 2000 and 2018, with Asia making the largest contribution. China used 1.8 million tonnes of pesticides in 2018, accounting for 43% of the world total, far surpassing Brazil and the United States. Similarly, in 2018, 188 million tonnes of chemical fertilizers were used in agriculture, calculated as the total of the three nutrients nitrogen (N), phosphorus (P2O5), and potassium (K2O). It was a 40% increase over the amount used in 2000 (FAO 2021). Due to the imbalance between the organic and inorganic soil composition, which is crucial to maintain the health of any region’s soil, multiplenutrient drainage is continuously expanding, and soil health is deteriorating very quickly as a result. It is extremely challenging to obtain healthier soil since inorganics are subsidized at a higher level, while organics are becoming less and less readily available. In addition, these agrochemicals may cause problems like water pollution that endanger human health and the environment. To improve efficacy and sustainability, slow-release fertilizers are developed using nanotechnology, and the bioavailability of nutrients that are weakly accessible is improved. Other uncontrollable elements that affect agriculture include weather, temperature, precipitation, anthropogenic climate change, and water supply. Therefore, it is extremely important to detect, record, control, and maintain accurate and trustworthy data on all biotic and abiotic variables to meet the difficulties of the amount and quality of agricultural production while preserving environmental sustainability. To do this, we need more electrical equipment and technology, which may also drive up the price of agriculture. For the screening, surveillance, and evaluation of biological host molecules in the agricultural sector, there is a high demand for quick, dependable, and affordable solutions in the 21st century. This high demand can be fulfilled by using nanosensors; farmers would be able to increase the productivity of their farms by using robust and portable in-situ nanotechnology-guided detection, observation, evaluation, and records. The safe administration of nanoparticles might promote plant development and crop yield. Other devices such as carbon nanotubes have the potential to function as biosensors and are beneficial for electrical sensing in challenging and harsh biological settings. Additionally, it has been demonstrated that nanomaterials are beneficial for managing the dose and regulated release of nutrients and pharmaceuticals for plants (Figure 2.1). This is how nanotechnology promotes sustainability (Mondal et al. 2022).

2.3 NANOTECHNOLOGICAL INTERVENTION TO IMPROVE CROP PRODUCTIVITY Nanotechnology is a convenient technology in biology that may be applied at the physiological, biochemical, and molecular levels to enhance crop development and production, plant disease diagnosis and management, insect and pest management, seed germination, and sustainable cultivation. It also has some beneficial effects on processes like photosynthesis through various nanoscience tools and techniques. These methods can also be applied to live plants. The fusion of nanotechnology and biotechnology offers new molecular transporter technologies that may be used to manipulate genes and even create new and disease-free species with desired characteristics (Tarafdar et al. 2013). Viral gene delivery vectors encounter several difficulties with traditional gene delivery techniques, including a restricted host range, a small amount of inserted genetic material, difficult transportation across the cell wall, a phospholipid bilayer, and a nuclear membrane. To deliver and distribute foreign DNA, RNA, oligonucleotides, and other drugs to the target cell for gene editing and other biochemical changes, nanoparticles, nanocapsules, and nanofibers can be

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Nanopesticides, Nanoherbicides, and Nanofertilizers

FIGURE 2.1  Nanotechnology Progresses Sustainably.

utilized as transporters. ZnS and gold nanoparticles, mesoporous silica nanoparticles (MSNs), and silicon dioxide nanoparticles, which are mostly employed in tobacco and maize plants, have been designed to transport DNA fragments to the target spot without creating any adverse side effects, the delivery of NPs with SiRNA trapped within, enabled for the target-specific control of insect pests, high tensile strength nanomaterials are used to transform pollen through massive pollen surface apertures, carbon-coated iron nanoparticles can be inserted inside the internal hallow petiole of pumpkin leaf, and starch nanoparticles can successfully pass the cell wall are a few examples of materials used to transfer genetic material (Torney et al. 2007). Several nano-diagnostic techniques, including nanofluidics, nanomaterials, and bioanalytical nanosensors (smart monitoring), among others, have the potential to enhance plant breeding programs as they are efficient diagnostic techniques for quickly identifying plant diseases; they are now crucial to ensuring agricultural sustainability and global food security. Devices made of carbon nanotubes have the potential to be used as biosensors and are advantageous for electrical sensing in challenging and harsh bioconditions. These devices are highly sensitive, stable, manageable, and cost-effective (Ghaffar et  al. 2020). Additionally, the creation and application of nanosensors aid in monitoring soil conditions such as alkalinity and salinity. It also helps in estimating the utilization, and the requirement for agrochemicals that positively impacted individual control of soil and plant health is greatly contributing to sustainable farming and limiting the use of agrochemicals as the enhanced use of pesticides and chemical fertilizers results in unavoidable accumulation of toxic agrichemicals on both soil surface and in groundwater as well. To increase soil fertility and crop production, enormous amounts of fertilizers are needed. It has also been established that fertilizers account for onethird of agricultural yields, with the remaining three quarters depending on the effectiveness of certain other farm inputs but that as a result of chemical leaching loss, drift, washout, hydrolysis, volatilization, photodissociation, and photodecomposition, or even biological destruction, only a very small quantity of fertilizer – far below the desired concentration – reaches the targeted region when applied directly to the soil or sprayed on the leaves. The nutrient use efficiency for nitrogen (N) is 30–35%, the nutrient use efficiency for potassium (K) is 35–40%, and the remaining portion

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Sustainable Nanotechnology in Agriculture

TABLE 2.1 Common Nanoformulations and Their Applications. Nanoformulation

Source

Application

Reference

Zinc oxide nanoparticles (ZnO NPs) Nanoclay, hydrogel

Citrus sinensis (orange), Citrus paradisi (grapefruit) CaO, SiO2, and Al2O3

Roles as catalysts, gas sensors

Dhanemozhi et al. 2017

Soil water management

Srivastava et al. 2018

Gold nanoparticle (Au NPs)

Leaf extract of Ziziphus zizyphus

Antimicrobial agents against a wide range of microorganisms

Aljabali et al. 2018

Silica nanoparticle

Silica

Seed germination, tomato seed treatment

Srivastava et al. 2018

Cerium oxide (CeO2) nanoparticle

Gloriosa superba leaves

Bio-imaging, and antibacterial activity

Arumugam et al. 2015

Silver nanoparticle (Ag NPs)

Zingiber officinale root extract, Azadirachta indica extracts

Antimicrobial agent

Vijaya et al. 2017

starts building up in the soil and then leaks into underground water, contributing to widespread eutrophication. It is estimated that less than 20% of the phosphorus applied as fertilizers reach the targeted site. The situation is considerably worse for micronutrients: the maximum absorption efficiency ranges from 17 to 23% for boron, 8.5% for zinc, 0.35% for copper, and 14.5% for molybdenum. Therefore, it is essential to develop alternative techniques to reduce the wastage of mobile nutrients by making unavailable minerals more accessible and providing slow-release fertilizers. In the context of sustainable agriculture, the use of engineered nanomaterials like nanopesticides and nanofertilizers has demonstrated a brand-new approach to overcome the limitation of conventional techniques and unpredictability in the agricultural sector with constrained resources. By encapsulating nutrients into the nanomaterials, they may readily develop. Table 2.1 shows several successful nanoformulations. When compared to traditional fertilizers, nanofertilizers had a median effectiveness boost of 18–29%, according to Kah et al. (2018)’s examination of a dataset of nanofertilizers. The potential for nanomaterials, which were specifically designed to control the delivery of nutrients based on the quantity and quality needs of the crops while avoiding differential losses, is enormous. To minimize a variety of pests, regulated and gradual medication release by nanoencapsulation of conventional pesticides is a useful approach. A variety of low-cost nanotech applications exist for improved seed germination, crop development, crop cultivation, and environmental adaptation (Figure 2.2).

2.3.1 Nanobiosensors The next generation of biosensors, known as nanobiosensors, are smaller, connected to sensitive elements, and can detect specific analytes at extremely low concentrations by use of a physicalchemical transducer (Usman et al. 2020). Real-time monitoring of crop conditions, pathogen distribution, field conditions, and environmental conditions is made possible using nanosensors. To identify the specific biological analyte present, these hybrid receptor-transducer systems monitor the physical and chemical characteristics of a medium. Bioreceptors that are covalently bonded to the transducer make up biosensors. Biosensors are primarily categorized into five groups based on the molecules that serve as their bioreceptors: (1) based on cellular interactions, (2) DNA, (3) enzymes, (4) antibodies or antigens, and (5) using bioinspired materials (e.g., synthetic bioreceptors). It is classified into three categories based on the transducer type: (1) electrochemical, (2) mass-based, and (3) optical biosensor (Usman et al. 2020; Gruber et al. 2017). To detect a single

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Nanopesticides, Nanoherbicides, and Nanofertilizers

FIGURE 2.2  A Diversity of Nanotechnology Interventions to Increase Crop Yield.

or multiplex analyte, a bioreceptor on a transducer sends a signal to a recognition element. These nanobiosensors use parts per trillion (ppt) to measure analyte concentration. Utilizing sensor technologies to automate irrigation systems has the enormous potential to increase water usage effectiveness. When there is a water shortage, real-time soil water tension estimation using nanosensors and autonomous irrigation control is used. For use in biosensors, nanomaterials such as metal (silver, gold, cobalt, etc.) NPs, carbon nanotubes, magnetic NPs, and quantum dots have all been extensively researched. The inclusion of the biological element in combination with an appropriate transducer, which provides a signal after interaction with the target molecule of interest, accounts for the improved specificity and sensitivity of biosensor systems compared with conventional approaches. Devices made of carbon nanotubes have the potential to function as biosensors. A variety of nanobiosensors are employed in agriculture to boost production (Kruss et al. 2013; Arduini et al. 2016).

2.3.2 Nanofertilizers Nutrient insufficiency issues now have a technical remedy, thanks to the nanoscale dimension of nanofertilizers. Nanomaterials that may be nutrients themselves (micro- or macronutrients) or serve as transporters or enhancers for the nutrients are known as nanofertilizers. To improve target-specific plant absorption efficiency, the needed nutrients were first encapsulated in the nanomaterials after they had been manufactured using several designed methods. These are fertilizer transporters with nanoscale dimensions between 30 and 40 nm, which can retain a large number of nutrient ions because of their high surface area and deliver them gradually and regularly by crop requirement. These are mainly strong sorbent fertilizers for phosphate and nitrogen. To create nanofertilizers for soil and/or foliar application, nanostructured materials such as clay minerals, hydroxyapatite, chitosan, polyacrylic acid, and zeolite are mainly employed. The nutrients that can be loaded in cationic forms like NH4+ and K+ are the only ones that can be added to slow-release fertilizers (SRFs) based on zeolites. To load the anionic form, adjustments are necessary. To effectively load the anionic nutrients for use as SRFs, these anionic materials must have a sufficient affinity for anions. Surfactants

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are mainly used for this modification. Synthesized nano-fertilizers are characterized by particle size analyzer (PSA), zeta analyzer, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscope (SEM), and Energy-dispersive X-ray analysis (EDAX), Transmission Electron Microscopy (TEM), and Atomic Force Microscopy (AFM) to validate size, shape, charge distribution, functional categories, elemental makeup, surfactant bonding, and sulphate attachment. Multiple nano-adsorbents have been tried to provide almost all necessary nutrients. Abundant nutritional ions are slowly and continuously adsorbed and desorbed over a lengthy period of time through this technique (Subramanian et al. 2015).

2.3.3 Nanopesticides Pest control agents are compounds known as pesticides. These plant protection products generally include herbicides, insecticides, nematicides, avicides, weedicides, rodenticides, bactericides, insect repellents, animal repellents, microbicides, and fungicides, to protect plants from weeds, fungi, pathogens, nematodes (roundworms), microbes, or insects. Pest control chemicals are often applied by dissolving the chemical in a solvent-surfactant mix (commonly hydrocarbon-based) to create a uniform formulation (Sarkar et al. 2021). Dusting with elemental sulfur, which was utilized in ancient Mesopotamia some 4,500 years ago, was the first known pesticide. Two other organic pesticides, pyrethrum, which comes from chrysanthemums, and rotenone were introduced in the 19th century. Due to its broad-spectrum action, Paul Müller discovered that DDT was a particularly efficient pesticide. The traditional class of insecticides has several significant drawbacks, including maximum concentration per unit crop, drifting risks, potential losses, remnants in the environment, vegetation, and perishable goods, as well as an adverse effect on nontarget species and has serious consequences on the food chain, human health, and environment (Abubakar et  al. 2020). Since pesticides are so widely used, weeds, insects, and pathogens may have evolved resistance to them. Therefore, they should be modified with a different pest management approach that can fill in the voids mentioned earlier. One solution to these issues is the use of nanopesticides. The main goal of developing nanopesticides is to increase a chemical’s effectiveness while reducing the environmental risks associated with a pesticide active component. The main advantages of these nanoparticles are their increased solubility of the active components, enhanced formulation stability, gradual release of the active ingredient, and increased mobility due to their smaller particulate matter and greater surface coverage. Different processes are used to create nanopesticides. Using Tween 20 as the surfactant, an oil-in-water nanoemulsion of neem oil has been produced for the control of insects. Other typical formulations include nanodispersions, polymer-based nanoparticles, nanoencapsulation, and hydrogel nanoparticles (Anjali et  al. 2012). The delayed release of the active substances was said to have boosted efficiency. The improved distribution and functionalization of pesticide molecules is a direct result of nanopesticide formulations, which increase droplet adherence to plant surfaces (and hence decrease drift wastage). In comparison to chlorfenapyr paired with microparticles, chlorfenapyr coupled with silica nanoparticles displayed two or three times better insecticidal action toward bollworms. Nanoparticles of silver, copper, and aluminum are three of the most significant inorganic nanoparticles with pesticidal characteristics (Song et al. 2012). The insect cuticle wax is damaged by sorption and abrasion when inert dust like silica, alumina, and clays are present. The bug may become dehydrated as a result of the physical trauma it has sustained (Rajna & Paschapur 2019). Insecticides that are hydrophobic, such as azadirachtin, combined with modified chitosan nanoparticles demonstrated promising results in inhibiting cell growth in Spodoptera litura ovarian cell lines while still maintaining drug release (Lu et al. 2013). These are the fundamental methods through which nanoinsecticides composed of solid nanoparticles function. Increasing active compounds solubility could boost their dispersion and biodegradation by microbial cells in the soil. Because of their ability to improve chemical solubility, nanoparticlebased pesticides are also thought to be safer for the environment than traditional treatments (Rajput et al. 2021).

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2.3.4 Nanoherbicides Crop growth and yield are typically negatively impacted when weeds (unwanted grasses) are coplanted. To get rid of weeds, it is best to eradicate their seedlings in the ground so they can’t germinate when the time and place are suitable. As a result, conventional herbicides are frequently employed to suppress the development of weeds; nevertheless, spraying of herbicides can occasionally have unintended consequences for the crop due to the herbicides’ high toxicity and extended half-life. In this scenario, the application of nanoherbicides (formulation of biocompatible and biodegradable compounds) as a solution to the problem can be quite beneficial. Since they are so tiny, nanoherbicides will be able to blend in seamlessly with the soil and eradicate weeds from their roots without damaging the crops that are intended to be harvested and because of this small size, herbicide can only be sprayed when it is essential by the requirements of the agricultural land. To encapsulate atrazine, for instance, poly (epsilon-caprolactone) has been utilized because of the favorable physicochemical characteristics that it possesses, as well as its increased bioavailability and biocompatibility (Pereira et al. 2014). The effectiveness of the atrazine-encapsulated polymeric nanoparticles was demonstrated on the target Amaranthus viridis L., Brassica spp., and Bidens pilosa L. with increased phytotoxic activity, longevity (for three months), and decreased mobility in the ground in comparison to free atrazine. Genotoxicity and cytotoxicity studies showed that nanoformulations of atrazine and paraquat had a lower hazardous impact on nontarget plants like onion compared to the pure chemicals (Grillo et al. 2014; Pereira et al. 2014).

2.3.5 Nanofiltration in Agriculture In many parts of the world, agricultural techniques are facing significant challenges as a direct result of a lack of available water. For the foreseeable future, wastewater restoration and recycling industrial wastewater for various reasons, such as potable water, irrigation water, and the manufacturing process, have become more significant. As a result of its low energy requirements and environmentally favorable working conditions, nanofiltration membranes have emerged as a potentially useful option for addressing the scarcity of clean water and the procedures involved in treating wastewater. For water filtration, nanotechnology is helpful in the production of a variety of lowenergy replacements, such as thin-film nanocomposite membranes, protein–polymer bioinspired membranes, and carbon nanotube membranes (Hoek et al. 2014). The water is purified by a process known as nanofiltration (NF), a pressure-driven membrane technique that uses subatomic-sized materials such as alumina fibers, nanoporous ceramics, carbon nanotubes, and magnetic nanoparticles. It may be performed cheaply. When it comes to the manufacture of commercial thin-film composite (TFC) membranes, the process known as interfacial polymerization is regarded as a procedure that is both quick and extremely effective. The selectivity layer is produced at the boundary between two liquid phases. The functional component of the layer may be adjusted by varying the monomer (its kind and proportion), the duration of time, the temperature, and any posttreatment that is applied. NF membranes have a great capacity for the removal of both inorganic and organic contaminants, in addition to the eradication of microorganisms (Srivastava et al. 2019). To remove synthetic agrochemicals and organic particles from water, such as endosulfan, dichlorodiphenyltrichloroethane (DDT), HCH, chlorpyrifos, difenoconazole, and malathion, nanoparticle filters can be used. The most effective use of nanoscale zero-valent iron is in the elimination of contaminants that are present in soil or groundwater. The hydrotalcite column, which is composed of a synthetic clay mineral, is employed as filtration system by allowing it to trickle down through the column. Leaching may be accomplished with the help of filtration candles or porous pots. Microorganisms and viruses with a negative charge are made to attract to the positive charge of the nanoceram filter, which is an example of a nanofilter (Karn et al. 2009) In recent years, magnetic separations have become feasible at extremely weak gradients of magnetic fields. Monodisperse magnetite (Fe3O4) and other nanocrystals exhibit a very potent and irreversible interaction with arsenic while keeping their magnetic characteristics. Water contaminated with arsenic may be filtered out using a simple

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portable magnet and nanocrystals; such a manner is possibly a useful filter for use in irrigation systems (Yavuz et al. 2006).

2.3.6 Application of Nanotechnology in Seed Science The formation of seeds is a time-consuming process that is especially laborious in wind-pollinated plants. Seeds are self-replicating living entities that are capable of surviving on their own in severe environments. It is also possible to imbue seeds with nanoencapsulations containing a particular strain of bacteria, creating what is known as smart seeds. This will result in a reduced seed rate, the establishment of the correct ground stand, and an improvement in seed yield. For reforestation throughout a mountain range, adaptive seeds can be designed to sprout only under specific conditions, such as when there is sufficient moisture in the soil (Sharma & Thakur 2019). Carbon nanotubes are used to improve the germination rate of tomato seeds by increasing the amount of moisture that can pass through them; using bio-nanosensors is one way to ensure the genetic purity of an organism. These sensors may also be used to detect other types of pollen contamination. The percentage of seed germination was observed to rise when multiwall carbon nanotubes (MWCNTs) were either sprinkled on the seed surface or combined in the nutrient broth of three distinct crops, namely, barley, beans, and corn. Wheat’s seed production, volume, stem length, flowering, productivity, glucose, and gluten content were all improved by 20g/L Ti NPs (Wang et al. 2012) (Zheng et al. 2005). By imparting plants resilience to different stresses, nano-priming is a cutting-edge seed priming technique that serves to increase seed germination, seed development, and yield. Priming is the process of treating seeds before sowing them using conventional techniques such as presoaking and covering. Some typical instances of current priming mechanisms include hydro-priming and osmo-priming. They have demonstrated possible agricultural advantages such as increased germination rates, development and proliferation, increased stress (both abiotic and biotic) tolerance, increased crop output, and increased micronutrient concentrations in grains. Nano-priming triggers the development of nanopores in shoots and aids in water absorption, activates reactive oxygen species (ROS) in seeds, creates hydroxyl radicals to loosen the walls of cells, and serves as a stimulant for rapid hydrolysis of starch via amylase stimulation, resulting in seed germination stimulation (Nile et al. 2022). It also promotes the expression of aquaporin genes, which are involved in water absorption, and it facilitates the dispersion of H2O2, or ROS, across biological membranes (Figure 2.3) (Khan et al. 2017).

FIGURE 2.3  Seed Nano-Priming.

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2.3.7 Nanomaterials to Control Plant Diseases The production of silver nanoparticles for use as antibacterial medications has become increasingly cost-effective as technology has advanced. Nanoparticles have the potential to be used as a safe and eco-friendly alternative to conventional fungicides and other biocides for managing a variety of plant infections due to their ability to inhibit microorganisms’ metabolism, diversity through a variety of mechanisms, including the expression of Adenosine triphosphate manufacturing related proteins and plasma membrane disorganization, the soil type and hydration level, as well as the characteristics and concentration of the nanoparticles themselves, which have a role in the toxicity they may cause or they may affect indirectly, by the enhancement of the bioavailability of additional hazardous chemicals originally existent in the soil (Bruna et al. 2021). According to research, silver nanoparticles are a more potent toxin for Gram-negative bacteria (Pal et al. 2007). Wood or food items preserved with either ZnO or MgO have also been proposed as antimicrobial agents (Aruoja et al. 2009). Nanocapsules with the right functional groups can penetrate the cuticle of the target weed more effectively and then release their contents slowly and steadily over time. Direct or indirect detection of pesticides, microbes, toxins, heavy metals, and other pollutants is just one use of nanobiosensors in the agricultural industry. Nano-Zn has been shown to prevent a wide variety of fungal infections in in vitro studies. Additional research is necessary to investigate the possibilities of their application.

2.4  NANO-BIO-FARMING: THE FUTURE OF AGRICULTURE Nanotechnology has the potential to increase crop output and nutritional content, as well as the overall value of agricultural products. The use of nanotechnology brings about significant improvements to organic farming. Monitors, global positioning systems, and other remotely sensed data equipment are used to measure highly localized environmental conditions and other agricultural characteristics such as relative humidity, warmth, planting, nutrient, and other such things to improve the productivity of organic agriculture. Despite advances in nanotechnology, nanoparticle use in crop development and agriculture is still lacking, and additional study is needed. A solution must be found to the environmental and agricultural threats if we are to survive. The World Health Organization (WHO) and the Food and Agricultural Organization (FAO) organized a strategic partnership in June 2009 to highlight the relevance of using nanotechnology in the agriculture and food sectors (WHO 2010). Improved nutrient uptake by plants, leading to higher yields, and molecular disease management are just some examples of how nanotechnology is paving the way for agricultural advancement. One promising area for the improvement of nanotechnology in agricultural applications is in the direct reduction of plant stress and disease through antibacterial, antioxidant, nanoherbicides, nanopesticides, etc. We should prioritize sustainable expansion in agriculture rather than continuing to degrade the environment, which will eventually harm humankind. This is where nanotechnology comes in; it has paved the path for scientists to offer a wide range of environmentally friendly choices that nevertheless ensure bumper crops (Duhan et al. 2017). There are several commercially accessible nanoformulations listed in Table 2.2.

2.5  CONCLUSION OF SUSTAINABLE DEVELOPMENT Ecological needs become more predictable as a result of sustainable development. To put it another way, it ensures that the next generation will have access to these materials. Incredible conservation efforts may be made with sustainable development. This may be accomplished by using materials and methods that are gentler on the planet. The resources at our disposal must be utilized responsibly to ensure that they will be available for future generations. The subject of plant sciences has benefited greatly from the advances in nanotechnology. It is now widely known that nanoparticles have beneficial impacts on plant growth and development, agricultural enhancement, and their roles

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TABLE 2.2 Commercially Available Nanoformulations. Commercially Available Nanoformulations

Common Constituents

Name of Manufacturer

Reference

Biozar nanofertilizers

Organic materials, micronutrients, macronutrients

Nanocapsule

N, 0.5%; P2O5, 0.7%; K2O, 3.9%; Ca, 2.0%; Mg, 0.2%; S, 0.8%; Fe, 2.0%; Mn, 0.004%; Cu, 0.007%; Zn, 0.004%

Fanavar Nano Pazhoohesh Markazi company Iran The Best International Network Co., LTD Thailand

Gade et al. 2023

Nano Green

Extracts of corn, grain, soybeans, potatoes, coconut, and palm

Nano Green Sciences, Inc., India

Prasad et al. 2017

Nano Micro Nutrient (Eco Star) Plant

Zn, 6%; B, 2%; Cu, 1%; Fe, 6%+; EDTA Mo, 0.05%; Mn, 5%+; AMINOS, 5%

Shan Maw Myae Trading Co., Ltd. India

Prasad et al. 2017

Nutrition Powder (Green Nano)

N, 0.5%; P2O5, 0.7%; K2O, 3.9%; Ca, 2.0%; Mg, 0.2%; S, 0.8%; Fe, 1.0%; Mn, 49 ppm; Cu, 17 ppm; Zn, 12 ppm

Green Organic World Co., Ltd. Thailand

Pitambara et al. 2019

Nano Calcium (Magic Green)

CaCO3, 77.9%; MgCO3, 7.4%; SiO2, 7.47%; K, 0.2%; Na, 0.03%; P, 0.02%; Fe, 7.4 ppm; Al2O3, 6.3 ppm; Sr, 804 ppm; sulphate, 278 ppm; Ba, 174 ppm; Mn, 172 ppm; Zn, 10 ppm

PAC International Network Co., Ltd. Germany

Mohammadi et al. 2022

TAG NANO (NPK, PhoS, Zinc, Cal, etc.) fertilizers

Proteino-lacto-gluconate chelated with micronutrients, vitamins, probiotics, seaweed extracts, humic acid

Tropical Agrosystem India (P) Ltd, India

Quezada et al. 2022

Gade et al. 2023

as fertilizers, insect control, and post-harvest technologies. More research is needed in a wider variety of plant species and with a wider range of nanoparticle combinations and concentrations because of the wide variation in plant species’ resistance to nanoparticles. Nanotechnology would boost the green revolution in the upcoming two decades.

REFERENCES Abubakar, Y., Tijjani, H., Egbuna, C., Adetunji, C. O., Kala, S., Kryeziu, T. L., Ifemeje, J. C., & PatrickIwuanyanwu, K. C. (2020). Chapter 3 - Pesticides, history, and classification. In C. Egbuna & B. Sawicka (Eds.), Natural remedies for pest, disease and weed control, pp. 29–42. Academic Press. Aljabali, A. A., Akkam, Y., Al Zoubi, M. S., Al-Batayneh, K. M., Al-Trad, B., Abo Alrob, O., . . . Evans, D. J. (2018). Synthesis of gold nanoparticles using leaf extract of Ziziphus zizyphus and their antimicrobial activity. Nanomaterials, 8(3), 174. Anjali, C. H., Sharma, Y., Mukherjee, A.,  & Chandrasekaran, N. (2012). Neem oil (Azadirachta indica) ­nanoemulsion—a potent larvicidal agent against Culex quinquefasciatus.  Pest Management Science, 68(2), 158–163. Arduini, F., Cinti, S., Scognamiglio, V., & Moscone, D. (2016). Nanomaterials in electrochemical biosensors for pesticide detection: Advances and challenges in food analysis. Microchimica Acta, 183, 2063–2083. Arumugam, A., Karthikeyan, C., Hameed, A. S. H., Gopinath, K., Gowri, S., & Karthika, V. (2015). Synthesis of cerium oxide nanoparticles using Gloriosa superba L. leaf extract and their structural, optical and antibacterial properties. Materials Science and Engineering: C, 49, 408–415. Aruoja, V., Dubourguier, H. C., Kasemets, K., & Kahru, A. (2009). Toxicity of nanoparticles of CuO, ZnO and TiO2 to microalgae Pseudokirchneriella subcapitata. Science of the Total Environment, 407(4), 1461–1468.

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Avila-Quezada, G. D., Ingle, A. P., Golińska, P., & Rai, M. (2022). Strategic applications of nano-fertilizers for sustainable agriculture: Benefits and bottlenecks. Nanotechnology Reviews, 11(1), 2123–2140. Bruna, T., Maldonado-Bravo, F., Jara, P., & Caro, N. (2021). Silver nanoparticles and their antibacterial applications. International Journal of Molecular Sciences, 22(13), 7202. DeRosa, M. C., Monreal, C., Schnitzer, M., Walsh, R.,  & Sultan, Y. (2010). Nanotechnology in fertilizers. Nature Nanotechnology, 5(2), 91–91. Dhanemozhi, A. C., Rajeswari, V., & Sathyajothi, S. (2017). Green synthesis of zinc oxide nanoparticle using green tea leaf extract for supercapacitor application. Materials Today: Proceedings, 4(2), 660–667. Duhan, J. S., Kumar, R., Kumar, N., Kaur, P., Nehra, K., & Duhan, S. (2017). Nanotechnology: The new perspective in precision agriculture. Biotechnology Reports, 15, 11–23. FAO. (2009). How to Feed the World in 2050, Food and Agriculture Organization, Rome. https://www.fao.org/ fileadmin/templates/wsfs/docs/expert_paper/How_to_Feed_the_World_in_2050.pdf FAO. (2021). The State of Food and Agriculture 2021, Food and Agriculture Organization, Rome. https://www. fao.org/documents/card/en/c/cb4476en Gade, A., Ingle, P., Nimbalkar, U., Rai, M., Raut, R., Vedpathak, M., .  .  . Abd-Elsalam, K. A. (2023). Nanofertilizers: The next generation of agrochemicals for long-term impact on sustainability in farming systems. Agrochemicals, 2(2), 257–278. Ghaffar, N., Farrukh, M. A., & Naz, S. (2020). Applications of nanobiosensors in agriculture. In: Javad, S. (eds) Nanoagronomy, pp. 179–196. Springer, Cham. Grillo, R., Pereira, A. E., Nishisaka, C. S., De Lima, R., Oehlke, K., Greiner, R.,  & Fraceto, L. F. (2014). Chitosan/tripolyphosphate nanoparticles loaded with paraquat herbicide: An environmentally safer alternative for weed control. Journal of Hazardous Materials, 278, 163–171. Gruber, P., Marques, M. P., Szita, N., & Mayr, T. (2017). Integration and application of optical chemical sensors in microbioreactors. Lab on a Chip, 17(16), 2693–2712. Hervé, G., Agneta, F.,  & Yves, D. (2011). Biofuels and world agricultural markets: Outlook for 2020 and 2050. Economic Effects of Biofuel Production, 129, 162. Hoek, E. M., Pendergast, M. T. M., & Ghosh, A. K. (2014). Nanotechnology-based membranes for water purification. Nanotechnology Applications for Clean Water, 133–154. Kah, M., Kookana, R. S., Gogos, A.,  & Bucheli, T. D. (2018). A  critical evaluation of nanopesticides and nanofertilizers against their conventional analogues. Nature Nanotechnology, 13(8), 677–684. Karn, B., Kuiken, T., & Otto, M. (2009). Nanotechnology and in situ remediation: A review of the benefits and potential risks. Environmental Health Perspectives, 117(12), 1813–1831. Khan, M. N., Mobin, M., Abbas, Z. K., AlMutairi, K. A., & Siddiqui, Z. H. (2017). Role of nanomaterials in plants under challenging environments. Plant Physiology and Biochemistry, 110, 194–209. Kruss, S., Hilmer, A. J., Zhang, J., Reuel, N. F., Mu, B., & Strano, M. S. (2013). Carbon nanotubes as optical biomedical sensors. Advanced Drug Delivery Reviews, 65(15), 1933–1950. Lu, W., Lu, M. L., Zhang, Q. P., Tian, Y. Q., Zhang, Z. X., & Xu, H. H. (2013). Octahydrogenated retinoic acid-conjugated glycol chitosan nanoparticles as a novel carrier of azadirachtin: Synthesis, characterization, and in vitro evaluation. Journal of Polymer Science Part A: Polymer Chemistry, 51(18), 3932–3940. Mansoori, G. A.,  & Soelaiman, T. F. (2005). Nanotechnology—An introduction for the standards community. Journal of ASTM International, 2(6), 1–22. Mohammadi, S., Cao, Y., & Abyaneh, M. H. (2022, January). Nanosized Products for Agriculture. Nanosized Products for Agriculture Report, 1–37. Mondal, S., & Palit, D. (2022). Chapter 12 - Prospects and implementation of nanotechnology in environmental remediation and clean up. In M. K. Jhariya, R. S. Meena, A. Banerjee, & S. N. Meena (Eds.), Natural Resources Conservation and Advances for Sustainability (pp. 271–287). Elsevier. Nile, S. H., Thiruvengadam, M., Wang, Y., Samynathan, R., Shariati, M. A., Rebezov, M., . . . Kai, G. (2022). Nano-priming as emerging seed priming technology for sustainable agriculture – recent developments and future perspectives. Journal of Nanobiotechnology, 20(1), 1–31. Pal, S., Tak, Y. K.,  & Song, J. M. (2007). Does the antibacterial activity of silver nanoparticles depend on the shape of the nanoparticle? A study of the Gram-negative bacterium Escherichia coli. Applied and Environmental Microbiology, 73(6), 1712–1720. Pitambara, Archana, Shukla, Y. M. (2019). Nanofertilizers: A recent approach in crop production. In: Panpatte, D., Jhala, Y. (eds) Nanotechnology for agriculture: Crop production & protection, pp. 25–58. Springer, Singapore. Pereira, A. E., Grillo, R., Mello, N. F., Rosa, A. H.,  & Fraceto, L. F. (2014). Application of poly (epsiloncaprolactone) nanoparticles containing atrazine herbicide as an alternative technique to control weeds and reduce damage to the environment. Journal of Hazardous Materials, 268, 207–215.

Sustainable Nanotechnology in Agriculture

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Prasad, R., Bhattacharyya, A., & Nguyen, Q. D. (2017). Nanotechnology in sustainable agriculture: Recent developments, challenges, and perspectives. Frontiers in Microbiology, 8, 1014. Rajna, S.,  & Paschapur, A. U. (2019). Nanopesticides: Its scope and utility in pest management.  Indian Farmer, 6(1), 17–21. Rajput, V. D., Singh, A., Minkina, T., Rawat, S., Mandzhieva, S., Sushkova, S., . . . Upadhyay, S. K. (2021). Nano-enabled products: Challenges and opportunities for sustainable agriculture. Plants, 10(12), 2727. Roco, M. C. (1999). Towards a US national nanotechnology initiative. Journal of Nanoparticle Research, 1(4), 435. Sarkar, S., Gil, J. D. B., Keeley, J., & Jansen, K. (2021). The use of pesticides in developing countries and their impact on health and the right to food. European Union. Sharma, P., & Thakur, A. K. (2019). Nanotechnology: An alternative approach to improve seed quality. Journal of Pharmacognosy and Phytochemistry, 8(1), 1492–1496. Song, M. R., Cui, S. M., Gao, F., Liu, Y. R., Fan, C. L., Lei, T. Q., & Liu, D. C. (2012). Dispersible silica nanoparticles as carrier for enhanced bioactivity of chlorfenapyr.  Journal of Pesticide Science,  37(3), 258–260. Srivastava, A., Selvaraj, K., & Prasad, K. S. (2019). Nanoparticles based adsorbent for removal of arsenic from aqueous solution. Asian Journal of Water, Environment and Pollution, 16(1), 97–103. Srivastava, R., Awasthi, K.,  & Tripathi, D. (2018). Nanotechnology towards sustainable agriculture. Nanotechnology, 6(6), 155–158. Subramanian, K. S., Manikandan, A., Thirunavukkarasu, M., & Rahale, C. S. (2015). Nano-fertilizers for balanced crop nutrition. Nanotechnologies in Food and Agriculture, 69–80. Tarafdar, J. C., Sharma, S., & Raliya, R. (2013). Nanotechnology: Interdisciplinary science of applications. African Journal of Biotechnology, 12(3), 219–226. Torney, F., Trewyn, B. G., Lin, V. S. Y., & Wang, K. (2007). Mesoporous silica nanoparticles deliver DNA and chemicals into plants. Nature Nanotechnology, 2(5), 295–300. Usman, M., Farooq, M., Wakeel, A., Nawaz, A., Cheema, S. A., ur Rehman, H., . . . Sanaullah, M. (2020). Nanotechnology in agriculture: Current status, challenges and future opportunities. Science of the Total Environment, 721, 137778. Vijaya, J. J., Jayaprakash, N., Kombaiah, K., Kaviyarasu, K., Kennedy, L. J., Ramalingam, R. J., . . . Maaza, M. (2017). Bioreduction potentials of dried root of Zingiber officinale for a simple green synthesis of silver nanoparticles: Antibacterial studies. Journal of Photochemistry and Photobiology B: Biology, 177, 62–68. Wang, X., Han, H., Liu, X., Gu, X., Chen, K., & Lu, D. (2012). Multi-walled carbon nanotubes can enhance root elongation of wheat (Triticum aestivum) plants. Journal of Nanoparticle Research, 14, 1–10. World Health Organization. (2010). FAO/WHO Expert Meeting on the Application of Nanotechnologies in the Food and Agriculture Sectors: Potential Food Safety Implications: Meeting Report. Yavuz, C. T., Mayo, J. T., Yu, W. W., Prakash, A., Falkner, J. C., Yean, S., . . . Colvin, V. L. (2006). Low-field magnetic separation of monodisperse Fe3O4 nanocrystals. Science, 314(5801), 964–967. Zheng, L., Hong, F., Lu, S., & Liu, C. (2005). Effect of nano-TiO 2 on strength of naturally aged seeds and growth of spinach. Biological Trace Element Research, 104, 83–91.

3 Formulation and Applications Nanopesticides

Anurag Chaudhary, Neha Krishnarth, and Prabhash Nath Tripathi 3.1 INTRODUCTION Nanotechnology is a rapidly developing technology that impacts every issue of the food system – from cultivation to food production to processing, packaging, transportation, shelf life, and bioavailability of nutrients (Bratovcic 2020a). It is an interdisciplinary promising research area that develops new equipment for plant sickness treatments and pathogen detection and improves the capability of plants to soak up nutrients (Ghormade et  al. 2011; Subramanian et  al. 2015). Additionally, nanotechnology is used during the creation of nanofertilizers to increase their effectiveness and bioavailability, hence reducing the amount of these materials that is lost to the environment (Salama et al. 2019). As those nanoparticles come in numerous packages in a huge variety of sectors, which include electronics, cosmetics, coatings, packaging, biotechnology (Khatoon et al. 2017), substances science, medicine, and agriculture, the potential and advantages of nanotechnology are tremendous. The accurate dosing of traditional fertilizers, insecticides, and herbicides to plants is made possible by using nanomaterials in nanoencapsulated conventional fertilizers, pesticides, and herbicides. Nanopesticides (nanoformulations of conventional active ingredients or inorganic nanomaterials) and nanofertilizers (nanoparticle-sized nutrients, nano-layered fertilizers, artificial metal oxide, or carbon-based nanomaterials) can deliver targeted release of agrochemicals aimed at achieving their maximum biological efficacy without overdosing. Employing nanosensors and nano-remediation techniques, nanomaterials can also aid in the identification and elimination of environmental toxins (Lavicoli et al. 2017). The industry may be transformed by the promise of using contemporary technologies and techniques based on nanotechnology to address several problems with conventional insect pest management (Duhan et al. 2017). The biggest requirements maker, International Organization for Standardization (ISO), has described nanomaterial as a fabric with any outward measurement of inner or floor shape in the nanoscale. Nanoscale is defined as a length range between 1 and 100 nm.

Nanomaterial Dimension

Nanomaterial type

3 Dimension