Nanotechnology Advancement in Agro-Food Industry 9819950449, 9789819950447

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Nanotechnology Advancement in Agro-Food Industry

Ragini Singh · Santosh Kumar

Nanotechnology Advancement in Agro-Food Industry

Ragini Singh College of Agronomy Liaocheng University Liaocheng, Shandong, China

Santosh Kumar Shandong Key Laboratory of Optical Communication Science and Technology School of Physics Science and Information Technology Liaocheng University Liaocheng, Shandong, China

ISBN 978-981-99-5044-7 ISBN 978-981-99-5045-4 (eBook) https://doi.org/10.1007/978-981-99-5045-4 © The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd. The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721, Singapore

Preface

Nanotechnology has emerged as a revolutionary discipline with immense potential to revolutionize numerous industries, including the agrifood industry. This book examines the recent advancements in nanotechnology and their profound effects on the agrifood industry. It functions as a comprehensive guide for researchers, engineers, and professionals seeking to understand and employ nanomaterials in smart packaging, processing, and food preservation. This book’s primary objective is to highlight the applications of nanotechnology in addressing significant challenges facing the agrifood industry. One of the primary foci is the use of nanomaterials as “smart” and “active” alternatives to conventional packaging techniques. These nanomaterials offer enhanced food protection and preservation due to their superior mechanical strength. In addition, they contribute to the improvement of safety measures, which inspires consumer confidence. In addition, this book investigates the function of nanomaterials in targeted delivery systems, which enable the efficient transport of bioactive compounds to specific body sites. Nanotechnology facilitates advancements in the fields of nutrition and functional foods by reducing deleterious effects and enhancing therapeutic value. In addition, the controlled discharge of pesticides and fertilizers to plants is discussed, thereby optimizing agricultural practices. The book also explores the fascinating realm of nanosensors, casting light on their use in detecting pathogens in contaminated food. Biosensors based on nanomaterials, such as colorimetric, electrochemical, and fiber-based sensors, provide exceptional sensitivity and precision, thereby enhancing food safety measures. In addition to practical applications, this book addresses comprehensively the risk assessment regulations and safety concerns associated with nanomaterial use in the food industry. For the responsible integration of nanotechnology in food-related applications, it is essential to comprehend the potential risks and implement the necessary safety measures. The book concludes with insightful discussions of future perspectives and emergent trends in the field of nanomaterials in the agrifood industry. By remaining at the vanguard of research and innovation, we can ensure the ongoing development of safe and effective nanomaterials for the sustainable production and consumption of food. The book is a valuable resource for academia, industry professionals, and regulatory bodies alike. It provides both theoretical and experimental insights into the use of v

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nanomaterials in agrifood applications. By encouraging the responsible application of nanotechnology, we can unleash its vast potential for addressing critical challenges and advancing the agrifood sector. We hope that this volume inspires interest, further research, and new innovations at the fascinating intersection of nanotechnology and the agricultural industry. In Chap. 1: “Overview of Nanomaterial Application in the Food and Agriculture Sector”, in the sphere of food and agriculture, nanotechnology has opened up new horizons and presented innovative solutions to various problems. This chapter functions as the book’s introduction and provides an overview of nanomaterials’ applications in the food industry. It investigates the properties of nanomaterials that make them appropriate for use in the food industry. This chapter explores the various applications of nanomaterials in food processing, including nanofluid thermal processing and nanofiltration. It also emphasizes their functions in food packaging, food preservation, and food quality enhancement. In addition, the chapter addresses the concept of nanoenabled foods as well as the crucial topic of the toxicity and safety concerns associated with nanomaterials in food packaging. Chapter 2: “Nanomaterials: Plethora of Opportunities as Smart Packaging, Preserving, and Processing Agent in Food Industry” focuses on the numerous opportunities nanomaterials present in the food industry as intelligent packaging, preserving, and processing agents. The chapter begins with an overview of nanomaterials and their applications in the culinary industry. It examines nanoencapsulation and nanoemulsification and highlights their significance. The utility of nanofiltration, nanoadsorbents, and nanoporous materials in the food industry is discussed in depth. The chapter also examines the use of nanomaterials as active and intelligent packaging materials, concentrating on their application to fruits and vegetables, meat, fish, seafood products, poultry, beverages, dairy products, and baked goods. The chapter concludes with a summary that provides a concise overview of the discussed topics. Chapter 3: “Major Applications of Nanotechnology in Food Industry” examines the main nanotechnology applications in the food industry. It begins with an introduction to the subject and emphasizes the function of nanomaterials in providing a protective effect under conditions of stress. This chapter examines the use of nanomaterials in culinary products such as color additives, anticaking agents, and flavors. Also discussed are the applications of nanotechnology in viticulture, including stress treatment, disease control, nanofertilizers, antimicrobial activity, and insect control. In addition, the chapter focuses on the synthesis and quality analysis of nanomaterials in oenology. The chapter concludes with a summary that provides a concise overview of the discussed topics. In Chap. 4: “Intelligent Nano-based Sensor for Quality Detection of Food Products”, the development of intelligent nanosensors for detecting the purity of food products is highlighted. The chapter begins with an introduction to the subject before discussing the detection of bacterial and fungal contamination in food. It discusses the detection of particular bacteria, including E. coli, Salmonella, Listeria, Staphylococcus, Clostridium spp., Vibrio parahaemolyticus, Shigella, and Bacillus cereus. Moreover, it explores the detection of fungal contamination. The chapter also emphasizes the use of intelligent sensors to detect the adulteration and authenticity of food. In addition, the article discusses nanomaterials in anticounterfeiting devices and

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nanobiosensors for detecting allergens and contaminants in food. A summary of the discussed subjects concludes the chapter. Chapter 5: “Nanofertilizers and Nanopesticides: Key to Healthier and Safer Food Products” examines the use of nanofertilizers and nanopesticides in the promotion of healthier and safer food products. It begins with an introduction to the topic and then examines various nanofertilizers, such as zinc, iron, nitrogen, carbon-based nanomaterials, silicon, nanoclays, hydroxyapatite nanoparticles, and polymeric nanoparticles. This chapter discusses the mechanisms of delivery and action of nanofertilizers. The article also addresses nanopesticides. The chapter concludes with a summary that provides a concise overview of the discussed topics. Chapter 6: “Nanomaterials-Based Nutraceuticals, Nutrigenomics, and Functional Food: Design, Delivery, and Bioavailability” examines the use of nanomaterials for designing, administering, and enhancing the bioavailability of nutraceuticals, thereby delving into the burgeoning field of nanonutraceuticals. It discusses the applicability of nanomaterials in a variety of fields, including cancer, immunity enhancement, inflammation, and oxidative stress reduction. In addition, the chapter examines the concept of nutrigenomics and the application of nanomaterials such as polymeric micelles, carbon nanotubes, dendrimers, liposomes, transferosomes, and nanoemulsions in nutrigenomic research. In addition, it discusses the role of nanomaterials in functional foods, concentrating on polysaccharides, lipids, and protein-based materials. The chapter concludes with a summary that provides a concise overview of the discussed topics. Chapter 7: “Nanocarriers as a Novel Approach for Phytochemical Delivery in Food” focuses on nanocarriers as an innovative method for conveying phytochemicals in food. In the chapter’s introduction, the limitations of phytochemicals and the need for efficient delivery systems are highlighted. This article investigates various nanomaterials used as nanocarriers, including liposomes, niosomes, bilosomes, archaeosomes, solid lipid nanoparticles, carbon nanotubes, dendrimers, quantum dots, and polymeric nanoparticles. The antimicrobial activity of nanophytochemicals is also discussed in this chapter. A summary at the conclusion of the chapter provides a concise summary of the topics covered. Chapter 8: “Regulatory and Safety Concerns Regarding the Use of Active Nanomaterials in Food Industry” addresses the regulatory and safety concerns related to the use of active nanomaterials in the food industry. The introduction is followed by a discussion of the toxicity and risk assessment of nanomaterials used in food applications. This chapter examines the safety requirements, case studies on the toxicity and risk assessment of nanomaterials, and future research directions in this field. In addition, it investigates the evaluation of nanomaterials used in agriculture and the associated environmental concerns. In addition, the chapter discusses public opinion and current regulations regarding the safety of nanomaterials in the food and agriculture industries. The chapter concludes with a summary that provides a concise overview of the discussed topics. Liaocheng, China

Ragini Singh Santosh Kumar

Acknowledgements

The authors, Santosh Kumar and Ragini Singh, would like to express their heartfelt gratitude to all those who have contributed to the writing and publication of the book Nanotechnology Advancement in Agro-Food Industry. Their support and contributions have been instrumental in making this endeavor a success. First and foremost, the authors would like to extend their deep appreciation to Springer Nature Press for their valuable support and for providing the opportunity to publish this book. They would like to specifically thank the dedicated editor who meticulously edited the manuscript, ensuring its quality and readiness for publication. The authors are also indebted to their meticulous students and colleagues for their invaluable input and insights. Whether as direct contributors to the book or through engaging discussions and suggestions, their contributions have enhanced the overall quality of the content. The authors are grateful for their involvement and collaboration throughout the writing process. Ragini Singh acknowledges the support from Natural Science Foundation of Shandong Province (ZR2020QC061), and Santosh Kumar gratefully acknowledges the support from the Liaocheng University (318052341) and Double-Hundred Talent Plan of Shandong Province, China. Santosh Kumar and Ragini Singh would like to express their heartfelt thanks to their son, Ayaansh Singh, for his unwavering support, and cooperation. His belief in their work and constant motivation has been a source of inspiration throughout the journey. Additionally, the authors extend their deepest appreciation to their loving parents for their continuous encouragement and unwavering support. Furthermore, the authors would like to extend their deep gratitude to the deans and leaders of Liaocheng University for their unwavering motivation, support, and encouragement throughout the process of writing this book. Their guidance and belief in the importance of this work have been instrumental in its completion. Lastly, the authors sincerely hope that Nanotechnology Advancement in AgroFood Industry serves as a solid foundation for future advancements in the field. They aspire for it to be a valuable reference for professionals in the food industry, engineers, researchers, and students working in the fields of agro-food industry, agriculture, and biosensors. The authors believe that the insights and advancements ix

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shared within these pages will contribute to the growth and development of these industries, as well as inspire further research and innovation. Once again, the authors express their deepest appreciation to all who have contributed to the realization of this book, including Springer Nature Press, the editor, colleagues, their son Ayaansh Singh, their loving parents, meticulous students, and the deans and leaders of Liaocheng University. Without their support, this work would not have been possible. Ragini Singh Santosh Kumar

Contents

1 Overview of Nanomaterial Application in Food and Agriculture Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Characteristic Feature of Nanomaterials for Utilization in Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3 Nanomaterials in Food Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3.1 Nanofluid Thermal Processing . . . . . . . . . . . . . . . . . . . . . . . . . 1.3.2 Nanofiltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4 Nanomaterials in Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5 Nanomaterials in Food Preservation . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6 Nanomaterials in Enhancing Food Quality . . . . . . . . . . . . . . . . . . . . . 1.7 Nanoenabled Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8 Toxicity and Safety Concern of Nanomaterials in Food Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.9 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 Nanomaterials: Plethora of Opportunities as Smart Packaging, Preserving, and Processing Agent in Food Industry . . . . . . . . . . . . . . . . 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Nanoencapsulation and Nanoemulsification . . . . . . . . . . . . . . . . . . . . 2.3 Nanofiltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 Nanoadsorbent and Nanoporous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Nanomaterials as Active and Intelligent Packaging Material . . . . . . 2.5.1 Fruits and Vegetables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.2 Meat, Fish, and Seafood Products . . . . . . . . . . . . . . . . . . . . . . 2.5.3 Poultry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.4 Beverages . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.5 Dairy Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.6 Bakery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 1 4 6 7 9 11 18 22 24 31 34 34 43 44 46 48 50 52 54 59 63 65 67 70

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2.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

73 73

3 Major Applications of Nanotechnology in Food Industry . . . . . . . . . . . 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Nanomaterial Mediated Protective Effect Under Stress Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3 Color Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Anticaking Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5 Flavors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6 Nanotechnology in Viticulture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.1 Stress Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.2 Disease Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.3 Nanofertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.6.4 Antimicrobial Activity of Nanoparticles . . . . . . . . . . . . . . . . . 3.6.5 Entomological Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7 Nanomaterials in Enology Study: Synthesis and Quality Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7.1 Odors Removal from Wine . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7.2 Aroma Removal from Wine . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7.3 Protein Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7.4 Antimicrobial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.8 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

81 81 82 86 89 89 90 90 94 95 96 100 102 104 106 107 109 111 112

4 Intelligent Nano-based Sensor for Quality Detection of Food Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2 Bacterial and Fungal Contamination Detection . . . . . . . . . . . . . . . . . . 4.2.1 Detection of Bacterial Contamination . . . . . . . . . . . . . . . . . . . 4.2.2 Detection of Fungal Contamination . . . . . . . . . . . . . . . . . . . . . 4.3 Smart Sensor to Detect Food Adulteration and Authenticity . . . . . . 4.4 Nanomaterials in Anticounterfeiting Device . . . . . . . . . . . . . . . . . . . . 4.5 Nanobiosensor for Detection of Food Allergens and Toxins . . . . . . . 4.6 Detection of Spoilage in Food Crop Grain . . . . . . . . . . . . . . . . . . . . . . 4.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

119 119 124 125 138 141 143 146 148 152 153

5 Nanofertilizers and Nanopesticides: Key to Healthier and Safe Food Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2 Nanofertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1 Zinc as Nanofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.2 Iron as Nanofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.3 Nitrogen as Nanofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.4 Carbon-Based Nanomaterials as Nanofertilizer . . . . . . . . . . .

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5.2.5 Silicon Nanofertilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.6 Nanoclays Nanofertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.7 Hydroxyapatite Nanoparticles as Nanofertilizers . . . . . . . . . . 5.2.8 Polymeric Nanoparticles as Nanofertilizers . . . . . . . . . . . . . . 5.3 Delivery of Nanofertilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4 Mechanism of Action . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5 Nanopesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

166 168 169 170 170 171 177 187 187

6 Nanomaterials-Based Nutraceuticals, Nutrigenomics, and Functional Food: Design, Delivery, and Bioavailability . . . . . . . . . 6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2 Nanonutraceuticals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2.1 Cancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2.2 Enhancing Immunity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2.3 Inflammation and Oxidative Stress . . . . . . . . . . . . . . . . . . . . . 6.3 Nutrigenomics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.1 Polymeric Micelles (PICM) . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.2 Carbon Nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.3 Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.4 Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.5 Transferosome . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.6 Nanoemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4 Functional Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4.1 Polysaccharides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4.2 Lipid-Based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.4.3 Protein-Based . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

195 195 196 197 202 205 210 215 216 217 217 217 218 218 219 224 225 226 227

7 Nanocarriers as a Novel Approach for Phytochemical Delivery in Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2 Limitations of Phytochemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2.1 Condition Optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2.2 Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3 Nanomaterials as Nanocarriers for Phytochemicals . . . . . . . . . . . . . . 7.3.1 Liposomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.2 Niosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.3 Bilosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.4 Archaeosomes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.5 Solid Lipid Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.6 Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.7 Dendrimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3.8 Quantum Dots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

233 233 235 235 235 236 236 238 239 240 240 242 245 249

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7.3.9 Polymeric Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4 Antimicrobial Activity of Nanophytochemicals . . . . . . . . . . . . . . . . . 7.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Regulatory and Safety Concerns Regarding the Use of Active Nanomaterials in Food Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.2 Toxicity and Risk Assessment of Nanomaterials Used in Food Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.2.1 Toxicity of Nanomaterials in Food . . . . . . . . . . . . . . . . . . . . . . 8.2.2 Risk Assessment of Nanomaterials in Food . . . . . . . . . . . . . . 8.2.3 Safety Requirements for Nanomaterials in Food . . . . . . . . . . 8.2.4 Case Studies of Toxicity and Risk Assessment of Nanomaterials in Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.2.5 Future Directions for Toxicity and Risk Assessment of Nanomaterials in Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.3 Assessment of Nanomaterials Used in Agriculture Sector . . . . . . . . 8.3.1 Applications of Nanomaterials in Agriculture . . . . . . . . . . . . 8.3.2 Environmental Concerns Associated with Nanomaterials in Agriculture . . . . . . . . . . . . . . . . . . . . . . 8.3.3 Risk Assessment and Safety Regulations . . . . . . . . . . . . . . . . 8.4 Public Opinion Regarding Use of Nanoparticles in Food and Agriculture Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5 Regulation Regarding Safety Concerns of Nanomaterials in Food and Agriculture Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5.1 Overview of Current Regulatory Landscape . . . . . . . . . . . . . . 8.5.2 Gaps in Current Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5.3 International Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5.4 Safety Assessment Requirements . . . . . . . . . . . . . . . . . . . . . . . 8.5.5 Labeling Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5.6 Future Regulatory Directions . . . . . . . . . . . . . . . . . . . . . . . . . . 8.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

253 258 261 263 269 270 275 276 276 277 278 285 286 287 288 289 290 294 294 296 296 297 298 299 301 301

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307

About the Authors

Ragini Singh is an accomplished biotechnologist and a dedicated educator. She obtained her Ph.D. degree in biotechnology from Ahmedabad University, India, in 2018. Currently serving as an assistant professor in the College of Agronomy at Liaocheng University in China, Dr. Singh has made significant contributions to the field. Her research interests encompass diverse areas, including nanotechnology, molecular biology, environmental biology, and immunology. Driven by a passion for innovation, she has been actively involved in pioneering studies that explore the applications of nanotechnology in various fields. Driven by a passion for scientific exploration, Dr. Singh has published her groundbreaking research in highly regarded and influential journals. Her work has appeared in prestigious publications such as Biosensors and Bioelectronics, Science of The Total Environment, Colloids and Surfaces B: Biointerfaces, Langmuir, and Nano Convergence. These publications highlight her significant contributions to the scientific community and showcase her ability to tackle complex challenges in the field of biotechnology. Dr. Singh’s expertise and research contributions have garnered recognition on a global scale. According to 2022 data ranking of Stanford University, she is among the top 2% of the world’s scientists, a testament to her exceptional work and impact in her field. In addition to her research endeavors, Dr. Singh has received prestigious funding for her projects. She successfully secured funding from the Natural Science Foundation of Shandong Province, further supporting her cutting-edge research initiatives. Dr. Singh’s dedication to academic xv

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About the Authors

excellence and her commitment to advancing biotechnology have earned her widespread respect. She is a valued member of the scientific community and serves as an inspiration to aspiring biotechnologists. Through her research, teaching, and project achievements, Dr. Ragini Singh continues to drive scientific innovation and contribute to the growth of biotechnology. Her work leaves a lasting impact on the field and inspires future generations of scientists. Santosh Kumar holds a Ph.D. degree from IIT (ISM) Dhanbad, India, and currently serves as a Professor in the School of Physics Science and Information Technology at Liaocheng University, China. He has been recognized as one of the world’s top 2% scientists by Stanford University in both 2020 and 2022. With extensive research experience, he has supervised twelve M.Tech. dissertations and six Ph.D. candidates. His contributions to the field include the publication of over 300 research articles in prestigious SCI journals and conferences, with more than 5000 citations and an hindex of 40. His work has been featured in renowned journals such as Biosensors and Bioelectronics, Biosensors, Journal of Lightwave Technology, Optics Express, and various IEEE Transactions. Santosh Kumar has presented his research at conferences in India, China, Belgium, and the USA, demonstrating his global reach. He recently filed a patent application for his groundbreaking optical fiber sensing technology. As a highly regarded expert, he has reviewed over 1700 manuscripts for esteemed SCI journals published by IEEE, Elsevier, Springer, OPTICA, SPIE, and Nature. Santosh Kumar’s professional achievements include being a fellow of SPIE, a life fellow member of the Optical Society of India (OSI), and a senior member of IEEE, OPTICA, and SPIE. He also serves as an OPTICA Traveling Lecturer. Through fruitful collaborations with renowned universities in India, China, Portugal, Brazil, and Italy, he conducts cutting-edge scientific research. With expertise in electronics, communications engineering, and physics, his research focuses on fiber optic sensors, photonics and plasmonic devices, nano and biophotonics, waveguides, and interferometers. Recognizing

About the Authors

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his contributions, Santosh Kumar has been appointed as the chair of the Optica Optical Biosensor Technical Group and as an associate editor for IEEE Sensors Journal, IEEE Internet of Things, and Biomedical Optics Express.

Abbreviations

4-EG 4-EP 5-FU A/C PET Ab ABA ABTS ACP AD AE AFB1 Agcl Nps Ag-MMT Agnps AI AITC ALI ALP ALT Amp-PEG-Mbs As ASA Asa Asc AST ATP ATRA Au@Ag Nrs Au@Ptncs Au-NC-Nbs

4-Ethylguaiacol 4-Ethylphenol 5-Fluorouracil Aminolysed/Charged Polyethylene Terephthalate Antibody Abscisic Acid 2,2' -Azinobis-3-Ethylbenzothiazoline-6-Sulphonic Acid Amorphous Calcium Phosphate Attack Degree Adsorption Efficiency Aflatoxin B1 Silver Chloride Nanoparticles Silver-Montmorillonite Silver Nanoparticles Artificial Intelligence Allyl Isothiocyanate Acute Lung Injury Alkaline Phosphatase Alanine Aminotransferase Mediated Ampicillin Functionalized Magnetic Beads Arsenic Aldehyde-Modified Sodium Alginate Ascorbate Aqueous Extract Aspartate Aminotransferase Adenosine Triphosphate Trans Retinoic Acid Au-Ag Core–Shell Nanorods Gold@Platinum Nanocatalysts Nitrogen-Doped Carbon Nanoballoons Loaded With Gold Nanoparticles xix

xx

Aunps Ax BBB Bcl2 BEO Ber BLG BNC Bonts BPB BSA Bt Ca CAP CAT Cd CDC2 Cds Cdte CEO Ceo2 CHI Chl A Cit-Au Nps Clps CLSM CMC Cnps CNS Cnts Co COX-2 Cqds Cs-PVA+Cu CS-SA Ncs Cu2+-Rgo Nps Cuo Nps CUR CZ DF DON DPPH DPV DW

Abbreviations

Gold Nanoparticles Astaxanthin Blood Brain Barrier B-Cell Lymphoma 2 Bergamot Essential Oils Bactericide Berberine B-Lactoglobulin Bacterial Nanocellulose Botulinum Neurotoxins Bacterial Panicle Blight Bovine Serum Albumin Bacillus Thuringiensis Calcium Captopril Catalase Cadmium Cell-Division-Cycle Kinase 2 Cadmium Sulfide Cadmium Tellurium Cinnamon Essential Oils Cerium Oxide Chitinases Chlorophyll A Citrate-Stabilized Gold Nanoparticles Colloidal Lipid Particles Confocal Laser Scanning Microscopy Carboxymethyl Cellulose Carbon Nanoparticles Central Nervous System Carbon Nanotubes Cobalt Cyclooxygenase-2 Carbon Quantum Dots Nanoparticles Chitosan-Polyvinyl Alcohol And Copper Nanoparticles Chitosan Based Salicylic Acid Nanocomposite Cu(II)-Modified Reduced Graphene Oxide Nanoparticles Copper Oxide Nanoparticles Curcumin Carrageenan/Zno Nanoparticles Diclofenac Sodium Deoxynivalenol 2,2-Diphenyl-1-Picrylhydrazyl Differential Pulse Voltammetry Dry Weight

Abbreviations

DXM E. Coli EAPM EC ECF EE EFSA EGCG ELISA Enms ENO EO EPA EPR EPS ESR EU FAO FBA FCM Fcnls FCP FDA FET FRET FTIR FW GA-Nps GCG GIT GO GOD G-Probe Gpx Gqds GRAS GSH H2 O2 HA HB HDP-P HHP HPLC HRP

xxi

Dexamethasone Escherichia Coli Electrically Active Polyaniline-Coated Magnetic European Commission Edible Coating And Films Encapsulation Efficiency European Food Safety Authority Epigallocatechin Gallate Enzyme-Linked Immunosorbent Assay Engineered Nanomaterials Engineered Nano-Objects Essential Oil Environmental Protection Agency Enhanced Permeability And Retention Exopolysaccharides Erythrocyte Sedimentation Rate European Union Food And Agriculture Organization Of The United Nations Fructose 1,6-Bisphosphate Aldolase Food-Contact Materials Fibrous Composite Nanolayers Fresh Cut Pepper Food And Drug Administration Field-Effect Transistor Förster Resonance Energy Transfer Fourier Transform Infrared Spectroscopy Fresh Weight Glycyrrhizic Acid Nanoparticles Gelidium Corneum-Gelatin Gastrointestinal Track Graphene Oxide Glucose Oxidase General Probe Glutathione Peroxidase Graphene Quantum Dots Generally Recognized As Safe Glutathione Hydrogen Peroxide Hyaluronic Acid Hypocrellin B High-Density Polyethylene High Hydrostatic Pressure High-Performance Liquid Chromatography Horseradish Peroxidase

xxii

IARC IBMP ICD ICMSF IL IOP JECFA LAMP LC LDPE LF LOC LPS LSPR MBC Mbs MDA MDR Mej Mg MIC Mips ML MMP-9 MMT-N6 Mno2 MNPs Msnps MVTR Mwcnts MWCO NF NIP1-1 NO Npasc NUE OECD OIV OTR OVA-CMC Ox-LDL

Abbreviations

International Agency For Research On Cancer 3-Isobutyl-2-Methoxypyrazine Irritant Contact Dermatitis International Commission On Microbiological Specifications For Foods Interleukin Intraocular Pressure Joint FAO/WHO Expert Committee On Food Additives Loop-Mediated Isothermal Amplification Loading Capacity Low-Density Polyethylene Lactoferrin Lab-On-A-Chip Lipopolysaccharides Localized Surface Plasmon Resonance Minimal Bactericidal Concentration Magnetic Beads Malondialdehyde Multiple Drug Resistant Methyl Jasmonate Magnesium Minimal Inhibitory Concentration Molecularly Imprinted Polymers Machine Learning Matrix Metalloproteinase 9 Montmorillonite Composite Nylon 6 Manganese Oxide Metal Nanoparticles Mesoporous Silica Nanoparticles Moisture Vapor Transfer Rate Multiwalled Carbon Nanotubes Molecular Weight Cut-Off Nanofiltration Nodulin 26-Like Intrinsic Protein1-1 Nitric Oxide Polymeric Nanoparticles Containing Asc Nitrogen Use Efficiency Organization For Economic Cooperation And Development Organization Of Vine And Wine Oxygen Transfer Rate Ovalbumin–Carboxymethylcellulose Low-Density Lipoprotein

Abbreviations

PAMAM Pb Pbps PBS PCL PCR PDI PDI PEG PEI PEO-PMAA PET PET/CT PICM PIMP PL PLA PLGA PNCs POCT POD POR Pox PPI PPO PS II PS PSBAC PSM Put PVA Qds R&D RBC RBCL RF RGR ROS RS SA SVA SAHS SCFAs SEB

xxiii

Polyamidoamine Lead Phycobiliproteins Phosphate Buffer Saline Poly(-Caprolactone) Polymerase Chain Reaction Polydispersity Index Polydispersity Index Poly(Ethylene Glycol) Polyethylenimine Poly(Ethylene Oxide-B-Methacrylic Acid) Polyethylene Terephthalate Positron Emission Tomography/Computed Tomography Polymeric Micelles Presumed Imprinted Magnetic Polymer Pulsed Light Polylactic Acid Poly(D,L-Lactic-Co-Glycolic Acid) Polymer Nanocomposites Point-Of-Care Testing Pyrogallol Peroxidase Protochlorophyllide Oxidoreductase 2-Methyl-2-Oxazoline Polypropylenimine Polyphenol Oxidase Photosystem II Photosensitizers Activated Carbon Made From Pecan Shells Propensity Score Matching Putrescine Polyvinyl Alcohol Quantum Dots Research And Development Red Blood Cell Ribulose-1,5-Bisphosphate Carboxylase Large Subunit Rheumatoid Factor Relative Growth Rate Reactive Oxygen Species Resistant Starch Salicylic Acid Streptavidin Superabsorbent Hydrogels Short-Chain Fatty Acids Staphylococcal Enterotoxin B

xxiv

SELEX SEM SERS SGF SIF Sinps Sio2 Nps Siqds SKEO Slns SO2. SOD SPE SPIONS SPR S-Probe Swcnts TA TFC THC Tio2 Nps TIP2-1 Tlps TM TMB TNF-Alpha TPC TQ UA UCNPS USDA USFDA UV VVC WBC WHC WHO WPMN WVTR XOs XRD YADH

Abbreviations

Systematic Evolution Of Ligands By Exponential Enrichment Scanning Electron Microscopy Surface-Enhanced Raman Scattering Simulated Gastric Fluid Simulated Intestinal Fluid Silicon Nanoparticles Silica Nanoparticles Silicon Quantum Dots Satureja Khuzestanica Essential Oils Solid Lipid Nanoparticles Sulfur Dioxide Superoxide Dismutase Screen-Printed Electrode Superparamagnetic Iron Oxide Nanoparticles Surface Plasmon Resonance Specific Probe Single-Walled Carbon Nanotubes Titratable Acidity Total Flavonoid Content Tetrahydrocurcumin Titanium Dioxide Nanoparticles Tonoplast Intrinsic Protein2-1 Thaumatin-Like Proteins 1 Trabecular Meshwork 3,3' ,5,5' -Tetramethylbenzidine Tumor Necrosis Factor-Alpha Capacity Total Phenolic Content Thymoquinone Ursolic Acid Upconversion Nanoparticles United States Department Of Agriculture US Food And Drug Administration Ultraviolet Vulvovaginal Candidiasis White Blood Cell Water-Holding Capacity World Health Organization Working Party On Manufactured Nanomaterials Water Vapor Transmission Rate Xylooligosaccharides X-Ray Diffraction Yeast Alcohol Dehydrogenase

Abbreviations

Zn2+ Znal2 si10 o24 ZnO NPs ZnO ZnS

xxv

Zinc Ions Zinc Aluminosilicate Zinc Oxide Nanoparticles Zinc Oxide Zinc Sulfide

Chapter 1

Overview of Nanomaterial Application in Food and Agriculture Sector

Abstract The purpose of this chapter is to provide a detailed review of the applications of nanomaterials in the food and agriculture sectors. The report starts off with an introduction to the subject matter, during which it discusses the growing application of nanomaterials in a variety of professional fields. The subsequent section of the chapter concentrates on the nanomaterials that are frequently used in the food and agriculture industries. These nanomaterials include nanoparticles of silver, gold, iron oxide, titanium dioxide, and zinc oxide. One of the most important features that have been talked about is the impact that the various forms, sizes, and structures of nanomaterials have on the roles that they play in food and agriculture applications. Because of their numerous qualities, nanomaterials have the potential to improve the quality of food, increase agricultural output, and provide new solutions to problems faced by various industries. The use of nanoparticles in the food and agricultural industries is investigated from a variety of perspectives, including the increased qualities of these materials, the possible applications they could have, and the obstacles connected with integrating them. In addition, the chapter discusses the dangers posed by active nanoparticles in terms of toxicity and safety, placing an emphasis on the significance of conducting exhaustive risk assessments and adhering to regulatory guidelines. In conclusion, the purpose of this chapter is to lay a foundation of knowledge regarding nanoparticles by concentrating on the many types of nanoparticles and the features of those nanoparticles that are often employed in the food and agriculture industry. It puts light on the crucial role that nanoparticles play in food applications and brings attention to the necessity of resolving safety concerns. The next chapters in the book go deeper into various applications of nanomaterials, providing a more in-depth examination of the benefits and drawbacks associated with these applications.

1.1 Introduction People are confronted with a number of critical issues in relation to food in the twentyfirst century. These challenges include rapid population increase, maintenance of population health, guaranteeing of food supply and safety, and the promotion of sustainable resource utilization. Exploring new avenues of scientific research and © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_1

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

technical development is required in order to find cost-effective solutions to these issues that do not compromise on quality of care. The fields of nanotechnology and nanoscience have a tremendous amount of potential to make significant contributions to the food business by improving many different facets of the food chain. This includes making changes to food production, processing, analysis, and packaging in order to suit the dietary and analytical needs of future populations as well as their health requirements. It is conceivable to revolutionize the entire food business by utilizing the possibilities of nanotechnology, which will allow for the achievement of desired results in terms of nutrition, health benefits, and sustainability [1]. There is a vast variety of nanoscale sugars, amino acids, peptides, proteins, carbohydrates, and lipids that are frequently discovered in a variety of food products that consumers ingest. Numerous nations, including the USA, Japan, South Korea, the European Union, India, Iran, China, and Thailand, have all made considerable expenditures in the research and development (R&D) of food nanotechnologies. In 2003, the United States Department of Agriculture (USDA) issued a plan addressing the application of nanotechnology in the agricultural and food industries. This publication was the impetus for the increased focus that has been placed on food nanotechnology in recent years. The improvements that have been made in nanoscience and nanotechnology have significant positive impact on a variety of materials, components, pieces of processing equipment, finished products, and other consumer items [1]. The miniaturization of electronic equipment is a direct result of the enormous breakthroughs in computing, communication, and data processing that have been made possible as a direct result of nanotechnology. The advancements that have been made are now having a discernible effect on the safety and security of food. In particular, improvements in tools and matrices used for product labeling, packaging, authentication, and traceability detection have been made possible by nanotechnology. The ability of nanoparticles to interact with the many parts of the human body, such as cells, tissues, and organs, is one of the most significant benefits offered by this type of material. Because of their smaller size, nanoparticles, particularly those with a diameter of less than 70 nm, have the inherent potential to enter cell nuclei and be taken up by them. In addition, nanoparticles with a size less than 300 nm can directly enter cells, which further expands the scope of potential applications for these particles in a variety of fields [2]. It is important to recognize the benefits of nanoparticles and nanocomposites, such as increased body absorption, in addition to their possible downsides, which may include the possibility of toxicity to humans. According to Brunner, Wick, and colleagues, the potential toxicity of nanomaterials can be affected by a variety of parameters, including size, chemistry, shape, surface structure, charge, catalytic capabilities, and the degree to which particle aggregation or disaggregation occurs [3]. Before considering the use of nanomaterials in food processing or preparation, it is essential to do exhaustive research on the potential detrimental effects and fate of nanomaterials within the context of human physiological circumstances and post-processing. Food-grade nanomaterials are employed in the production of smart packaging, as food additives, for the preservation and improvement of the bioavailability of

1.1 Introduction

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nutraceuticals, and for the development of biosensors for the detection of pesticides, toxins, and pathogens [4, 5]. Foods contain engineered nanomaterials (ENMs), which are purposefully introduced to enhance food quality and safety, as well as naturally occurring nanomaterials, such as the casein micelles in milk. Delivery methods based on nanoparticles are an example of ENMs. Even if they are not ingested directly, some nanoparticles may come into contact with food because they are utilized in packaging or nanosensors. The European Food Safety Authority (EFSA) identifies four categories of nanomaterials commonly used in the agrifood sector: nanostructured materials, nanoparticles and their aggregation in the nanoscale, nanoencapsulates, and nanoproducts. In order to carry fertilizers, insecticides, herbicides, and plant growth stimulants to plants, these nanoparticles are used in agriculture as nanocarriers. Nanomaterials have received approval from the US Food and Drug Administration (USFDA) and the European Commission (EC) for use in the food industry, and they are recognized as generally recognized as safe (GRAS) materials. Since there are 55 distinct types of nanomaterials utilized in the agro-sector, according to EFSA, nanoencapsulates, nanometals (such as silver, gold, iron, and aluminum), nanometal oxides (such as silicon dioxide, zinc oxide, and titanium dioxide), nanocomposites, and nanosalts have received the most attention [6]. The food business is unquestionably being revolutionized by nanotechnology. A large number of reported uses for the nanostructures in food include improving food quality, incorporating bioactives into foods, regulating the release of bioactive compounds using nanocarrier encapsulation, modifying the structures and textures of foods, and utilizing intelligent packaging techniques to detect and neutralize microbiological, biochemical, and chemical changes [7]. Numerous applications for various nanomaterials exist in the production of food products and the enhancement of nutritional values. For instance, protein solubility aids in the construction of protein nanoparticles with desired functional qualities in food components, which is why protein nanoparticles are employed in the production of food products [8]. Nanosensors and nanoencapsulated structured bioactive food ingredients are two major applications of nanotechnology in the food sector, which include quality and safety detection as well as food packaging and formulations. Nanopolymers replace conventional food packaging materials [9]. The advancements in nanotechnology have made it possible for the food business to create novel, functional foods. Another possible use for nanotechnology is new engineering methods based on nanomaterials for the tailored distribution of nutrients and bioactive substances in functional foods [10]. There are new prospects for nanotechnology in the food sector due to the development of nanosensors, nanocarriers, nanotubes, nanocapsules, and nanopackages [11]. Nanotechnology also facilitates both food preservation and processing approaches. This program provides a shield to mask various tastes and flavors. Additionally, controlled release and improved dispersibility are provided by nanotechnology for water-insoluble food supplements as well as food ingredients [12]. The food processing industry can greatly benefit from nanotechnology, offering advantages such as the ability to create desired textures in food components, encapsulate food additives, develop innovative flavors and sensory experiences, and enhance scent

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

Fig. 1.1 Role of nanotechnology in various sectors of the food industry, adapted from [16]

release and bioavailability in nutritional supplements [13]. Recently, nanotechnology has found industrial application in the development of interactive and intelligent packaging for food. An emerging term in the field of food packaging is “active packaging,” which refers to packaging that modifies the condition of the packaged food to improve sensory quality and safety while also extending shelf life by preserving product quality [14]. Nanotechnology-based solutions and advanced food packaging reduce food losses caused by various microbial diseases. Numerous nanoparticles have demonstrated significant antimicrobial effects, including silver nanoparticles, carbon nanotubes, titanium dioxide, magnesium oxide, zinc oxide, zerovalent iron, and fullerene derivatives [15]. This chapter offers a fundamental introduction to the utilization of nanotechnology in different sectors of the food industry. Subsequent chapters in this book delve deeper into specific applications and provide more detailed explanations. Figure 1.1 illustrates the diverse range of applications of nanotechnology in the food sector.

1.2 Characteristic Feature of Nanomaterials for Utilization in Food Industry The physiochemical and structural characteristics of the nanoparticles contained in food and beverage products vary greatly, which affects their gastrointestinal destiny and propensity to induce toxicity [17]. The many characteristics of nanoparticles that determine their fate in the food industry are shown in Fig. 1.2. The nanoparticles

1.2 Characteristic Feature of Nanomaterials for Utilization in Food Industry

5

present in food may be made up of organic (such as carbohydrates, proteins, and lipids) or inorganic (such as silicon dioxide, silver, titanium dioxide, zinc oxide, and iron oxide) elements depending on their composition. The lower gastrointestinal tract (GIT) will get any nanoparticles that were not absorbed or digested in the upper GIT, where they may change the microbiome [18]. The chemical reactivity of inorganic nanoparticles, which depends on their composition, is usually associated with toxicity. As an illustration, certain inorganic nanoparticles, such as silver nanoparticles, dissolve and release ions that promote unfavorable chemical or biological interactions, whereas other inorganic nanoparticles, such as titanium dioxide nanoparticles, are comparably innocuous [19]. Lipids, proteins, and carbohydrates are frequently used to create organic nanoparticles, which can either be digestible or indigestible depending on the specific makeup of the constituents [20]. For instance, whereas certain lipids, like triacylglycerols, may be digested, others, such as flavoring, essential, and mineral oils, cannot. Similar to proteins, some carbohydrates (like starch) are digestible while others (like cellulose and chitosan) are not. Furthermore, the type of macronutrients employed and how they are organized inside the nanoparticles may affect the pace of digestion. Food nanoparticles exhibit a range of sizes, from a few nanometers for surfactant micelles to several hundred nanometers for nanoparticles composed of lipids, proteins, or carbohydrates. The specific size of these nanoparticles is determined by the ingredients and manufacturing methods employed during their production. There are several strategies to link nanoparticle dimensions to their toxicity and GIT destiny [21]. Smaller nanoparticles typically dissolve or digest more quickly

Fig. 1.2 Various characteristics of nanoparticles determine their fate in the food sector, adapted from [19]

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

in GIT fluids and interact more readily with gastrointestinal tract constituents (such as phospholipids, mineral ions, bile salts, or digestive enzymes) due to their large surface area [22]. Consequently, with decreasing size, smaller nanoparticles have a greater ability to penetrate the protective mucus layer surrounding epithelial cells. Furthermore, the size of nanoparticles plays a crucial role in determining their uptake by intestinal epithelial cells, which can occur through various mechanisms such as tight junctions, active transport, or passive transport pathways. Although spherical nanoparticles are the most prevalent in foods, other shapes like fibers, ellipsoids, and cuboids are also feasible [23]. It would also be expected that the shape of ingested nanoparticles will affect food characteristics and their biological fate. For instance, as the ratio of a nanoparticle’s length to breadth rises, so does its propensity to make food viscous. Furthermore, spheres often have an advantage over fibers in terms of the capacity of nanoparticles to get through the mucus layer [17]. Food-grade nanoparticles can be found in clusters of various sizes, morphologies, and densities or as solitary, isolated particles. The cohesion of nanoparticle clusters is commonly driven by physical interactions such as van der Waals forces, electrostatic interactions, hydrogen bonds, and hydrophobic interactions. Consequently, the aggregation state of nanoparticles is highly sensitive to environmental factors including pH, ionic strength, intercomponent interactions, and mechanical forces. The capacity of nanoparticles to pass through the gastrointestinal tract’s fluids, mucus layer, or epithelial cells depends greatly on the size of their clusters, which may be far larger than the diameters of the individual nanoparticles [19]. Hence, it is crucial to determine the actual effective size of nanoparticles at their targeted sites of action, rather than relying solely on the dimensions of the initial nanoparticles added to food products. Food-grade nanoparticles’ GIT destiny, and consequently their ability to cause health problems, are frequently controlled by their interfacial properties [24]. An adsorbate coating that surrounds the nanoparticles in food and the GIT normally has an impact on the interface’s digestibility, electrical charge, chemical reactivity, hydrophobicity, and thickness. This coating is sometimes referred to as “corona.” The GIT nanoparticles’ behavior will be governed by their surface properties.

1.3 Nanomaterials in Food Processing The qualities of some components used in food that function on the nanoscale or are referred to as “nanostructured” vary depending on whether they enhance texture, consistency, flavor, etc. Food nanotechnology has been used in a variety of ways to extend shelf life [25]. At present, nanocarriers are employed in food production as delivery systems for enhancing food flavors without altering their morphology. Particle sizes play a crucial role in determining the distribution of bioactive substances within the body. Notably, it has been observed that submicron-sized particles exhibit distinct behavior at the nanoscale [26].

1.3 Nanomaterials in Food Processing

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Food additives are currently incorporated into food items using nanocarriers without changing their basic shape. The size of a particle can directly influence the distribution of bioactive drugs within the body, as certain cell lines have been found to selectively absorb submicron nanoparticles while excluding larger microparticles. This emphasizes the significance of particle size in targeting specific areas of the body with bioactive drugs [27]. The use of easily absorbed chemicals that increase the shelf life of goods is another important application. Colloids, emulsions, and packed nanocapsules made of nanoparticles do not settle, extending the shelf life of the product [28]. The encapsulation of chemical additives and food ingredients is one of the most popular applications of nanotechnology. Nanoencapsulated meals may be modified by consumers to meet their dietary demands and tastes. Nanoencapsulation provides protective barriers, flavor and fragrance concealment, prolonged release, and increased dispensability for water-insoluble food components, supplements, and additives. Additionally, nanocapsules can be added to food items to provide nutrients and increase their bioavailability. An increase in nutritional absorption may result from the addition of nanoparticles to already existing food items. Additionally, nanoparticles can serve as food additives to lengthen the shelf life of foods and promote their effective absorption by the body. An optimal delivery system should be able to efficiently keep active compounds at the correct levels for lengthy periods of time (in storage state), ensure availability at the right time and rate, and transport the active component exactly to the intended place. Nanotechnology has been used to create emulsions, simple solutions, biopolymer matrices, encapsulation, and association colloids, which offer efficient delivery systems with all the aforementioned characteristics [29].

1.3.1 Nanofluid Thermal Processing A new application of nanofluids in the food industry has emerged, aiming to enhance the efficiency of heat processing equipment, reduce processing durations, safeguard bioactive compounds from degradation, and enhance the overall quality of food products [30, 31]. The many benefits and drawbacks of employing nanofluids in thermal processing are shown in Fig. 1.3. According to Shah and Sekulic, heat exchangers are an essential component in a wide variety of food processing procedures, including distillation, sterilization, fractionation, concentration, and pasteurization, as well as the heating or cooling of fluids [32]. The utilization of nanofluids in heat exchangers for the purpose of optimizing food processing facilities has recently attracted attention due to the potential benefits that these nanofluids offer in terms of both the technical efficiency of these facilities and the impact that they have on the quality of food products [33, 34]. The presence of aluminum oxide nanoparticles in water has been shown to result in a large increase in the thermal conductivity, viscosity, and density of the water, while also producing a notable reduction in the specific heat capacity of the water. These findings are based on the findings of experimental research. For example,

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

Fig. 1.3 Several advantages and disadvantages of using nanofluids in thermal processing. Reprinted with permission from Trends in Food Science and Technology, Copyright 2020, Elsevier [30]

in a study that focused on the thermal processing of tomato juice, the addition of Al2 O3 /water nanofluids with nanoparticle concentrations of 2% and 4% resulted in an increase in the heat transfer coefficient of 5.42% and 11.94%, respectively. This was the outcome of an increase in the heat transfer coefficient. Another study that was done on the processing of watermelon juice found that using Al2 O3 /water nanofluids with nanoparticle concentrations of 1%, 2%, and 4% correspondingly led to an improvement in the total heat transfer of 5%, 8%, and 13%, respectively [34, 35]. Other crucial technical characteristics impacted by the use of nanofluids include processing time, energy consumption, and the efficiency of food processing equipment. It has been shown that employing nanofluids instead of traditional heat transfer fluids will greatly cut processing time and energy consumption while dramatically increasing efficacy [36]. According to Zhang et al., the utilization of ZnO nanofluids has been found to enhance the inactivation of Escherichia coli through the improvement of the sonophotocatalysis technique [37], even though reactive oxygen species (ROS) have a more pronounced effect on bacterial inactivation in comparison to Zn+ ions. Authors assessed the sonophotocatalytic process’ inactivation effectiveness utilizing zinc oxide nanofluids, taking into account ultrasonic factors such as power density, frequency, and time [37]. The results indicate that the combination of ultrasonic irradiation, photocatalytic process, and natural light led to a 20% increase in the effectiveness of inactivating E. coli. E. coli was selected as the model bacterium to compare the inactivation efficiency among the photocatalytic, ultrasonic, and sonocatalytic processes. Additionally, a potential inactivation mechanism for sonophotocatalysis was identified. Studies comparing the release of zinc ions (Zn2+ ) and ROS showed that ROS play a more important role in the inactivation of bacteria than Zn2+ does. According to studies on the permeability of the outer and inner membranes of E. coli bacterial cells, sonophotocatalysis significantly boosted their permeability. The improved effect of bacterial inactivation in the sonophotocatalytic process was attributed to the influence of acoustic cavitation, ZnO sonocatalysis, and the phenomenon of sonoporation.

1.3 Nanomaterials in Food Processing

9

1.3.2 Nanofiltration Based on the characteristics of nanofiltration, agro-food processing applications such as fractionation, water softening, wastewater treatment, the processing of vegetable oils, and the treatment of products from the dairy, beverage, and sugar sectors are becoming more and more desirable [38]. It has already been claimed that nanofiltration can take the place of some of its competitors, such as reverse osmosis [39]. Governments around the world are increasingly enacting stringent laws governing food items’ processing-related hygiene. Additionally, specialized food categories like low-fat and low-calorie goods demand greater separation and advanced processing. Nanofiltration membranes offer a great deal of promise for this application because of their capacity to discriminate between multivalent ions and monovalent as well as organic solutes of different sizes from other species [40]. Several literature publications that address various topics, including the purification of water and sugar, the processing of whey, the clarity and concentration of juices, as well as fractionation, demonstrate the potential of nanofiltration application in food processing [38, 41]. It is possible to use nanofiltration in the manufacture and formulation of functional foods and drinks in addition to its typical application in juice processing to concentrate and separate valuable bioactive ingredients from fruit juices [42]. Arriola et al. used a spiral-wound PVDF membrane module with a molecular weight cut-off (MWCO) ranging from 150 to 300 Da in order to investigate the possibility that nanofiltration may be used to increase the concentration of beneficial chemicals in watermelon juice [43]. According to the findings of the study, utilizing nanofiltration as part of the juice processing procedure can result in a sizeable rise in the juice’s content of beneficial components. Average permeate flows of 2.3 L/m2 h were seen for lycopene, flavonoids, and total phenolic content, along with high rejection rates of 99%, 96%, and 65%, respectively. Concentrating the main bioactive compounds using nanofiltration was deemed to be a promising alternative. Arend et al. utilized a nanofiltration technique to effectively concentrate the bioactive substances in strawberry juice [44]. A PVDF nanofiltration membrane from GE Osmonics with a MWCO of 150–300 Da was employed for this purpose, and two distinct juices—untreated and microfiltered—were processed. Independent of the processed juice, the results revealed an increase in the overall phenolic concentration and anthocyanin content. When compared to untreated and microfiltered juice, the antioxidant activity of the nanofiltration concentrates increased by 99% and 51%, respectively. The global color variation (E*) analysis revealed that there was no color deterioration throughout the phenolic compound concentration. The outcomes supported the feasibility of creating beverages with enhanced nutritive and sensory qualities. Due to social and health concerns, there has been an increase in the demand for low-alcohol beverages in recent years in a number of nations [40]. This makes nanofiltration appear like a different method to get low-alcohol wines. Compared to

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

reverse osmosis, this method can offer higher alcohol flow rates and higher penetration rates. The organoleptic properties of the original product can also be preserved by using modest pressures and temperatures during such a procedure. For instance, in order to regulate the amount of sugar in grape must, Garca-Martn et al. examined the retention properties of various nanofiltration and tight ultrafiltration membranes toward glucose and fructose in model combinations [45]. The ultimate goal was to lower wine’s alcohol concentration within a conventional range that the consumer might tolerate without changing the product’s unique organoleptic balance. All three of the GE Osmonics examined membranes—UF-GH, NF-HL, and NF-DK—showed varying rejections toward fructose and glucose (in the ranges of 0.8–09 and 0.15–0.38 for nanofiltration and ultrafiltration membranes, respectively). It was discovered that polyphenols, anthocyanins, and tartaric acid caused nanofiltration membranes to reject them more frequently. Additionally, writers developed a two-step nanofiltration procedure to produce wines that are rich in low- and high-molecular-weight components yet have less alcohol. As part of the process, an initial nanofiltration step was performed on the non-fermented must, resulting in a solution with a satisfactory sugar content. The membrane effectively retained highmolecular-weight compounds like polyphenols and anthocyanins. The majority of the sugars in the retentate were subsequently concentrated by sending the nanofiltration permeate through a second nanofiltration phase. The goal at this time was to keep low-molecular-weight substances in the permeate, such as ions and tartaric acid. Nanofiltration finds significant applications in the dairy industry, including partial demineralization of whey, production of lactose-free milk, and volume reduction of whey [46]. The dairy industry uses nanofiltration extensively throughout the world to desalt brines, mother liquors, and whey [47]. This is because nanofiltration membranes, which have a selectivity that is halfway between ultrafiltration and reverse osmosis membranes, offer an intriguing alternative to ion exchange and electrodialysis if just mild demineralization is needed. With this method, whey is demineralized while also being concentrated, resulting in cost, time, and water disposal savings. It has been suggested that nanofiltration could be used for a variety of purposes in the dairy industry, including the concentration of whey protein (reaching levels of up to 0.2–0.22 dry matter concentration), the removal of acid from acid whey (approximately 0.42 acid removal), the reduction of salt content in salty whey (reaching levels of up to 0.84 salt reduction), and the reduction of mineral content by 0.2–0.5. In addition, nanofiltration membranes are utilized in the dairy sector for the purposes of concentrating and demineralizing ultrafiltration-whey permeate that has the necessary amount of lactose, as an alternative to the process of vacuum evaporation for the purpose of concentrating milk in the manufacturing of yoghurt, and for selectively demineralizing yoghurt [40]. Nanofiltration can selectively separate monosaccharides and di/trisaccharides with interesting yields despite the small changes in their molar masses. For instance, it can separate glucose from sucrose, lactose, or even raffinose [48]. Numerous studies have demonstrated that xylose and glucose may be successfully separated using

1.4 Nanomaterials in Food Packaging

11

nanofiltration membranes, which is crucial for the commercial purification of xylose for the production of xylitol. For instance, three distinct nanofiltration membranes (Desal-5 DK, Desal-5, DL 270) with a MWCO in the range of 150–300 Da were employed by Sjöman, Mänttäri, Nyström, Koivikko, and Heikkilä to process solutions containing xylose and glucose in varying mass ratios and concentrations of total monosaccharide [49]. Comparable fractionation results were produced by the chosen membranes. It was discovered that the main process implying the separation of these uncharged molecules was molecular sieving. The permeate flux primarily had an impact on monosaccharide retention. The disparity between xylose and glucose retention was reduced by raising the permeate flux. The best xylose separation from glucose was accomplished at high pressure with a concentrated monosaccharide mixture. All of the selected membranes had a xylose separation factor of at least two. The experimental findings show that nanofiltration technology increases yield and has the potential to partially replace chromatographic processes in the synthesis of xylose. Additionally, for the competitive purification of disaccharides or monosaccharides, nanofiltration represents an alternative to conventional methods [50]. For instance, Xu, Wang, and Zeng suggested using nanofiltration membranes to separate out maltitol from a complicated combination that also contained sorbitol, maltitol syrup, multisugar alcohol, and other ingredients [51]. Nanofiltration has also been used to successfully purify xylooligosaccharides (XOs), which are interesting compounds because of their distinctive health advantages. Actually, nanofiltration was employed to remove contaminants from raw XOs syrups, such as salts, organic acids, and monosaccharides (mostly xylose and arabinose), which could result in off-flavors and pose safety problems [52]. It is well known that pressure-driven membrane procedures like nanofiltration, ultrafiltration, and microfiltration aim to separate and recover valuable solutes from by-products of agro-food processing in addition to removing organic matter [53, 54]. Smaller molecules (such as sugars and phenolic compounds) can be recovered using nanofiltration depending on the molecular weight cut-off of the membranes, which is typically done using solvent and supercritical fluid extraction techniques. Last but not least, resin adsorption and chromatography are the most sought-after techniques for the purification and concentration of target substances, and nanofiltration technology also satisfies their requirements. Since these technologies have been employed in various facets of the food processing business for many years, they are all widely considered safe, well-established, and well-documented [40].

1.4 Nanomaterials in Food Packaging Because of its numerous advantageous qualities, such as its antioxidant and antibacterial effects, researchers have described nanofood packaging as a revolutionary packaging technique that replaces conventional food packaging [55, 56]. Nanomaterials as additives can extend the shelf life of food packaging [57, 58]. Nanotechnology

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

employment as food packaging material can effectively reduce the growth of microorganisms including E. coli, L. planatarum, S. aureus, and various molds and yeasts [59–61]. It has been primarily reported that involvement of antimicrobial nanomaterials like zinc oxide, silver nanoparticles or nanocomposites can enhance the shelf life of various products like fruit juices and meat [55, 62]. The utilization of highperforming, lightweight nanoparticles to replace non-biodegradable plastic packaging materials in nanofood packaging has excellent potential in the food industry [63]. The numerous commercially available nano-based packaging materials are displayed in Table 1.1. Nanoscale reaction engineering, chemical synthesis, heat and mass transfer, and nanobiotechnology are all used in the manufacturing of nanofood packaging, as shown in Fig. 1.4. Polymer nanocomposites play a crucial role in nanofood packaging due to their various benefits. They enhance barrier properties such as moisture, carbon dioxide, oxygen, and the emission of ethanol and flavors [64]. Additionally, they enable active packaging, which helps in delay or inhibit microbial growth and food spoilage [65]. Furthermore, they contribute to intelligent packaging, allowing for the monitoring of food conditions [66]. Lastly, the utilization of degradable biopolymers in nanocomposites helps improve the chemical and physical properties of the packaging materials [67]. Inorganic nanoparticles can be utilized as a suitable additive for polymers to improve their performance since they have special physical and chemical properties that distinguish them from other materials. As a result of their increased stability during storage and ability to maintain color, flavor, and texture while reducing spoilage, graphene, carbon nanotubes, silica nanoparticles, and enhanced nanofillers like silicate and clay nanoplatelets may all be used in the food industry in a number of ways [69, 70]. Their antimicrobial activity allows for their enhanced application in food packaging. The rupture of the cell wall, interaction with DNA’s thiol groups, proteins, enzymes, ROS generation, and cell respiration are a few of the potential processes by which nanoparticles can exert their antimicrobial effect [71]. Food packaging material can be comprised single polymer layer to restrict O2 and H2 O entry, which may be strengthened with a layer of nanocomposite material to improve the barrier qualities, as shown in Fig. 1.5 [72]. Inorganic metal oxide nanoparticles that are often used in food packaging include zinc oxide nanoparticles [73]. It has been reported that the bacterial cellulose film has been modified using polypyrrole-ZnO nanocomposite for active and intelligent packaging in order to restrict the bacterial growth in food and also regulate pH alteration [73]. Another study reported that the effect of zinc oxide nanoparticles is more prominent in gram-positive bacteria in comparison to gram-negative bacteria [74]. Silver nanoparticles are a substance that is encouraged for usage in many applications, including food packaging. Ex situ and in situ techniques can both be used to develop silver nanoparticles [55]. The use of a chitosan silver nanoparticle based nanocomposite layer in food packaging, which was made of 70% polyvinyl alcohol and 30% aqueous chitosan solution with silver nanoparticles, showed remarkable antibacterial activity against both gram-positive and gram-negative bacterial species. In addition, silver nanoparticles have been shown to have the ability to prevent the

Brand

Aegis HFX Resin and OXCEResin

OMACO Imperm@

OxyGuard@

ATCORDE10S/ 100 OS/200OS

Cryovac@OS systems

Ageless@E

Ageless®Ga

UlraZap RXtenda Pak pads

Microspheres

RipeSenseT sensor

TimeSrip®

S.no.

1

2

3

4

5

6

7

8

9

10

11

Material type

Iron oxidation

Cerium oxide

TimeSrip UK Ltd, UK

Ripesense limited, New Zealand

Bernard Technologies, Inc., USA

Paper Pak industries, Canada

Mitsubishi Gas Chemical Inc., Japan

Mitsubishi Gas Chemical Inc., Japan

TTI based on enzyme, Lipase, and pH indicating dye

Changing color based on aromatic compounds

Chlorine dioxide

Allylisothiocyanate (AIT) or scavenging molecular O2 (Listeria populatons)

Ferous carbonate/a mixture of sodium bicarbonate and ascorbic acid

Sodium carbonate/sodium glycinate

CryovacDiv., sealed air Polymer oxidation corporation, USA

Emco packaging systems, UK

Clariant Ltd., Swaziland

Mitsubishi Gas Chemical Inc., Japan

Honeywell Nylon 6-nanoclay composite International Inc., USA

Company

Table 1.1 Commercially available nanopackaging materials, adapted from [82]

Seafood, oysters

Fruits

Meat, poultry, fish, dairy, confectioneries, and baked goods

Ham, ready-to-eat meat product

Meat

Strawberries, eggplant

Cooked food

Cooked meat

Fried snacks

Retort product and hot full of meat and fish products

Beer and favored alcoholic beverage bottles, PET

Product type

Barrier nylon resins

Form

Freshness (based on color)

Freshness indicators

Microbial contamination

CO2 emitter and antimicrobial pad

CO2 emitters

CO2 scavenger

(continued)

Stickers

Stickers

Tray/ Pads

Sachets

Sachets/ Labels

Oxygen scavenger Tray, films

Oxygen scavenger Labels

Oxygen scavenger Sachets and film

Oxygen scavenger Film

Oxygen scavenging

Application

1.4 Nanomaterials in Food Packaging 13

Brand

N-coat

Biomaster

Ethysorb®

TipTop bread

Carnaton instant food

S.no.

12

13

14

15

16

Table 1.1 (continued)

PE-Nanoclay composite

Nanosilver

Canation Breakfast Essential, Switzerland

Titanium dioxide (Nanoencapsulation)

Powdered milk-based products

Bread

Fruits and vegetables

Fruits and vegetables

Antcaking

Nano capsule with tuna fish oil

Ethylene Scavengers

Antimicrobial packaging

Dried fruits, cheeses, coffee Gas barrier

Nanoclay Al2 O3 ·2SiO2 ·2H2 O

Application

Product type

Material type

George Weston Foods, Nanosized self-assembled liquid Enfield, Australia structure

Stay Fresh Ltd.

Addmaster Limited, USA

Multiflm Packing Corporation, USA

Company

Powder

Bags

Bag, spray

Film

Form

14 1 Overview of Nanomaterial Application in Food and Agriculture Sector

1.4 Nanomaterials in Food Packaging

15

Fig. 1.4 Diagram illustrating the preparation methods employed in the production of nanofood packaging. Reprinted with permission from Food and Chemical Toxicology, Copyright 2020, Elsevier [68]

Fig. 1.5 Comparison of the barrier properties of packaging material prior to a and subsequent to b integration of nanocomposites. Reprinted with permission from Food and Chemical Toxicology, Copyright 2020, Elsevier [68]

action of ethylene by soaking up and dissolving the ethylene that is produced as a byproduct of fruit metabolism [75, 76]. Fernandez et al. investigated the antibacterial activity of newly created cellulose-silver nanoparticle hybrid materials during storage of little-processed “Piel de Sapo” melons [75]. Silver nanoparticles with diameters ranging from 5 to 35 nm were generated through an in situ reduction process using physical methods. This involved the utilization of 1% silver nitrate adsorbed on cellulose fibers. Freshly cut melon pieces were stored in natural modified environment

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

packaging for ten days at 4 °C, with or without absorbent pads that had been silverloaded. Changes in head gas composition, quality indicators, and antibiotic action against microorganisms linked to deterioration were all examined. The cellulosesilver nanoparticle hybrid materials showed evidence of the release of silver ions upon reaching saturation with melon juice. In cellulose-based absorbent pads that came into contact with vegetable matrices, the presence of silver ions, which have limited chelating activity, was found to be favorable in the process of lowering the population of bacteria that are associated with the process of spoiling. The microbial loads in the pads were on average roughly 3 log10 CFU/g lower than the control over the examined storage period. The addition of silver-loaded absorbent pads also resulted in the melon slices having considerably lower Brix values and yeast counts after ten days of storage, as well as seeming to be juicier. Due to their enhanced stability, easy availability, low cost, and high benignity, nanoclay can be efficiently used in food packaging applications [77]. Research has shown that the storage time of beer can be increased from 77 to 210 days by the incorporation of nanoclay into bottles. Additionally, in nylons and plastic bottles, nanoclays thicken packaging, lessen gas permeability, and also lessen the amount of foods that are sensitive to oxygen [78]. In a separate investigation, Tajeddin et al. showcased the utilization of the nanomaterial as an ingredient in the composition of packaging material. They incorporated nanoparticles into carboxymethyl cellulose (CMC)/polyvinyl alcohol (PVA) films through the solution-casting evaporation process, employing three distinct concentrations of nanoparticles (0.5, 1, and 3%) [79]. The impact of adding nanoclay to a CMC/PVA-based film’s mechanical, water vapor permeability, and oxygen barrier properties was examined. The best outcomes were obtained with the nanocomposite layer comprising 3% nanoclay. The next stage was packing walnuts using the CMC/PVA/nanoclay sheets. After 90 days of ambient storage, the nanocomposite layer with 3% nanoclay generated the best results in terms of the moisture content, oil content, acidity, and peroxide indices of walnut. Considering the comprehensive findings, it is advisable to consider the utilization of CMC/PVA film strengthened with 3% nanoclay as a viable choice for manufacturing food packaging materials with superior barriers against the ingress of oxygen and water vapor. Additionally, it is possible to significantly improve the properties’ resistance to gas intrusion. According to certain studies, the tortuosity effect of nanoclays allows for the application of nanocomposite materials, such as nanoclays, to improve antibacterial agents and effectively prolong retention in food packaging [79–81]. Pandey et al. demonstrated the combination of polyvinyl alcohol (PVA) with stable silver nanoparticles (AgNPs) of size 80 ± 11 nm generated by chitosan-assisted green synthesis to create electrospun fibrous composite nanolayers (FCNLs) [55] (Fig. 1.6). The electrospun composite demonstrated efficient antibacterial action against the bacterial species E. coli (gram − ve) and L. monocytogenes (gram + ve). When used as a meat packaging medium, the electrospun composite demonstrated bioactivity and increased the meat’s shelf life by one week. The electrospun nanocomposite can improve the shelf life of packaged food while also preventing microbiological deterioration. Result showed that P70-CH30 and P70-CH30-Ag biocomposite FCNLs have effective antibacterial activities against bacterial degraders. Chitosan’s

1.4 Nanomaterials in Food Packaging

17

characteristics give them their inherent antibacterial capabilities, which are synergistically enhanced when greenly synthesized AgNPs are added to P70-CH30-Ag NLs. The innovative food packaging materials made from these chitosan-based composite nanolayers may be just as helpful as traditional plastics while having a far less negative environmental impact. This would allow for the replacement of conventional plastic packaging.

Fig. 1.6 Packaging of fresh meat using chitosan silver nanocomposite. Reprinted with permission from International Journal of Biological Macromolecules, Copyright 2020, Elsevier [55]

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

1.5 Nanomaterials in Food Preservation Nanomaterials are widely used in water treatment, against numerous pathogenic bacteria, and in healthcare, crop protection, food safety, and preservation because of their outstanding physiochemical nature and antimicrobial capabilities [83–85]. Encapsulation of nutritional supplements and functional antimicrobial compounds is essential for food processing, food storage, and transit through the gastrointestinal system. It also depends on the preservation and bioavailability of bioactive chemicals [86]. The addition of macromolecule-based nanoparticles to food not only increases the bioavailability of bioactive polyphenolics like resveratrol, curcumin, and epigallocatechin-3-gallate but also makes these polyphenols more soluble and prevents them from degrading in the gastrointestinal environment [87]. Studies have shown that edible coatings that are less than one nanometer in size are a useful alternative for food preservation, shelf life extension, and microbial deterioration prevention [88]. Coatings made by combining gelatin with cellulose nanocrystals, chitosan or nanosilica, chitosan with nanosilica, alginate or lysozyme nanolaminate, and gelatin have been shown to be particularly effective for maintaining the freshness of fresh meals over prolonged storage [89]. Yu et al. conducted a study to investigate the impact of a chitosan coating with a concentration of 1%, incorporating 0.04% nanosilicon dioxide, on the qualitative characteristics of jujube fruit during storage at room temperature [90]. After 32 days, the coated jujubes’ decay incidence, red index, weight loss, and respiration rate decreased when compared to the control. The chemical coating is responsible for the coated jujubes’ decreased phenylalnine ammonialyase activity and increased scavenging antioxidant enzyme activities (such as superoxide dismutase, peroxidase, and catalase). The coated jujubes’ increased malonaldehyde content was controlled. The study revealed that the chitosan coating alone was not as effective as the composite coating in preserving the total flavonoid content of jujube fruit. However, there were no significant differences in the loss of vitamin C or total polyphenol content between the composite coating and the control. Therefore, the combination of chitosan and nanosilicon dioxide coating could be a promising option for preserving the quality of jujube fruit, pending the approval of nanosilicon dioxide for food applications. Another study looked at how a unique nanopacking material affected the ability of Chinese jujube to maintain its quality while being stored at room temperature (Ziziphus jujuba Mill. var. inermis (Bunge) Rehd). The development of a novel packaging material that incorporates polyethylene and a variety of nanomaterials (nano-Ag, kaolin, anatase TiO2 , and rutile TiO2 ) led to a reduction in relative humidity as well as an increase in oxygen transmission rate and longitudinal strength (2.05 g/ m2 24 h, 12.56 cm3 /m2 24 h, 0.1 MPa, and 40.16 MPa, respectively). In comparison to conventional packaging materials, the physicochemical and sensory properties of the nanopackaging material were found to have undergone significant advancements as a result of the findings of the experiments. The nanopackaging was efficient in preventing the fruit from browning, losing weight, becoming softer during the course of the storage duration of 12 days, and undergoing climacteric changes. Therefore,

1.5 Nanomaterials in Food Preservation

19

nanopacking could be used to preserve Chinese jujube in order to increase its shelf life and preserve its quality. The development of a unique packaging material that incorporates polyethylene and a blend of nanomaterials (kaolin, nano-Ag, anatase TiO2 , and rutile TiO2 ) led to a reduction in relative humidity, an increase in the oxygen transfer rate, and an improvement in the longitudinal strength of the material. When compared to conventional packaging materials, the novel nanopackaging material had superior features, including enhanced strength, enhanced control over humidity levels, and efficient oxygen transport. This novel packaging solution has the capacity to maintain the quality and freshness of items even after they have been stored, which demonstrates its potential as a promising choice in the field of food packaging [91]. The effect of nanopackaging on the quality maintenance of strawberry fruits (Fragaria ananassa Duch. cv. Fengxiang) was tested while the strawberries were stored at 4 °C. According to the findings of the study, the sensory, physicochemical, and physiological qualities of strawberry fruits were better preserved using nanopackaging than conventional polyethylene bags. The nanopackaging saw a considerable drop in total soluble solids, titratable acidity, and ascorbic acid levels following a storage period that lasted for a period of 12 days. In addition, the traditional packaging had a higher decay rate (26.8%), anthocyanin content (31.9 mg/100 g), and malondialdehyde content (75.4 mol/g), while the nanopacking had a lower decay rate (16.7%), anthocyanin content (26.3 mg/100 g), and malondialdehyde content (66.3 mol/g). In addition, the activities of polyphenoloxidase (PPO) and pyrogallol peroxidase (POD) were dramatically reduced in the nanopackaging in comparison to the control group. According to these findings, nanopackaging may represent a promising potential as an attractive alternative for boosting the quality of preservation of strawberry fruits throughout extended storage periods. Electrostatic complexation was used in a study that was carried out by Duarte and Picone, and it resulted in improvements to the antibacterial capabilities of lactoferrin (L), chitosan (C), and gellan (G) nanoparticles (Fig. 1.7a) [92]. Using different proportions of biopolymers, authors investigated both binary complexes (lactoferrin-gellan and chitosan-gellan) and ternary complexes (lactoferrin-chitosangellan). Taking into account characteristics such as nanoparticle size, charge density, and shape, a comparison was made between the antibacterial activity of the nanoparticles against S. aureus and that of the pure biopolymers. The antibacterial efficacy of the samples with a ratio of 4.5L:4.5C:1G was found to be the highest, with a minimum inhibitory concentration of 0.0117 mg/ml. In addition to having the highest positive charge density (+57.90±1.50 mV), these samples had a lower hydrodynamic diameter (53.53 ± 2.06 nm). When the nanoparticle coatings were applied on fresh strawberries, the physicochemical properties of the fruit were effectively retained. This was especially true when carboxymethylcellulose was included in the formulation in order to improve the adherence of the coatings. According to the findings of this study, the aggregation of biopolymers at the nanoscale increased the antibacterial characteristics beyond what lactoferrin and pure chitosan could achieve on their own. The generated nanoparticles show excellent potential for use as natural food preservatives.

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

Fig. 1.7 a Antimicrobial activity of nanoparticles composed of lactoferrin, chitosan, and gellan was investigated in a study. Reprinted with permission from Food Research International, Copyright 2022, Elsevier [92]. b Application of titanium dioxide in food preservation. Reprinted with permission from Food Research International, Copyright 2022, Elsevier [93]

A dual-photon system that is based on TiO2 nanoparticles and hypocrellin B (HB) was developed through research carried out by Wan et al. [93] and has been shown in Fig. 1.7b [93]. When exposed to visible light with a wavelength of 460 nm (9 J/cm2 ), the combination of these two photosensitizers indicated a considerable decrease in staphylococcal survival, with a maximum decrease of 4–5 logs recorded. Only in the mixed phase of anatase and rutile, employing 10 nM HB and 100 M TiO2 nanoparticles, and more specifically with the Degussa P25 formulation, synergistic photokilling has been observed. The antimicrobial mechanisms involved a severe compromise of the membrane integrity of S. aureus, a modification in surface shape, leakage of potassium and DNA from the cell, and a major suppression of biofilm

1.5 Nanomaterials in Food Preservation

21

formation due to the excitation of sensitized photosensitizers. All of these factors contributed to the antimicrobial effect. The use of quantitative PCR allowed for the discovery of dysregulation in the genes of S. aureus that code for membraneassociated cell death effectors and antioxidant response. It is important to note that LrgA was found to be one of these effectors since the mutant strain that constitutively expressed LrgA was able to improve the bactericidal activity of the dual-photon system. In addition, under conditions of visible light, the dual-photon technique substantially decreased microbial contamination in apples while keeping the apples’ quality intact. The creation and validation of this innovative dual-photon system combining TiO2 nanoparticles and HB for the photokilling of S. aureus in order to ensure food safety provide a promising approach. Recently, various nanosystems, including nanoemulsions, polymeric nanoparticles, and nanocomposites, have been applied to the development of edible coatings in an effort to control the release of essential oils, polyphenols, and fat-soluble vitamins relative to their function in microcapsules and other forms of incorporation into polymeric matrices [94]. Future advancements in bionanocomposite packaging employing polymeric polymers and inorganic nanoparticles for food preservation are envisaged [95, 96]. Since there is not much research currently available examining the impact of edible coatings and films (ECF) with nanoparticles on the storage quality of fresh fruit. The manufacture and use of ECF and nanostructured materials to increase the shelf life of fresh agricultural products have grown in recent years. Sorrentino et al. also analyzed the various bio-based material types, their uses as packaging materials, and emerging trends [69]. Figure 1.8 shows how ECF with nanoparticles has induction defense properties as well as a preservation strategy that includes gas modification. A thin coating film can be formed on the surfaces of fresh items following treatment and drying. Then, by altering the amounts of O2 , CO2 , and ethylene in the packages, the matrix carriers, such as chitosan-based coatings with semipermeable characteristics, could slow the pace at which fruits breathe. According to several studies, this gas change may prevent items from losing water and nutrients. On the other side, pathogens found in packaging and those that have formed on the surface of fresh food may be resistant to pathogens because of the nanoparticles in coating materials on the produce surface, especially when UV radiation is present. These antimicrobial processes might make a big difference in preventing vegetables from rotting and losing quality. In addition, some coating polymers, such as chitosan, may also have antibacterial characteristics that protect against fungus and bacteria while fruits and vegetables are being stored. The ECF, such as chitosan with nanoparticles, may also be able to reduce free radicals and activate defense-related enzymes in fruit cells, increasing the defensive activity of fruits and vegetables during storage, as shown in Fig. 1.8. The firmness, bioactivity, and internal color of the treated fresh items would all be preserved by the combined efficacy. This would also retain the products’ good quality and appropriate shelf life. Uncoated strawberries and mangos were compared to samples that had been exposed to nanocomposite and kept at room temperature for 7 days by Xu et al. [98]. The nanocomposite coating that comprised GO and CS-loaded TiO2 inhibited the polyphenol oxidase activity, and they found that the coated samples had a

22

1 Overview of Nanomaterial Application in Food and Agriculture Sector

Fig. 1.8 ECF preservation mechanism on pulp quality, adapted from [97]

reduced rate of weight loss and retained a superior appearance. Fruits covered in three different kinds of nanocomposite films had greater levels of superoxide dismutase (SOD) activity than untreated samples, indicating considerable potential for the food preservation industry.

1.6 Nanomaterials in Enhancing Food Quality The term “food quality” is typically used to describe any characteristic of a food product that is related to that product’s acceptability in terms of its safety and nutritional worth. These features pertain to the appearance, texture, and flavor of the product as well as its chemical makeup, physical attributes, and microbes [99]. Numerous opportunities exist to enhance the nutritional content and flavor of food using nanotechnology. Nanotechnology is widely utilized to enhance food properties like color, flavor, nutritional value, and flow character or to lessen the negative effects of excess fat, sugar, salt, and other ingredients in food products [100]. At the nanoscale, food’s color, flavor, texture, and utility can be drastically changed. For instance, nanoemulsions can be used to develop the required textures for customers in mayonnaise, puddings, processed meat items, and sauces. Customized nanoemulsions or nanostructures act as thickeners, emulsifiers, and foaming agents to improve the texture as well as to enhance flavor. Because they are more accessible to tongue receptors, salt particles that are nanoscale or almost nanoscale may enable the use of less salt without compromising flavor in meals. It has been noted that customers’ desires for healthier foods with fewer amounts of salt, sugar, and fat (although these nutrients might help suppress bitterness) make the problem of food bitterness more challenging. Recent examples include functional foods with high-molecular-weight phytochemicals that display health-promoting properties, such as bitter and astringent polyphenols [101, 102]. Bitter compounds are predominantly hydrophobic in nature. Substances such as lipoproteins, cyclodextrins, and cyclofructans have the ability to selectively obstruct the regions of the taste receptor membrane that are specifically

1.6 Nanomaterials in Enhancing Food Quality

23

targeted by bitter compounds while leaving the perception of salts, acids, sugars, or sweet amino acids unaffected [102, 103]. One approach to mitigating the bitter taste is to prevent the interaction between bitter molecules and taste receptors. This can be achieved by creating intricate nanostructures that offer steric hindrance or form complexes with the bitter compounds, thereby reducing their impact on taste perception [102]. Techniques for nanoencapsulation are frequently used to preserve a culinary balance while also allowing for gradual flavor release [104]. A large number of bioactive complexes, including carbohydrates, lipids, vitamins, and proteins, are susceptible in a very acidic environment due to the presence of enzyme activity in the duodenum and stomach. Bioactive multilayered encapsulation gives them the ability to not only overcome that difficult situation but also to willingly change into food goods [105]. The use of non-capsulated bioactive chemicals with lower solubility makes it extremely challenging to achieve these phenomena. Currently, ordinary foods are used to increase the delivery of vitamins, sensitive micronutrients, and drugs to produce favorable health benefits. These tiny edible capsules are covered with nanoparticles [106]. Since nanoemulsions may be employed to boost bioavailability and water-dispersion, they are far more frequently used to create lipidsoluble, bioactive compounds [107]. Figure 1.9 shows the role of nanoemulsion on food quality improvement. The utilization of nanofluids in a shell, and tube heat exchanger has shown notable advantages over water in maintaining the color, pH, acidity, and total soluble solids of tomato and watermelon juices. Furthermore, the degradation of essential components such as vitamin C, total phenolic compounds, and lycopene was considerably reduced

Fig. 1.9 Nanoemulsion in improving food quality, adapted from [108]

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

when nanofluids were employed instead of water. Due to its ability to shorten the time required for heat operations, nanofluids have been shown to perform better than water in relation to food quality [109, 110].

1.7 Nanoenabled Food Foods are made up of a complex matrix of macronutrients (proteins and carbohydrates) and micronutrients (vitamins and minerals), each of which has a unique chemical makeup, molecular structure, and physical state. Nanoparticles, which comprise carbohydrates, amino acids, lipids, enzymes, and bacteria from dietary sources, are present in water, the atmosphere, and food. Human toxicity from ingesting nanoscale components is rare. Food safety may vary as a result of additives that influence food stability, texture, and processability. Thus, only 1000 designed nanoenabled foods (mostly premarket model foods) are on the market [1]. It has been established that one alternative strategy to treat issues or diseases caused by diet is the management of digestion and the release of nutrients and bioactives from a food matrix. Such a strategy is made possible by the combination of food processing and nanotechnology. It has been established that one alternative strategy to treat issues or diseases caused by diet is the management of digestion and the release of nutrients and bioactives from a food matrix. Such a strategy is made possible by the combination of food processing and nanotechnology. R&D efforts to utilize nanotechnology in food development during the previous ten years have mostly focused on enhancing sensory qualities, nutritional intake, and bioactive stability and availability. Efficiency of processing, handling stability, and safety of consumption have all been questioned [1]. The success of intensive R&D from major global food producers including Unilever, Kraft, Nestle, Heinz, and Altria has led to a steady increase in the manufacturing of nanoenabled foods. Various examples were reported as (i) Toddler Health’s fortified chocolate and vanilla “nutritional drinks” (marketed as “an all-natural balanced nutritional drink for children from 13 months to 5 years”), which contain SunActive® iron particles (300 nm diameter). (ii) Aquanova’s innovative approach to weight control involves the utilization of nanosized micelles known as “NovaSol.” These micelles contain two key active ingredients, CoQ10, which aids in fat reduction, and alpha-lipoic acid, which promotes satiety. Together, these components contribute to effective weight management. (iii) RBC Life Sciences’ nanoceuticalsTM Slim Shake Chocolate is specifically designed for individuals adhering to a low-sugar diet. This product incorporates nanoclusters™ to enhance both moisture and taste, providing an improved sensory experience.

1.7 Nanoenabled Food

25

(iv) To effectively provide health-promoting omega-3 lipids without leaving a fishy aftertaste, Tip-Topts Up bread in Western Australia is supplemented with nanocapsules containing omega-3 fatty acid-rich tuna fish oil. (v) BASF’s SoluTM E 200 BG transparent sports beverages incorporate LycoVit 10%, a nanoscale lycopene food ingredient with a size of 200 nm. This ingredient is utilized to provide a vibrant red color and deliver potent antioxidant properties. Nanotechnology also has the power to improve food safety and change how food is produced. Food ingredients interact with one another both intra- and intermolecularly in a food matrix. Proteins, lipids, carbohydrates, enzymes, nucleic acids, and antioxidants are examples of other dietary components that interact with nanoparticles. The quality, digestibility, and distribution of bioactives in food may therefore be impacted by customized food formulation and processing, particularly those that can change the nanostructure of foods’ architecture [1]. The next generation of “functional foods,” “interactive foods,” or “on-demand foods” are specialty goods with better safety, effectiveness, and nutrition that require chemicals in nanoparticulate form to enable protection or absorption [111]. Although nanotechnology may offer opportunities for innovation, quality assurance, and food supply, it also poses risks for human use and consumption. The application of nanotechnologies in agro-food applications, such as adding nanoparticles to meals and drinks, packaging food, and edible coatings over food, raises questions about their safety, environmental concerns, ethics, and regulatory issues. Efforts should be undertaken to mitigate these risks and ensure the safety of food growers, processors, and consumers. Nanotechnology-based applications are showing great potential as alternative solutions, particularly in the areas of microbiological food safety and quality. These applications include the development of “active/intelligent” food packaging that offers improved food protection, biodegradable features, and utilizes engineered nanoparticles such as Ag, ZnO, and TiO2 with photocatalytic properties. Additionally, antimicrobial food contact surfaces and coatings, as well as nanoenabled sensors for rapid detection of pathogens and substances, are emerging as effective measures. Surface disinfection techniques are also being enhanced through the utilization of nanotechnology [9, 113]. Figure 1.10 shows the advantages of nanoenabled food in different food sectors. A variety of nanoenabled antimicrobial food contact surfaces and coatings with the ability to inactivate microorganisms or prevent their attachment and subsequent biofilm development can help maintain cleanliness during food manufacturing and storage. These kinds of surfaces can be found in kitchen and cooking appliances, cutting boards, equipment, conveyor belts, and other places where food is prepared and processed. In addition, the diverse photocatalytic surfaces based on TiO2 , ZnO, CeO2 , etc. are among the most commonly utilized nanoenabled antimicrobial surfaces [114]. A significant restriction for photocatalytic surfaces is the use of UV light; however, in recent years, photocatalytic nanoparticles that use visible light have been produced [115]. In addition, using natural antibacterial extracts in

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

Fig. 1.10 Advantages of nanoenabled food in various sectors of food application. Reprinted with permission from Current Opinion in Biotechnology, Copyright 2017, Elsevier [112]

place of harsh chemicals on a variety of surfaces has gained popularity recently. Cinnamaldehyde, for instance, was immobilized on glass surfaces and nanoencapsulated, displaying strong antibacterial action against E. coli [115]. Similar outcomes were attained when thyme oil was immobilized on a glass surface after being emulsified with soluble soybean polysaccharide (a nanoemulsion) [116]. Donsi et al. paired a non-thermal treatment, such as high hydrostatic pressure (HHP) or pulsed light (PL), with an antimicrobial edible coating to test against green bean samples that had been inoculated with Listeria innocua while also assessing the effects on product color and firmness over the course of 14 days of refrigeration at 4 °C. The coating formulation, comprised of modified chitosan, contained a nanoemulsion of mandarin essential oil. Non-thermal treatment conditions were established in early inactivation testing against L. innocua inoculated on coated green beans. These investigations showed that L. innocua population may be decreased by about 4 and 2 Log cycles with 400 MPa and 5 min for HHP and 1.2 105 J/m2 per bean side for PL, respectively. The application of coating in conjunction with HHP was the most successful tactic due to the establishment of a strong antibacterial synergism, which resulted in a considerable reduction in L. innocua throughout the course of the storage period but also had a major influence on green bean firmness. On the other hand, the application of the coating in combination with the PL revealed a little antagonistic activity and had a slight detrimental effect on the color properties. Table 1.2 summarizes the application and impact of various nanomaterials in food industry.

Application

Packaging

Packaging

Edible coating

Food packaging

Nanomaterials

Zinc oxide

Silver

Silver

Silver

Chitosan, gelatin, polyethylene glycol

Chitosan

Bacterial cellulose

Carrier/Dispersant

Red grapes

Chicken sausages

Meat

Chicken thigh

Food

Table 1.2 Various nanomaterial-based applications in the food industry References

Studies on the packaging of red grapes revealed that when using a hybrid film, the fruit’s shelf life was increased by an additional two weeks

(continued)

[118]

The antibacterial properties of AgNPs demonstrated a [117] significant (p < 0.05) ability to inhibit lactic acid bacteria in sausages, resulting in an extended shelf life of 30 days. Furthermore, the incorporation of AgNPs had an impact on the texture of the sausages, possibly due to the interaction between silver ions and the proteins’ phosphorus and sulfur components. After 30 days, it was shown that treated sausages had more lipid oxidation than control samples

When used as a meat packaging medium, the [55] electrospun composite demonstrated bioactivity and increased the one-week shelf life of meat. The electrospun nanocomposite can prolong the shelf life of packaged food and prevent microbiological deterioration in an environmentally friendly way

Film may be able to control pH escalation and reduce [73] microbial load increase in chicken thighs. By boosting antioxidant and antibacterial activity as active packaging, the BC-PPy-ZnO film may lengthen the shelf life and stabilize the rheological characteristics of chicken thighs

Result

1.7 Nanoenabled Food 27

Application

Packaging

Preservation

Preservation

Sensor

Nanomaterials

Gold and graphene oxide

Carbon nanotubes

Graphene oxide

Gold

Table 1.2 (continued) Carrier/Dispersant

Salicylaldehyde

Polylactic acid and chitosan

Poly(vinyl) alcohol

Food

Raw meat, fish, crustaceans, and preserved meat

Banana

Strawberry

Banana

Result

References [119]

AuNPs can detect dimethyl sulfide and histamine at limits of 0.5 and 0.035 g/mL, respectively. The probe also exhibits remarkable selectivity for such markers even in the presence of other volatiles, which are typically created by spoiled actual meat and seafood

The final composite demonstrates effective preservative release in response to stimuli from overripe fruit juice and extends the shelf life of the fruit. The composite exhibits lower toxicity in addition to more reusability potential than the free preservative

(continued)

[122]

[121]

The strawberry preservation trials revealed that [120] nanocomposite fibers with various CS contents had good preservation effects, with the fiber containing 7 wt% CS demonstrating the best outcomes. As a result, these fibers can postpone strawberry physiological changes and increase their shelf life

In the qualitative evaluation of banana shelf life, the PVA-glyoxal-AuNPs film had the best preservation effect on bananas, highlighting its relevance as a potential material for food packaging applications

28 1 Overview of Nanomaterial Application in Food and Agriculture Sector

Application

Absorbent materials

Nanofluid/ Food processing

Nanofluid/ Food thermal processing

Nanofluid/ Food thermal processing

Nanomaterials

Copper

Multiwalled carbon nanotubes

Aluminum oxide

Aluminum oxide

Table 1.2 (continued) Carrier/Dispersant

Water

Water

Surfactant

Cellulose

Food

Watermelon juice

Tomato juice

Milk

Pineapple and melon juice

Result

References

Water could be replaced with 4% nanofluids while retaining higher levels of vitamin C and lycopene by around 6 and 10%, respectively

(continued)

[110]

The treated tomato juice’s greatest lycopene content [33] (45 mg/kg) was attained when larger nanoparticle quantities and shorter thermal processing times or temperatures were used. The original pH and acidity values of tomato juice were not significantly altered by the concentration of nanoparticles; however, treated tomato juice with nanofluid processing retained a higher lycopene content than tomato juice treated thermally (with hot water)

Increased heat transfer efficiency led to increased heat [124] exchange with milk fluid in a short period of time, which allowed for the pasteurization of milk and the creation of the products before the development of fouling in the exchanger plates

Melon and pineapple juice consist of copper oxide [123] composites demonstrated remarkable antifungal action, resulting in a reduction of about 4 log cycles in the loads of spoilage-related yeasts and molds. The presence of metallic copper composites in pineapple juice led to a significant reduction of yeasts and molds by 4 log cycles. However, it should be noted that their antifungal activity was found to be reduced when in contact with melon juice

1.7 Nanoenabled Food 29

Application

Nanofiltration

Nanofiltration

Nanomaterials

PVDF

NF270 membrane

Table 1.2 (continued) Carrier/Dispersant

Food

Blackberry juice

Strawberry juice

Result

References [44]

The best potential for concentration of the primary [125] polyphenolic chemicals found in blackberries was demonstrated by NF270 membrane at 3 MPa (maximum permeate flux and solute retention). Since sugars were totally maintained and acids were only kept to a lesser extent at high pressures, the NF270 membrane may also be useful for deacidifying the juice

Nanofiltration has proven to be a successful alternative for concentrating the primary bioactive components of strawberry juice while preserving the juice’s key phenolic compounds and red color

30 1 Overview of Nanomaterial Application in Food and Agriculture Sector

1.8 Toxicity and Safety Concern of Nanomaterials in Food Packaging

31

1.8 Toxicity and Safety Concern of Nanomaterials in Food Packaging Numerous products developed as a result of the rapidly expanding field of nanotechnology pose a serious threat to the general public’s health. Despite the fact that many food ingredients and constituents have a nanostructure as part of their natural makeup, adding synthetic nanoparticles to the food supply chain could cause dangerous contaminants to accumulate in foods, endangering human health as well as having an adverse impact on the environment. Thus, despite the many benefits of adopting nanotechnology for food packaging, one of the biggest drawbacks is its hazardous migration into food [126]. To improve the mechanical and barrier properties of conventional and biodegradable food packaging materials, nanoparticles have been engineered and used in the packaging of food products. In addition to this, they provide novel active and intelligent functionalities, which means that the packaging materials incorporate active or intelligent components with the intention of releasing substances into, onto, or out of the packaged food or the environment around it, as well as providing pertinent information regarding the conditions under which they are to be used [127]. Consuming food that has come into contact with nanopackaging may provide an exposure pathway and pose a serious health risk due to the particle nanomaterials that are transferred from the packaging into the food. This is especially true in terms of toxicity and ecotoxicity. The degree of migration, the toxicity of the used nanoparticle, and the velocity of absorption of the particular food would have a significant effect on the toxic effect of particles [128]. The increasing body of evidence highlights the potential health hazards associated with the absorption of nanoparticles, particularly in foods. The excessive intake, bioaccumulation, and overactivity of nanoparticles can have adverse effects on health, exposing individuals to various risks and hazards [129, 130]. There has only been a small amount of research done on how foodborne nanoparticles might affect health. The possible dangers that are linked to nanoparticles are dependent on their chemical makeup, their physical and chemical properties, the ways in which they interact with tissues, and the degree of exposure they get. Prior to evaluating a nanomaterial for potential usage in the food and feed business, it is necessary to first solve a number of universal concerns [28]. EFSA has just recently amended its risk assessment standards to include nanoscience and nanotechnology uses in the food and feed supply chain, as well as their implications on human and animal health. This was done in order to ensure that consumers are receiving the most accurate information possible. EFSA now has authority over a wider range of topics, including novel foods, food and feed additives, food contact materials, and pesticides. Concern has been raised about the possibility of nanoparticles migrating into packaged food; however, there have not been nearly enough migration studies or risk assessments conducted to fully grasp the scope of this phenomenon. The transfer of mass that occurs when nanoparticles enter food can be thought of as a process similar to mass transfer, in which it is possible for smaller molecules to become entrapped

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

inside the packaging material and then be released into the food product. In the past, people thought that it followed a diffusion process similar to the one described by Fick’s second law, which posed a substantial number of possible dangers. Having said that, additional research is necessary in order to accurately analyze and evaluate these hazards [131]. The six unresolved issues with nanoparticle dispersion from food packaging based on polymer-based materials to consumers are depicted in Fig. 1.11 [132]. In this context, low-density polyethylene (LDPE-ZnO) was examined for ZnO nanoparticle migration under the following four conditions: distilled water, ethanol (50%), acetic acid (4%), and n-heptane at 70 °C for 30 min [133]. ZnO moved from

Fig. 1.11 Six unresolved issues with nanoparticle dispersion from polymer-based food packaging films are shown in an illustration (FCM food contact materials, ENO engineered nano-objects). An example of a problem or difficulty with foodborne nanoparticles and suggestions for how to overcome it, adapted from [28]

1.8 Toxicity and Safety Concern of Nanomaterials in Food Packaging

33

0.009–0.029 mg/L in distilled water to 0.017–3.416 mg/L in acetic acid, and 0.006– 0.013 mg/L in 50% ethanol, with no migration seen in n-heptane. The dissolution of ZnO nanoparticles in artificial lysosomal fluids (pH = 5.5) was larger than that in interstitial fluids (pH = 7.4), and Zn nanoparticle migration is predominantly determined by the pH of the media [134]. In a study conducted by Ozaki et al., the migration of silver (Ag) and zinc (Zn) from food contact polymers containing nanosilver and silver ions (Ag + ) labels into various food simulants was evaluated [135]. In addition, the presence of hazardous metals like cadmium (Cd), lead (Pb), and arsenic (As) was evaluated during the course of the study. Six different nanosilver compounds were investigated, and their levels of silver and zinc ranged from 8.4 to 140 mg kg−1 and 21 to 200 mg kg−1 , respectively. The nanosilver products and the five Ag+ products exhibited comparable levels of the elements silver and zinc. None of the samples had any traces of lead, cadmium, or asbestos. It was most noticeable in 4% acetic acid, although it was also seen in water and 20% ethanol. The migration of silver and zinc was visible. The migration ratios of Ag+ and nanosilver products did not exhibit any significant differences from one another. The data obtained from ultrafiltration showed that the silver that migrated from nanosilver products into 4% acetic acid was in its ionic form, but the silver that migrated into water and 20% ethanol stayed in its nanoparticle form. Another study showed that when Ag (0.02 mg/kg) and TiO2 nanoparticle migration in cottage cheese was taken into account, the migration of Ag grew over time. However, the migration of silver nanoparticles was below the 10 mg/kg threshold set by EFSA [136]. Another study also investigated the migration of AgNPs from polylactic acid (PLA) in the presence of 50% ethanol [137]. The findings demonstrated that decreasing Ag nanoparticle migration from the polymer was caused by increasing treatment pressure (200–400 MPa). At treatment pressures of 200–400 MPa, Ag nanoparticle migration was 0.354 and 0.409 mg/kg, respectively. Due to their water resistance, antibacterial, antimicrobial, and protective properties, engineered nano-objects have become widely used in the food business. Sadly, despite the fact that engineered nano-objects can be widely used and distributed, their toxicity and potential for hazards have not been adequately investigated. Engineered nano-objects, however, can be tailored to fit certain requirements and are preferred for their low toxicity to people. They could also be used to immediately detect pollutants. Due to all of these qualities, engineered nano-objects are an effective remedy for environmental contamination [138]. Because the use of nanomaterials in food packaging will eventually be discarded, there must be some safety regulations indicating the permitted ranges or restrictions of nanoparticles used in food applications. The use of nanoparticles in food packaging may also cause problems with environmental standards. The rules governing the use of nanotechnology to food have been compiled with information [139]. In order to determine the possible toxicity of nanostructured materials utilized in the food business, more research is required. Additionally, a worldwide knowledge-sharing framework is needed so that food scientists, researchers, and consumers may collaborate and address all concerns about implementation, consumption, disposal, and long-term impacts. It will enable improvements in food-related applications and research.

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1 Overview of Nanomaterial Application in Food and Agriculture Sector

1.9 Summary In the first chapter of this book, a complete review of the use of nanomaterials in the food and agriculture industries is presented. The report starts out with an introduction that discusses the significance of nanoparticles in the food sector in general as well as in specific areas. This chapter examines the distinctive properties of nanomaterials, such as their size, surface area, and reactivity, which make them suited for application in the food business. These properties include size, surface area, and reactivity, among others. The use of nanoparticles in a variety of food processing applications is being researched. This includes nanofiltration, a technology that can be used in separation and purification processes, as well as nanofluid thermal processing, which is a method that uses nanofluids to enhance the efficiency of heat transmission in the manufacturing of food. The use of nanoparticles in food packaging is investigated, with a particular focus on the potential of these materials to improve the mechanical and barrier aspects of the packaging. It is also important to highlight their capacity to deliver active capabilities, such as antibacterial characteristics. The significance of nanomaterials to the preservation of food is explored, highlighting their capacity to lengthen the shelf life of food while still preserving its quality by means of controlled release mechanisms and barrier qualities. In addition, the chapter examines the various ways in which nanomaterials can improve the quality of food, such as by changing the texture, adding or removing nutrients, or altering sensory qualities. In this article, we propose the idea of nanoenabled food, which entails putting nanoparticles directly into food products in order to confer particular functionality on them. There is discussion of the toxicity and safety risks related with the use of nanoparticles in food packaging. In order to protect the safety of the general public, it is essential to conduct exhaustive risk assessments and adhere to all applicable regulations. In a nutshell, the purpose of this chapter is to provide an extensive review of the several ways in which nanomaterials might be utilized in the food and agriculture industries. It underlines their potential benefits in food processing, packaging, preservation, and quality enhancement, while at the same time addressing concerns over their toxicity and safety.

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27. Ezhilarasi, P., et al., Nanoencapsulation techniques for food bioactive components: a review. Food and bioprocess technology, 2013. 6: p. 628–647. 28. Biswas, R., et al., Application of nanotechnology in food: processing, preservation, packaging and safety assessment. Heliyon, 2022. 8(11): p. e11795. 29. Bratovˇci´c, A., et al., Application of polymer nanocomposite materials in food packaging. Croatian journal of food science and technology, 2015. 7(2): p. 86–94. 30. Salari, S. and S.M. Jafari, Application of nanofluids for thermal processing of food products. Trends in Food Science & Technology, 2020. 97: p. 100–113. 31. Salari, S. and S.M. Jafari, 2 - Nanofluid thermal processing of food products, in Handbook of Food Nanotechnology, S.M. Jafari, Editor. 2020, Academic Press. p. 39–71. 32. Shah, R.K. and D.P. Sekulic, Fundamentals of heat exchanger design. 2003: John Wiley & Sons. 33. Jabbari, S.-S., et al., Changes in lycopene content and quality of tomato juice during thermal processing by a nanofluid heating medium. Journal of Food Engineering, 2018. 230: p. 1–7. 34. Jafari, S., et al., Heat transfer enhancement in thermal processing of tomato juice by application of nanofluids. Food and Bioprocess Technology, 2017. 10: p. 307–316. 35. Jafari, S.M., et al., Evaluation of performance and thermophysical properties of alumina nanofluid as a new heating medium for processing of food products. Journal of Food Process Engineering, 2017. 40(5): p. e12544. 36. Longo, G.A., G. Righetti, and C. Zilio, Development of an Innovative Raw Milk Dispenser Based on Nanofluid Technology. International Journal of Food Engineering, 2016. 12(2): p. 165–172. 37. Zhang, L., et al., Sonophotocatalytic inactivation of E. coli using ZnO nanofluids and its mechanism. Ultrasonics Sonochemistry, 2017. 34: p. 232–238. 38. Salehi, F., Current and future applications for nanofiltration technology in the food processing. Food and Bioproducts Processing, 2014. 92(2): p. 161–177. 39. Chen, Z., et al., Fully recycling dairy wastewater by an integrated isoelectric precipitation– nanofiltration–anaerobic fermentation process. Chemical Engineering Journal, 2016. 283: p. 476–485. 40. Castro-Muñoz, R. and E. Gontarek, 3 - Nanofiltration in the food industry, in Handbook of Food Nanotechnology, S.M. Jafari, Editor. 2020, Academic Press. p. 73–106. 41. Van Der Bruggen, B., et al., A review of pressure-driven membrane processes in wastewater treatment and drinking water production. Environmental Progress, 2003. 22(1): p. 46–56. 42. Conidi, C., E. Drioli, and A. Cassano, Membrane-based agro-food production processes for polyphenol separation, purification and concentration. Current Opinion in Food Science, 2018. 23: p. 149–164. 43. Arriola, N.A., et al., Potential of nanofiltration for the concentration of bioactive compounds from watermelon juice. International Journal of Food Science & Technology, 2014. 49(9): p. 2052–2060. 44. Arend, G.D., et al., Concentration of phenolic compounds from strawberry (Fragaria X ananassa Duch) juice by nanofiltration membrane. Journal of Food Engineering, 2017. 201: p. 36–41. 45. García-Martín, N., et al., Sugar reduction in musts with nanofiltration membranes to obtain low alcohol-content wines. Separation and Purification Technology, 2010. 76(2): p. 158–170. 46. Kumar, P., et al., Perspective of Membrane Technology in Dairy Industry: A Review. AsianAustralas J Anim Sci, 2013. 26(9): p. 1347–1358. 47. Pouliot, Y., Membrane processes in dairy technology—From a simple idea to worldwide panacea. International Dairy Journal, 2008. 18(7): p. 735–740. 48. Pontalier, P.-Y., A. Ismail, and M. Ghoul, Mechanisms for the selective rejection of solutes in nanofiltration membranes. Separation and Purification Technology, 1997. 12(2): p. 175–181. 49. Sjöman, E., et al., Separation of xylose from glucose by nanofiltration from concentrated monosaccharide solutions. Journal of Membrane Science, 2007. 292(1): p. 106–115. 50. Catarino, I., et al., Assessment of saccharide fractionation by ultrafiltration and nanofiltration. Journal of Membrane Science, 2008. 312(1): p. 34–40.

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Chapter 2

Nanomaterials: Plethora of Opportunities as Smart Packaging, Preserving, and Processing Agent in Food Industry

Abstract The immense potential of nanomaterials in revolutionizing smart packaging, food processing, and food preservation across a wide spectrum of food products is explored in this book chapter. The use of nanopackaging materials, both existing on the market and with future potential, is thoroughly investigated. The goal of developing nanostructured food additives is to improve texture, consistency, and flavor while also prolonging food shelf life and minimizing food waste caused by microbial infestation. Nanocarriers serve an important role in food additive delivery systems, ensuring minimal disruption to the product’s natural morphology. The particle size of nanomaterials is an important factor in the efficient absorption of bioactive chemicals, with submicron nanoparticles outperforming bigger microparticles in some cell lines. A perfect delivery system should provide exact compound distribution, customized release rates, and long-term compound stability. Nanotechnology in emulsion synthesis, encapsulating techniques, and biopolymer matrices provides an optimal delivery system with the required qualities. Nanopolymers are gradually replacing traditional food packaging technologies, while nanosensors detect mycotoxins, pollutants, and infections. Nanoparticles outperform older techniques in terms of release and encapsulation efficiency. Controlled release, effective interaction with the food matrix, taste modulation, targeted availability, and protection against heat, moisture, and chemical degradation during processing and storage are all made possible by nanoencapsulation. The importance of nanotechnology in improving the flavor, texture, appearance, shelf life, and nutritional content of food products is emphasized. Bioactive substance nanoencapsulation extends shelf life by delaying degradation until the compounds reach their designated target location. Furthermore, the use of edible nanoparticle coatings functions as a moisture barrier, provides acceptable color, and contains enzymes, antioxidants, and antibrowning agents, increasing shelf life even after package opening. Chemical degradation is substantially mitigated by encapsulating functional components within droplets and controlling interfacial layer characteristics. Mechanical strength, moisture and gas permeability, and biodegradability are all desirable properties of nanomaterial-based packaging materials, making them intelligent and active alternatives to traditional approaches. Nanocomposites are widely used in packaging and coating materials because of their antibacterial qualities, mechanical and thermal stress tolerance, and long shelf life. Inorganic nanoparticles are of special interest for antimicrobial food © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_2

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packaging due to their outstanding antibacterial activity at low concentrations and good durability. This book chapter focuses on nanoparticles’ critical role in the evolution of smart packaging, preservation, and processing in the food business.

2.1 Introduction The propensity of foods to biodegrade makes them unacceptably bad for consumers. For this reason, food encapsulation is essential for proper food handling and quality preservation. The main functions of traditional food encapsulation are protection, communication, convenience, and preservation. These fundamental functions are enhanced by design enhancement as well as intelligent encapsulation [1, 2]. The significance of overwrapping in the food industry is limited to food preservation and, furthermore, to transportation and sale. Reportedly, the four most important effects of encapsulation are protection, convenience, communication, and containment [3]. Concerning defective containment, defective containment causes leakage of materials from seals or closures, whereas inadequate protection may result in exposure of food to external conditions such as odors, humidity, and compression state. What is more, inefficient and complicated packaging may arouse concerns regarding handling, opening, and storage of food products, and poor communication may deter customers from purchasing them [4]. In recent years, nanotechnology has been used to create intelligent, interactive, and responsive packaging for foods with improved functionalities, which is fleetingly replacing passive or conventional food packaging [5]. Nanotechnology is an emerging field involving the characterization, manipulation, fabrication, and production of materials at the nanoscale from 1 to 100 nm [6]. Nanomaterials and nanoparticles contained in edible coatings are superior to conventional packaging substances for preserving and maintaining the quality of products. Meanwhile, the containing nanoparticles can change the mechanical and physical properties of polymers used for packaging by enhancing the barrier, flexibility, durability, strength, and reusability [7]. Each use of nanomaterials in the food packaging industry is justified by their added value. The significant aspects of food quality such as appearance, color, flavor, texture, and nutritive value should be protected from undesirable deterioration, thereby significantly increasing the shelf life of the product. “Active” and “intelligent” packaging provided a more thorough explanation in Robertson’s report. Author described “intelligent” packaging as having an inside indicator that offers details about the history of the package and/or the quality of the food. Although the term “active” packaging refers to a particular auxiliary component, it is frequently explicitly labeled in or on packing materials to improve the system’s performance [3, 4]. Numerous studies have demonstrated that nanomaterials can exert their antibacterial effects through a variety of mechanisms, making them particularly suitable for use as polymer fillers in active packaging materials for long-term food preservation. The utility model can effectively take into account both the current economy and

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the security. In addition, by filling particles in the polymer, the stiffness and tensile strength of the material can be improved to a certain extent, despite the fact that the addition of particulate fillers can result in composites that are brittle or opaque [8]. In the present chapter, nanomaterial-based food packaging has been classified into different aspects like “passive,” “active,” or “intelligent.” As depicted in Fig. 2.1, the fundamental category addresses the particular function of nanomaterials in food packaging. Meanwhile, the functionality of the corresponding nanomaterials also increases proportionally as the role changes to active or intelligent. From the report, the lower category in the pyramid model refers to the “improved” function of nanomaterials. This specific function is related to the presence of nanomaterials, which passively change the performance of food packaging [9]. The middle category depicts the “active” function of nanomaterials, which contributes to food preservation. Lastly, the top option shows the keywords about the quality of food.

Fig. 2.1 Pyramid model on the role of nanomaterials in food packaging, where the function of the respective nanomaterials from bottom to top increased. Reprinted with permission from Novel Approaches of Nanotechnology in Food, Copyright 2016, Elsevier [4]

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2.2 Nanoencapsulation and Nanoemulsification New food packaging can be created using nanoencapsulation technology, which is a practical alternative for protecting bioactive chemicals while ensuring their regulated release [10, 11]. According to Huang, Li, and Zhou, the primary goal of encapsulating bioactive chemicals is to improve the stability, adaptability, and bioavailability of food packaging [12]. There are two key benefits: the potential for the dispersion of water-insoluble compounds and the increased control over additive release. At the same time, a small amount of expensive compounds can be required to provide effective protection for food [13, 14]. Although flavors are great chemicals for active packaging systems, problems like their unpredictable nature and high volatility make them challenging to use on an industrial scale. A promising method for overcoming these restrictions by shielding them and enabling their application to polymer matrices is nanoencapsulation [15]. Numerous studies have been reported on the application of nanocapsules in active food packaging for a variety of foods and their antioxidant and antibacterial effects [16–18]. In order to develop systems capable of effectively releasing the active chemicals, the best encapsulation approach must be chosen. This decision has advantages like the physicochemical characteristics, necessary particle size, kind of active ingredient, and wall material of nanocapsules [19]. The development of nanocapsules can be done using top-down and bottom-up methodologies, as depicted in Fig. 2.2a. Here, the top-down operations entail size reduction of particles into smaller ones without the strong solvents. This kind of method usually employed a variety of wet-milling techniques like media milling, microfluidization, as well as the highpressure homogenization. However, all top-down processes need a lot of energy, and in some situations, they are also expensive and time-consuming. The bottom-up method involves using the organic solvent to dissolve the active ingredient, followed by the addition of an antisolvent while stabilizers are present, which precipitates the mixture further. In the last few years, a few variations of the bottom-up strategy have gained popularity, such as spray drying, emulsion-solvent evaporation, as well as the supercritical fluid processes [20]. Thereafter, authors investigated the effect of a chitosan coating containing free or nanoencapsulated Satureja khuzestanica essential oils (SKEO) on meat. In the experiment, they stored different groups of mutton samples and corresponding additives at 4 °C for 20 consecutive days to explore the chemical, microbial, and sensory characteristics of meat [16]. The nanoliposomes with an average diameter of 93– 96 nm were prepared by thin-film ultrasonic hydration, and four different ratios of soybean lecithin were selected, which were 60:0, 50:10, 40:20, and 30:30, respectively. According to the calculation, the distribution of nanoliposome size as well as the encapsulation efficiency (EE) was 0.83–0.88 and 46–69%, respectively. In addition, the nanoliposomes with the highest EE and lowest droplet size were employed for coating meat samples. The final results indicated that the suitable 2-thiobarbiturate acid value and lower pH had significant effects on preventing microbial chemical deterioration and growth. In addition, the encapsulation technology can slow down

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Fig. 2.2 a Summary of the key methods for nanoencapsulation of active agents. Reprinted with permission from Novel Approaches of Nanotechnology in Food, Copyright 2016, Elsevier [15]. b Schematic of nanoemulsions in food packaging. Reprinted with permission from Food Engineering Reviews, Copyright 2021, Springer Nature [21]

the release of SKEO, prolong its antibacterial and antioxidant activity, and improve its sensory quality. It was also pointed out that chitosan- and SKEO-coated mutton may be an effective choice to extend shelf life. The usage of nanoemulsions in the food packaging sector is one of the pertinent applications [21] (Fig. 2.2b). Water-inoil or oil-in-water nanoemulsion delivery systems can be developed using a number of preparation processes, including low- and high-energy methods. Depending on the application, nanoemulsion-based delivery systems may additionally include nutrients, flavorings, preservatives, or colors. Compared to samples packaged in conventional packaging, this technology may stop microorganism development, changes in food color and appearance, weight loss, moisture content reduction, unwanted flavor and taste, as well as slow down the pace of oxidation and browning. Nanoemulsions have a lot of potential, but there are several unique problems that need to be

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solved. Some food characteristics, including taste, texture, flavor, color, spoilage, and stability, can be managed using these potential nanotechnologies. Further research is required to determine the use of nanoemulsions and their acceptable carriers, optimize consumption, and remove production and processing barriers in order to secure their commercial use.

2.3 Nanofiltration In comparison with previous pressure-driven membrane separation technologies, nanofiltration (NF) is a fairly novel and complicated research strategy [22]. Numerous literature publications on various topics, including the purification of sugar and water, the specific treatment of whey, the clarity and concentration of juices, and fractionation, show the promising evaluation of nanofiltration’s application in food processing [23, 24]. It is possible to use nanofiltration in the manufacture and formulation of functional foods and drinks in addition to its typical application in juice processing to concentrate and separate valuable bioactive ingredients from fruit juices [25]. Arriola et al. assessed how well watermelon juice might be concentrated by nanofiltration [26]. The results showed that with an increase in the volume reduction factor, the concentration of total phenolic flavonoids and lycopene in the proposed samples also increased accordingly. In terms of concentration, the volume reduction factor of those three produced the highest values for flavonoid, lycopene, and total phenolic contents. The presence of lycopene, ascorbic acid, phenolic compounds, and flavonoids and their promotion potential in both hydrophilic and lipophilic fractions were found to be closely correlated. Furthermore, nanofiltration also appears to be an alternative technology that can be used to get low-alcohol wines; as due to social and health concerns, low-alcohol beverages are more in demand internationally [27, 28]. Compared to reverse osmosis, this method can offer higher alcohol flow rates and higher penetration rates. The organoleptic properties of the original product can also be preserved by using the modest pressures and temperatures during such a procedure. By using nanofiltration, Gracia-Martin et al. research the sugar decrease in essentials to create wines with a modest alcohol decrease accordingly [29]. In particular, two subsequent nanofiltration stages are used to reduce the amount of sugar. The authors have used two different musts to test the method: the red and white, here, must be made from Tinta de Toro grapes and Verdejo grapes, respectively. To lower the alcohol concentration of the produced wines by 2°, it is necessary to evenly mix the lees obtained from nanofiltration with the untreated lees or the retention of the first step of nanofiltration. Each sample must be fermented with a control sample to confirm the validity of the experiment. The wines’ alcohol reduction has been satisfactory. There has been a minor loss of color and scent in some compounds, nevertheless. Figure 2.3 shows the two-step process in the production of low-alcohol wine by nanofiltration. Nanofiltration is largely utilized in the dairy sector for specific purposes such as lactose-free milk, partial demineralization of whey, and whey volume reduction [30].

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Fig. 2.3 Two-stage nanofiltration (NF) procedure for producing low-alcohol wine is illustrated graphically. Reprinted with permission from Handbook of Food Nanotechnology, Copyright 2020, Elsevier [22]

The dairy industry uses nanofiltration extensively throughout the world to desalt brines, mother liquors, and whey [31]. This is because nanofiltration membranes, which have a selectivity that is halfway between ultrafiltration and reverse osmosis membranes, offer an intriguing option to ion exchange and electrodialysis if just mild demineralization is needed. With this method, whey is demineralized while also being concentrated, resulting in cost, time, and water disposal savings. Additionally, nanofiltration has been suggested for the partial removal of acid from acid whey (approximately 42%) and salt removal from salty whey (reaching up to 84%). The concentration of whey protein can be regulated in the dry matter range of about 20–22%; meanwhile, the mineral content can be reduced by 20–50%. Nanofiltration

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membranes have additional applications in the dairy industry. For example, ultrafiltration of whey permeates containing the desired lactose for concentration and mineral removal, instead of traditional vacuum evaporation methods, could be used for milk concentration in yoghurt production. In addition, nanofiltration membrane can be used for selective demineralization to meet the needs of yoghurt production. Nanofiltration can selectively separate monosaccharides and di/trisaccharides with interesting yields despite the small changes in their molar masses. For instance, it is able to distinguish glucose from raffinose, lactose, and even sucrose [32]. Numerous studies have shown that nanofiltration membranes can effectively separate xylose from glucose, which is important for the industrial purification of xylose for the manufacturing of xylitol. For example, here, three distinct nanofiltration membranes (Desal-5 DK, Desal-5, and DL 270) with molecular weight cut-off (MWCO) ranging from 150 to 300 Da were employed to process solutions containing xylose and glucose in varying ratios of mass and concentrations of overall monosaccharide [33]. Research investigated the dextrose retrieval from the crystallization mother liquid, which is a significant by-product of the production of dextrose [34]. Commercial nanofiltration membranes like K-MPS34, K-SR2, Desal-DL, and Desal-DK were used in the recovery operations in order to produce dextrose with a high purity (> 95%). The separation efficiency of the membranes varied depending on their inherent features; in process applications, only one membrane meets industry standards and requirements, which is the Desal-DL. Dextrose purity of greater than 97% was provided by such a membrane in the permeate stream.

2.4 Nanoadsorbent and Nanoporous Nanoadsorbents are distinctive because of their high reactivity, small size, great stability, large surface area, and capacity to renew themselves [35, 36]. The adsorbent molecules adhere to the porous surface of the adsorbent material by the attractive force between the molecules through interaction, which is the mechanism of adsorption. There are two ways that this phenomenon might happen: either physically or through the Diderik van der Waals force or chemical bond force to provide the interaction between the adsorbent and the adsorbent to be adhered together [37]. Regarding the capacity for sorption, compound regeneration from extraction, cost of manufacture, and ease of application, graphene is preferred over other sorbents for a variety of substances, including phenols, cocaine, adenosine, and squalene [38]. The separation of pesticides from vegetables, fruits, and even liquid samples is claimed to be possible using graphene oxide coated with modified chitosan hydrogel. This specific material is an efficient magnetic solid-phase extraction adsorbent; meanwhile, its adsorption capacity is 27 mg/g, according to the report [39]. These researchers came to the conclusion that the delocalized π-electron system enabled pesticides to interact with nanoadsorbents in an efficient manner [40]. The film made of graphene allows for the packaging of food due to its gas barrier qualities. These nanocomposites could be used as coatings or films for food preservation.

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When combined with biopolymers like chitosan, the graphite family can enhance chitosan’s technical properties. However, graphitic materials’ antibacterial properties can lengthen the shelf life of food goods. In the drinking water and food industries, activated carbon is utilized in diverse applications [41] including the adsorption of phenolic chemicals from food factory wastewater [42]. Aliakbarian et al. examined the phenolic adsorption of olive wastewater. Maximum adsorption capacity was attained under this condition; according to the results, the optimum conditions can be achieved by using 8 g of activated carbon per 100 mL of solution [43]. In addition, the pseudo-second-order model was determined to be the best fit for the kinetic outcomes, while the Langmuir isotherm was the best model for the sorption system. In conclusion, the olive mill wastewater plant’s polyphenols and carbohydrates were completely recovered by activated carbon, which could then be used to produce bioethanol and polyphenols that can be used in a variety of industries. The activated carbon made from pecan shells (PSBAC) has been developed with a large specific surface area (1500 m2 /g) and pore volume (0.7 cm3 /g) [44]. It was discovered that the PSBAC’s maximum adsorption capacity was pH = 3, 3 g/L adsorbent dosage, 41.66 mg/g at 55 mg/L iron(II) at 30 °C for 90 min. The pseudo-second-order model, here, is the most effective approach to explain iron(II) adsorption. The adsorption system was endothermic, increased entropy, and had favorable thermodynamics. Kim et al. developed flexible, biodegradable nanoporous polycaprolactone-based (FNP) films for food packaging systems by applying a plasma-enabled surface modification technique [45]. By examining different criteria (mold production, hardness, freshness, cosmetic changes, weight loss, and total soluble solids contents), their ability to preserve bananas, tangerines, and tomatoes at room temperature and the refrigerator temperatures were examined under this condition (Fig. 2.4). By regulating moisture evaporation and preventing mold growth, the proposed system improved the fruit storage quality (i.e., preserved appearance, better firmness, decreased weight loss, and sugar contents) as compared to conventional polyethylene terephthalate-based containers. The results showed that the FNP film-based food packaging system prevented the growth of mold mycelia as well as noticeable alterations to the surfaces of tangerine, tomato, and even banana peels. These results were attributable to the FNP film’s nanoporous structures’ favorable control of moisture evaporation and chemically modified surface. Compared with the traditional polyethylene terephthalate (PET) container and FF film packaging systems, the FNP film food packaging system has shown significant advantages in fruit storage and brought revolutionary innovation to the industry. By introducing active ingredients and functional additives into FNP films, this packaging technology provides a more efficient solution for freshness preservation and extended shelf life.

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Fig. 2.4 Image above depicts the preparation and characterization of flexible nanoporous polycaprolactone (FNP) films for active food packaging systems. a It mainly outlines the methodology and strategy of the study. Grouping experiments were used to compare the ability of open and closed PET packaging systems (the control group) and flexible flat polycaprolactone polymer (PCL) and FNP film packaging systems to maintain Solanum lycopersicum, orange, and banana during storage. b FNP films were fabricated for food packaging systems and prepared by oxygen plasma modification of the surface of flexible flat PCL films. This modification can form a nanoporous structure on the surface of the film and increase its adsorption performance and surface area, thus improving its application in food packaging systems, adapted from [45]

2.5 Nanomaterials as Active and Intelligent Packaging Material It has been well reported that, as a packaging agent, nanomaterials play an intelligent role by communicating information about the packaging history of food materials and their quality. Smart nanomaterials play many important roles in the field of food packaging. Examples include oxygen and carbon dioxide sensors, time– temperature indicators, freshness indicators, and traditional and static food quality indicators, just like “Best Before.” Packaging nanomaterials may produce a visual or electrical signal response depicting food’s quality either by interacting with the packet’s internal materials, like headspace or food components, or by interacting with external environmental conditions that correlate with [4, 46]. This information provides customers with information about the safety and quality of food materials and enables producers to take action according to it during the production and distribution processes [47]. Figure 2.5a shows the involvement of nanotechnology in various aspects of intelligent food packaging. Active packaging systems usually use active compounds to interact with microorganisms, oxygen, water vapor, ethylene, and other harmful factors in order to extend

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Fig. 2.5 a Diagram illustrating the concept of intelligent packaging and its integration with nanotechnology. b Diagram depicting the concept of active packaging and its incorporation of nanotechnology. Reprinted with permission from Trends in Food Science & Technology, Copyright 2014, Elsevier [46]

the shelf life of food and maintain its quality. Common additives are antibacterial compounds, ethylene, oxygen absorbents, preservatives, and water vapor absorbent removers. Figure 2.5b depicts the basic components of a typical nanotechnologyactivated active packaging system that are the active components and carriers assembled by nanotechnology. The carrier can integrate active ingredients into food packaging to improve the shelf life, food quality, and/or safety of the product. The carrier

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can interact with internal and/or external factors to achieve the desired effect through predetermined actions. This interaction can be triggered by the factors shown in the blue arrow to trigger the desired action shown in the red arrow. Through the application of nanotechnology, active packaging systems can achieve better food preservation effects and improve product quality and safety levels.

2.5.1 Fruits and Vegetables In order to maintain their quality, safety, and expiration life, fresh fruits and vegetables typically require stringent control of processing conditions throughout the production-to-consumption distribution chain. These products are alive and continue to breathe after being harvested, consuming oxygen and emitting carbon dioxide. Post-harvest metamorphosis is influenced not only by cultivars, maturity, and other internal factors but also by treatment conditions and external factors. To maintain the quality of these products throughout the supply chain, it is necessary to control temperature, humidity, gas composition, and other environmental factors. These control conditions will aid in slowing the metabolism of fresh fruits and vegetables, delaying their quality decline and deterioration, so that their nutritional value and eating quality are preserved [48]. Temperature control and monitoring are of utmost importance during all phases of the distribution and storage of food and vegetables. Temperature is unquestionably considered one of the crucial conditions employed to slow the deterioration of fresh agricultural products like vegetables and fruits, as it has a significant impact on respiration, ethylene production, and transpiration rates [48]. Other than this, handling conditions and surrounding gas production also have a major impact on food storage. It has been shown that senescence can be accelerated by mechanical damage brought on by impact, compression, or vibration [49, 50]. Further, as the oxygen concentration falls, so does the rate of respiration. Generally, carbon dioxide has the opposite effect, though this can vary based on the product type, level of maturity, concentration range, and exposure duration [48]. Today, those fresh agricultural products are frequently coated with various edible coatings and nanocomposite layers to extend their shelf life using techniques similar to modified atmosphere methods, which have already demonstrated success in preserving the quality of fresh agricultural products [51]. Antimicrobial nanoparticles can be added to edible coatings and films (ECF) as a matrix in order to extend the shelf life and improve the quality of fruits and vegetables. The quality of fruits and vegetables can be preserved, which suggests that numerous ECFs with nanoparticles were employed as the best materials for food applications. An effort is made to keep an eye out for emerging trends in this industry by taking a look at the introduction to these characteristics [52]. The use of coating film as carriers for metal nanoparticles as protective barriers and antimicrobial agents may lower respiration rates, prevent deterioration, extend the shelf life of fresh produce, maintain storage quality, and reduce color changes [53]. To

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demonstrate the nanomaterial coating effect, the researchers compared the uncoated strawberries and mangos to samples that had been exposed to nanocomposites and kept at room temperature for a week period [54]. The activity of polyphenol oxidase (PPO) was suppressed by the nanocomposite coating that contained graphene oxide and chitosan-loaded titanium dioxide nanoparticles (TiO2 NPs). The results showed that the coated samples showed a smaller weight loss and an improvement in appearance. Fruits coated with three different types of nanocomosite films showed higher superoxide dismutase activity levels than untreated samples, suggesting substantial potential for the food preservation sector. Emamifar and Bavaisi demonstrated the antimicrobial effect of alginate and zinc oxide nanoparticles (ZnO NPs) over strawberries [55]. The polysaccharide coating of alginate was found to significantly improve the physical chemistry, sensory quality, and microbial quality of fresh strawberries during cold storage. This is due to the increased antimicrobial activity and antioxidation property of ZnO nanoparticles in the coating, which inhibited the growth of microorganisms and the chemical deterioration of strawberries. Specifically, the addition of nanozinc oxide to an alginate-based coating formulation extends the shelf life of strawberries. In addition, studies have shown that the combination of alginate-based coatings and nanozinc oxide can be used as a potential method to improve the freshness, extend the shelf life, and preserve the quality of strawberries. As the nanozinc oxide concentration in the alginate-based coating solution gradually increased (to 1.25 g/L), the strawberry’s fresh-keeping effect was further improved. Under the specific conditions, a significant reduction in the microbial counts (yeasts and molds) has been observed with improved physiochemical characteristics, enhanced superoxide dismutase (SOD), and reduced peroxidase activity in coated strawberries compared to uncoated strawberries after 20 days of cold storage. In addition, the sensory evaluation revealed a statistically significant (p < 0.05) difference between the panelists’ perceptions of the overall scores of fruits coated with 1.5% SA + 1.25 g/L nano-ZnO versus the other coated and uncoated samples up to 20 days in storage. Thus, the result revealed that strawberries coated with 1.5% sodium alginate and 1.25 g/L nano-ZnO exhibited the lowest levels of microbial proliferation. The incorporation of nano-ZnO into the formulation of the coating enhances its antimicrobial qualities and extends the shelf life of fresh fruit products by up to 20 days. However, it appears that the combination of sodium alginate and nanozinc oxide produces uniform edible coatings. This discovery is beneficial for advancing food preservation technology and improving the quality of fruits. These results demonstrate the antimicrobial effects of combining nanoparticles (such as nanozinc oxide) with other technologies (such as coating) for the preservation and processing of fruits. The related effect of nanocomposite coatings on fruits is depicted in Fig. 2.6A (a and b). Further, Chi et al. [56] demonstrated the impact of various packaging materials on mango quality and preservation. Comparisons were made between polylactic acid (PLA) films, PLA nanocomposite films (PLA/BEO/nano-TiO2 + nano-Ag film and PLA/BEO/nano-TiO2 film), as well as PLA/bergamot essential oil (Beo) films. On the basis of weight loss, fruit hardness, color, total soluble solids content, total

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Fig. 2.6 A Two different internal working mechanisms of nanocomposite (a) the antimicrobial activity and (b) the repel mechanism appeared on the surface of cherry. Reprinted with permission from Advances in Colloid and Interface Science, Copyright 2021, Elsevier [60]. B Schematic to preserve the storage quality of mango through a nanocomposite coating with the help of ZnO nanoparticles and carrageenan. Reprinted with permission from Food Packaging and Shelf Life, Copyright 2018, Elsevier [57]

acidity, vitamin C content, microbial characteristics, and sensory quality measurements, the quality changes of mango stored at room temperature for 15 days were evaluated. During 9–12 days of storage, the weightlessness of mango packed with PLA nanocomposite film was significantly lower than that of mango packed with PLA and PLA/BEO films (p < 0.05). In addition, a mango wrapped in a PLA nanocomposite film could delay the fruit’s hardening and retard the deterioration of its color, total acidity, vitamin C content, and microbial properties. At the conclusion of the storage period, the overall acceptability of the mango packaged with PLA nanocomposite film was still greater than 5 score, remaining within the range of marketability. These findings suggest that PLA nanocomposite film is an efficient packaging material that could be employed to preserve the freshness of mango and extend its storage life for a half-month period.

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In another study, Meindrawan et al. demonstrated a coating technique to reduce mango quality loss [57] (Fig. 2.6B). A traditional carrageenan coating was used to cover the mango, along with fillers of 0, 0.5, and 1% ZnO nanoparticles by weight of carrageenan. The findings showed that compared to the ZnO nanocomposite film, the tensile strength of the carrageenan film was increased, but the water vapor transmission was dramatically reduced. Interesting enough, the carrageenan ZnO nanocomposite films’ (CZ) elongation parameters were not considerably greater than those of the carrageenan-only films. Additionally, the ZnO nanoparticles added to the regular carrageenan coating made it exhibit antibacterial qualities and have an antibacterial effect on Escherichia coli. Mangoes exposed to CZ 0.5% and CZ 1% of nanocomposite coating treatments experienced a considerably slower reduction in total acidity on day 13 of storage than the control samples. After 7 days of storage, the mangoes in the control sample emitted the most carbon dioxide, reaching a peak at that time. In comparison with samples without coatings, the mangoes with CZ 0.5 coatings showed no damage up until day 33. In comparison with coverings made of carrageenan, adding ZnO nanoparticles encouraged weight loss in the fruit. Last but not least, the CZ-1 coatings’ properties could prolong the shelf life of fresh mangoes. Due to their high metabolic activity, relative water content sensitivity to microorganisms, and weight loss during storage, a few fruits have a short postharvest life. To solve these problems, carboxymethyl cellulose (CMC)-guar gumsilver nanocomposite films (CG-Ag0 NC) have been developed [58]. The reduction of Mentha leaf extract led to the development of silver nanoparticles in the CMCguar gum matrix. Zone inhibition data with ten food pathogenic microorganisms was used to calculate the antibacterial activity of CG and CG-Ag0 NC. Strawberries were used as the model fruit in a test to determine the shelf life of CG-Ag0 NC films and to compare them to other packaging films. In terms of freshness, shelf life, and weight loss, the results are promising. The result showed that strawberries packaged with antimicrobial films lost significantly less weight than those packed with control films. The film containing silver nanoparticles (AgNPs) had a stronger fresh-keeping effect and may extend the shelf life of strawberries when compared to the control film and the commercial film. Costa et al. also showed a procedure for creating silver-montmorillonite (Ag-MMT) antibacterial nanoparticles. The process involves adding silver ions to a nitrate solution to replace the Na+ in natural montmorillonite, followed by a heat reduction reaction [59]. The shelf life of salad made from fresh fruit can be effectively extended by using Ag-MMT as an antibacterial agent. During storage, sensory and microbiological quality have been monitored to determine their impact on product shelf life. Monitoring the principal deterioration microorganisms served to determine the microbiological quality (yeasts and molds, lactic acid bacteria, coliforms, psychrotrophic bacteria, and mesophilic bacteria). In addition, a few traits and attributes of the product can be empirically observed in order to assess the evolution of sensory quality. The findings demonstrated that the active packaging comprising Ag-MMT nanoparticles significantly inhibited microbial growth, particularly at the highest tested concentration. As a result, the samples preserved using this active packaging method exhibit higher sensory quality. Therefore, using Ag-MMT nanoparticles to preserve the sensory qualities of meals and

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increase their shelf life may be a potential strategy. These results offer a valuable scientific foundation for the creation of more sophisticated food preservation technology. The result suggests that the sensory qualities of a product are crucial in determining its acceptability. At the same time, to further support the investigation into the effectiveness of the product in microbial control and to guarantee the quality and safety of the product, it must be emphasized that none of the samples had a microbiological concentration that was higher than the permissible limit. For this reason, the 20-NP fruit salad, even though it contained the lowest microbial concentrations, 15-NP, 10-NP, and CNT samples exhibited a kinetic of deteriorating sensorial quality that was remarkably similar. Contrariwise, the 20-NP sample demonstrated higher product acceptability. Specifically, a five-day increase in shelf life was observed for sample 20-NP. In conclusion, the final results stated that Ag-MMT nanoparticles optimized in a suitable packaging system can be used to provide a golden key for preventing the deterioration of fresh-cut fruit’s quality. Saravanakumar et al. proposed a method for synthesis and characterization of silver nanoparticles polyvinylpyrrolidone (PVP) using glycerosomes (C/G-PVPAgNPs) via chemically and green synthesis approach and compared their antimicrobial activity. Authors were able to extend the shelf life of fresh-cut pepper (FCP) by successfully using the synthesized nanomaterial as an antibacterial nanocoating agent [61]. The UV spectrophotometer results indicated the formation of C-PVPAgNPs and G-AgNPs with a peak at 400–420 nm. With the help of Fourier transform infrared spectroscopy (FTIR), the creation of G-AgNPs was reportedly aided by plant compounds found in pedicel extract. After amplification, G/C-PVP-AgNPs showed the corresponding PVP and glycerol peaks. The presence of Ag in G/CPVP-AgNPs was confirmed by an X-ray diffractometer (XRD), which promoted the synthesis of G-AgNPs. According to the results of antibacterial activity testing, GPVP-AgNPs showed greater antibacterial activity than C-PVP-AgNPs, with lower minimum bactericidal concentrations (MBC) as well as inhibitory concentrations (MIC). These findings suggested that G-PVP-AgNPs had a somewhat superior bacteriostatic impact. When used, the G-PVP-AgNPs nanocoating may extend the shelf life of freshly cut red or yellow sweet peppers to 12 days at a low temperature (around 4 °C) without negative effects on the physicochemical properties or physical chemical characteristics. Additionally, whereas uncoated fresh-cut sweet pepper juice damaged roundworm cells, G-PVP-AgNPs-based FCP juices were not harmful to roundworm survival. The findings indicate that G-PVP-AgNPs has a wide range of potential applications in the food business as a preservative. This research offers solid scientific justification for the creation of improved food preservation methods as well as a potential long-term fix for the food business.

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2.5.2 Meat, Fish, and Seafood Products Likewise for fruits and vegetables, nanotechnology is a swiftly developing method for extending the shelf life of meat, fish, poultry, and seafood products that operates throughout the entire production chain, from processing to packaging [62].

Meat Because of some effective conditions like high water content, pH, and nutrient content, raw meat products are easily perishable; therefore, the primary concern of the food industry is to increase the expiration life of their products [63]. Several studies have been conducted on the use of essential oils in conjunction with nanoparticles to extend the microbiological shelf life of livestock and meat products. For instance, a pullulan/chitosan-based multifunctional edible composite film was effectively created for packaging pork belly by boosting the action of ZnO nanoparticles and propolis essential oils. Significant antibacterial action was demonstrated against E. coli and Listeria monocytogenes by ZnO nanoparticles and propolis essential oils. The nanocomposite film exhibited a 100% bactericidal impact on E. coli and Listeria monocytogenes after 6 and 12 h in an appropriate storage environment. The results obtained indicate that ZnO nanoparticles and propolis essential oil may have a synergistic bactericidal effect. The change in total aerobic bacterial count was further investigated during an eight-day period when the pork was wrapped in a nanocomposite membrane made of pullulan, chitosan, ZnO nanoparticles, and propolis essential oil and stored at 10 °C. In accordance with the International Commission on Microbiological Specifications for Foods (ICMSF), the permitted microbial limit for beef products is 7 log CFU/g. However, the results showed that after eight days, the total aerobic bacterial count remained at 6.7 log CFU/ g. This demonstrates the internal working principle that the nanocomposite layer may successfully increase the fresh-keeping duration of pork and have an excellent antibacterial impact. The nanocomposite membrane (pullulan/chitosan/zinc oxide/ propolis essential oil) significantly decreased lipid oxidation by roughly 55% because of propolis’s capacity to scavenge oxidative radicals. Alizadeh-Sani and coworkers additionally developed a biopolymer packaging material, the functional components of which were created by adding TiO2 nanoparticles and essential oil droplets to a cellulose nanocellulowhey protein matrix at a ratio of 1 and 2 wt.%, correspondingly. In conclusion, the prepared pullulan/chitosan-based multifunctional edible composite film demonstrated excellent antibacterial and antioxidant properties in the packaging of pork belly, providing a potential solution for food preservation and quality assurance. This was accomplished by enhancing the action of ZnO nanoparticles and propolis essential oils [64]. The ability of this packaging to prevent chemical and microbial deterioration of lamb meat for 15 days of refrigeration at 4 °C can be evaluated. Periodically, the optical properties, chemical stability, and microbial count of the meat samples were evaluated. During storage, the active packaging

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substantially reduced microbial growth, lipid oxidation, and lipolysis in the lamb meat, extending its shelf life from approximately 6–15 days. The results showed that only a small amount of TiO2 nanoparticles had been released into the meat product during storage. Therefore, these specific active packaging materials using biopolymer materials could behave well for use with meat products. Further, Mathew et al. also demonstrated the development of biodegradable silver nanoparticle-mediated ginger extract-PVA-montmorillonite K10 clay nanocomposite blend films [65]. For the quick and environmentally friendly in situ synthesis of ginger extract-mediated silver nanoparticles in the composite, a photo-assisted technique using sunlight irradiation was utilized. S. Typhimurium and S. aureus, two prevalent foodborne pathogens, were clearly susceptible to the nanocomposite mix film’s antibacterial properties. In comparison with control films, it also exhibited better mechanical, water, and light barrier qualities. A soil burial test conducted inside demonstrated that the nanocomposite mixture would totally deteriorate after 110 days. In order to create new packaging pouches, the nanocomposite mix film was then manufactured. It was discovered to be significantly more effective than control polyethylene pouches at lowering the microbiological burden in samples of chicken sausage, indicating its potential to increase the shelf life of chicken meat products. The incorporation of nanoparticles into processed meat formulations is also a viable strategy for enhancing functional and nutritional attributes. Meat products can be infused with nanoscale ingredients to enhance flavor and texture while concealing flavors. It has been suggested that the kind of meat emulsion-based fatty acid profile could be improved by substituting alternative oils for animal fat [62]. In this context, Marchetti et al. studied the application of bacterial nanocellulose (BNC, 0–0.534 g of dry BNC/100 g batter) in a novel way to low-lipid, low-sodium meat emulsions that are made with pre-emulsified high-oleic sunflower oil (Fig. 2.7) [66]. Analyses were conducted on the water-holding capacity, process yield, water condition, basic foundation, shelf life, and rheological properties. Thermo-rheological curves displayed the typical meat system gelation behavior, while BNC addition resulted in a 3D network that was more solid-like. Up to 0.267 g of dry BNC per 100 g of batter increased the water-binding qualities, hardness, cohesiveness, and chewiness; however, it exhibited a negative effect on these parameters when used at higher concentrations. As a result, using oil that has already been pre-emulsified with BNC as a fat mimic has no detrimental effects on the qualitative characteristics of lowsodium meat and low-fat sausages. This product can be efficiently stored with a 45-day shelf life under vacuum refrigeration. Ahmed et al. conducted intriguing work on chicken active packaging in which they developed compression-molded polylactic (PLA) active films that contained cinnamon essential oils (CEO) and bimetallic copper–silver nanoparticles [67]. The production of the films as well as their further application in the packaging of chicken meat was examined in addition to their physical characteristics and antibacterial qualities. The composites of PLA/PEG/Ag–Cu/CEO demonstrated a very complicated rheological system, with both antiplasticizing and plasticizing actions being noticeable. The addition of nanoparticles could be used to promote the thermal properties of the plasticized polylactide film made with PEG, whereas the addition of CEO

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Fig. 2.7 Bacterial nanocellulose as an additive in low-lipid, low-sodium meat sausages. Reprinted with permission from Food Structure, Copyright 2017, Elsevier [66]

lowered the glass transition, melting, and crystallization temperatures. With a rise in CEO loading, the composite films’ barrier qualities decreased (p < 0.05). Both CEO and Ag-Cu nanoparticles were added, which changed their optical characteristics as well. FTIR spectra were used to visualize the changes in the molecular structure of PLA composite films. Scanning electron microscopy revealed the films’ porous and rough surfaces. When composite films were tested for resistance to Listeria monocytogenes, Campylobacter jejuni, Salmonella, and even Typhimurium inoculated in chicken samples, it can be concluded that the films containing 50% CEO and Ag–Cu nanoparticles displayed the strongest antibacterial action over the course of 21 days when kept refrigerated. Active food packaging can use the manufactured PLA/Ag–Cu/CEO composite films.

Fish and Sea Food Products Fish preservation is an essential component of the fisheries’ operations. The locations of fish farms and other fish collecting locations are frequently remote from retail locations, and where fish is collected, they are usually located far from retail outlets [68]. Fish must be preserved and processed in order to be used in the future when they are gathered in vast quantities that exceed market demand [69]. Due to the

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delicate nature of seafood production, it is incredibly important for nanotechnology to address issues related to managing related concerns. The use of nanomaterials has accelerated the study process in the food packaging industry due to the fact that new properties can be easily provided, like oxygen depletion, pathogen detection, antifungal activities, and enzyme activity, which improve product stability [70]. In relation to the preservation of seafood, literature reviews reveal that the employment of nanoparticles and nanoemulsions is the only use of nanotechnology that is relevant. Fish products can be preserved by using nanofibers as a replacement. The use of nanofibers may be able to minimize microbial activity because it has been scientifically demonstrated that they could be utilized to prevent microbial infectiousness and disease and encapsulate various kinds of antimicrobial compounds. As a new method to prevent the formation of microorganisms in fish meat, electrospun nanofibers applied to the exterior surface layer of the fish would be revered [71]. Ice has been essential to the preservation and freshness of food since the beginning of time. Due to their antimicrobial activity, silver nanoparticles in nano-ice were found in the vein extract from Musa paradisiacal (banana) midrib, and these particles exhibited antibacterial activity. Additionally, it has been demonstrated to lessen the microbial load on the mullet’s surface. Silver nanoparticles biosynthesized using M. paradisiacal midrib extract and present in nano-ice have been shown to be able to reduce the microbial load on the surface of Mugil cephalus (mullet fish) [72]. In terms of preserving seafood, biosynthesized silver nanoparticles are becoming more important than those created chemically. Ice that has been impregnated with nanoparticles could also be employed to package food in a variety of other directions. Because of the antimicrobial action of silver nanoparticles in Mugil cephalus, it has been discovered that the antimicrobial ice shows more significant inhibition in Acinetobacter proliferation. Additionally, fish products may experience unfavorable effects during frozen storage, which could shorten the amount of time they can be stored. Protein denaturation and lipid oxidation are the causes of these unfavorable alterations [73, 74]. By acting as vapor barriers, solutes and gases, and the edible coatings of some organic compounds, can promote the shelf life of foods. Due to the presence of positively charged polycations, chitosan is regarded as a potent antibacterial agent [75]. Additionally, chitosan nanoparticles have exceptional physiochemical and bioactivity characteristics [76]. In contrast to chitosan’s and its coating’s efficacy on silver carp filets (Hypophthalmicthys molitrix), it was discovered that nanochitosan is more antibacterially effective and extra dense. In Indonesia, the use of chitosan as a preservative for recently captured fish has been thoroughly researched. However, the focus of this investigation was on pond-raised species like catfish (Pangasius hypopthalmus) and Nile tilapia (Oreochromis sp.) [77]. Nanotitanium oxide has potent antibacterial properties and can eliminate fish infections in vitro. As a result, adding nanotitanium oxide to fish farm reservoirs is advised to avoid bacterial infection-related illnesses [78, 79]. Earlier, it was determined that fish neutrophil function can be powerfully immune-modulated by nanotitanium oxide [80]. Aeromonas hydrophila, E. coli, and other pathogenic bacteria can be sterilized with nanotitanium oxide to achieve the desired sterilization efficacy.

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2.5.3 Poultry By 2025, according to current worldwide forecasts, chicken meat will be produced and consumed at a higher rate than beef, veal, hog, and sheep meat. In OECD nations, poultry is already the meat that is most frequently consumed. Increased consumption of poultry may be due to the low cost, accessibility, and low-fat content of chicken meat, as well as the lack of significant religious or cultural restrictions on its eating. Salmonella and Campylobacter are the foodborne pathogens that the poultry industry is most concerned about [81, 82]. These infections can exist in the stomach or skin of healthy birds and may be transferred to the meat [83]. The industry of processing meat and fish is closely tied to that of animal feeding. According to Yausheva et al., using arginine and iron nanoparticles together increased weight gain in poultry by up to 9.2% when compared to the control, and using iron nanoparticles along with a combination of amino acids (arginine, lysine, and methionine) increased weight gain by up to 20% [84]. However, amino acids and nanoparticles show reduced weight gain when used alone. Iron nanoparticles were also administered intramuscularly, promoting an immunological response that showed up as an increase in leukocyte levels. In addition, Lactobacillus casei and iron nanoparticles have been employed as probiotic in rainbow trout [85]. Here, the results showed a significant increase in rates of growth like daily growth, specific growth, weight gain, as well as the circumstance factor and meal conversion, when iron nanoparticles (50 g/kg) and Lactobacillus casei (108 CFU/g) were added to the proposed diet accordingly. This supplemented diet also increased intestinal bacterial counts. Hashemi et al. studied the impact of silver nanoparticle-treated clinoptilolite on the characteristics of the meat quality of frozen, stored grill chickens [86]. Following slaughter, the experimental groups were housed at − 17 °C for 3 or 7 days while being fed various meals, including supplements containing 1% clinoptilolite and 1% clinoptilolite coated with 25, 50, or 75 ppm nanosilver in the basal diets. An examination of the texture profile of chicken meat revealed that the nanosilver coating on clinoptilolite had no negative impact on the sensory or textural properties of the meat. The breast muscle of broilers fed clinoptilolite coated with 25 ppm nanosilver had the lowest values for springiness and chewiness. Treatment had no effect on the values of adhesion, cohesion, or gumminess. After seven days of frozen storage, the integration of nanosilver-coated clinoptilolite promoted the water-holding capacity (WHC) in thigh muscles at all levels. In conclusion, clinoptilolite coated with nanosilver can be employed as a potential feed addition in grill diets without having a positive impact on the properties of meat. To ensure food safety and product shelf life, poultry meat products must be packaged properly [87]. Further, Jang et al. examined the antibacterial capabilities of the composite film containing thymol as a chicken breast packaging material to enhance the physical features of Gelidium corneum-gelatin (GCG) film by adding nanoclay to the film-forming solution [88]. The physical qualities of the GCG film were improved by the addition of nanoclay. In comparison with the GCG film’s tensile strength of 26.65 MPa, the GCG film with 1% Cloisite Na+ has a tensile strength of 38.13 MPa.

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Fig. 2.8 Diluted ZnO nanoparticle suspension was first injected into the three-dimensional paper tube to make sure it was entirely filled before the tube was functionalized. The cellulose fibers were subsequently immobilized by drying the nanoparticles at an appropriate temperature (22 °C). SEM allows for precise observation of the sample’s surface. The outcomes demonstrated that cellulose fibers and ZnO nanoparticles were bonded successfully, adapted from [89]

The GCG film had a water vapor permeability of 3.56 ng mm−2 sPa, compared to 3.24 ng mm−2 sPa for the GCG film containing 1% Cloisite Na+ . Thymol was added to the film and used for its antibacterial properties against Escherichia coli O157:H7 and Listeria monocytogenes. The GCG/nanoclay film with thymol suppressed microbiological development when used to package chicken breast for preservation. In another study, Hakeem et al. prevented Campylobacter from growing in raw chicken meat by seeking to add ZnO nanoparticles to packing materials [89] (Fig. 2.8). Hakeem et al. developed the 2D-functional absorption pad through ultrasonicassisted impregnation having strong antibacterial activity against C. jejuni. Firstly, 3D paper tube is initially integrated with ZnO nanoparticles in order to find the lethal concentration of ZnO nanoparticles. The C. jejuni and the dominating flora were inactivated after a week of storage at 4 °C, and the functioning mat was then placed beneath the raw chicken. These procedures are crucial to making sure the 2D-functional absorbent pad generated utilizing the ultrasonic-assisted impregnation process has a successful working concentration. Utilizing 0.856 mg/cm2 of ZnO nanoparticles fixative, C. jejuni counts in raw chicken meat were successfully suppressed from 4 log CFU/25 g after a three-day resting time. Through the use of inductively coupled plasma emission spectrometry, zinc concentration increased from 0.02 to 0.17 mg/cm2 at the same time. The nanoparticles did not travel inside raw chicken, as determined by scanning electron microscopy. While the level of C. jejuni was successfully reduced and the Zn2+ content was enhanced by the application of

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the functional mat to raw chicken flesh, the migration of nanoparticles after treatment was not noticed. Furthermore, for treated raw chicken, a pH-dependent inactivation of C. jejuni was then linked to enhanced lactic acid generation by Lactobacillus. At neutral pH, less than 5% of Zn2+ was released from ZnO nanoparticles, but up to 88% was liberated within 2 days when the pH was 3.5. ZnO nanoparticles had a wide range of effects on genes involved in different cellular developmental processes as identified by gene ontology, according to a whole-transcriptome sequencing (RNASeq) study. Overall, the findings showed that immobilized ZnO nanoparticles and the controllably released Zn2+ from functionalized absorbent pads inactivated C. jejuni in raw chicken meat. Food storage circumstances under typical household use were experimentally recreated as a way to ascertain whether silver nanoparticles move from packaging into food substrates with chicken. First, pick food packaging designed with silver nanoparticles that is easily available on the market. Upon exposure to chicken samples, the packages were stored under predetermined conditions for a predetermined amount of time to restrict the spread of food spoilage bacteria [90]. A maximum level limitation of 0.010 mg/kg for the migration of non-authorized substances through functional barriers, as an indicator of nanoparticle migration, could be evaluated as well for the benefits of food preservation, according to the current regulation of the European Union (EU) No. 10/2011. A chemical analysis demonstrated that under the experimental conditions, no silver was discovered in the chicken meatballs. Silver nanoparticle abuse must be prevented, and any environmental concerns must be minimized. However, there were no discernible variations in the levels of bacteria between meatballs placed in silver nanoparticle-containing bags and those placed in control plastic bags in terms of microbiological tests (including microbial counts, Pseudomonas spp., and Enterobacteriaceae). Microbiological experiments failed to indicate a substantial impact of silver nanoparticles on bacterial levels, although chemical analysis did not disclose any evidence of silver migration.

2.5.4 Beverages Since bottle packaging of drink substantially enhances storage, handling, shipping, and product protection from any potential pollutants, packaging is a crucial part of the beverage industry [91]. Consumers are becoming more mobile than ever before, choosing bottled drinks that are portable. Because of their ease of handling (a polymer container is lighter and more portable than a conventional one), attractive design, and affordability, polymer materials have replaced traditional packaging materials (glass, metal, and paper) [92]. Novel drink packaging features are offered by polymer nanocomposites (PNCs) materials. PNCs could be divided into four categories according to their intended use: biodegradable PNCs, active packaging PNCs, intelligent packaging PNCs, and better drink packaging PNCs [92, 93]. Figure 2.9a shows the interaction between the drink package and the environment.

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Fig. 2.9 a Package–drink–environment potential interactions. Reprinted with permission from Nanotechnology in the Beverage Industry, Copyright 2020, Elsevier [94]. b Platforms for simultaneous detection, presentation, and communication with the end-users concerning the product history, quality, and environment are under consideration as part of the development of smart beverage packaging systems. Reprinted with permission from Trends in Beverage Packaging, Copyright 2019, Elsevier [95]

Use of nanomaterials as nanocoatings and nanolayers in beverage packaging has various advantages, including enhanced mechanical performance, stability in temperature and humidity, O2 and CO2 barrier qualities, and protection against UV light, moisture, and volatile chemicals [91, 92]. Figure 2.9b shows the various aspects of smart packaging in beverages. Incorporation of astaxanthin into waterbased food formulations by solubilizing it in nanodispersion systems is a viable strategy [96]. Nanodispersions of astaxanthin’s chemical resistance have been investigated in deionized water as a control and in orange juice and skimmed milk [97]. In comparison with the control, the nanodispersions showed noticeably (p < 0.05) improved stability in food systems. Additionally, the impact of stabilizers and the dilution factor were examined. The kind of stabilizer had a significant impact (p < 0.05) on astaxanthin degradation during storage in both skim milk and deionized water. Additionally, the in vitro cellular astaxanthin uptake from diluted astaxanthin nanodispersions in particular dietary systems was assessed. When compared to astaxanthin nanodispersions in orange juice and deionized water, the cellular absorption in skimmed milk was considerably higher (p < 0.05). By adding astaxanthin to protein-based foods like milk, astaxanthin nanodispersions can be used to produce high levels of in vitro cellular absorption. In another study, Tamjidi et al. investigated the astaxanthin-loaded NLCs’ (Ax-NLCs) stability in actual (non-alcoholic beer), semi-actual (whey), and model (solutions with 0 or 12% sucrose; pH 3, 7) drinks during 30–60 days of storage at 6 or 20 °C [98]. Tween 80 and lecithin were used to stabilize Ax-NLCs (Z-average size: 94 nm), which contained EDTA and α-tocopherol as antioxidants. They were then blended in at a volume ratio of 3:97

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with the aforementioned beverages. The physical stability of Ax-NLCs in the acidic model beverage was enhanced by the presence of sugar. For whey that had AxNLCs added, there was no astaxanthin loss and there was particle size expansion. Beer that had NLCs added to it significantly increased in particle size after carbonation and/or heat pasteurization, and astaxanthin was lost. The result showed that at low storage temperatures, Ax-NLC stability in non-pasteurized CO2 -free beer has increased significantly. The organoleptic quality of the beers with NLCs added was still respectable. These findings suggest that the creation of functional beverages and foods may make use of NLCs containing hydrophobic nutraceuticals. The majority of drink packaging are made of non-biodegradable materials, which do not match the rising standards for environmental safety and sustainability. Therefore, biopolymers are the perfect material to use in the future generation of biodegradable drink packaging. Because of its subpar mechanical and barrier qualities, however, their use has been restricted. By incorporating nanofillers, these qualities can be improved. Additionally, biodegradable nanoparticles can enhance product security and open up new functionality, including preserving beverage quality, flavor, color, and freshness [99]. Here, biodegradation can be inhibited during drink storage. Moreover, it should not start until the package is thrown away in the case of biodegradable drink contact nanomaterials. Further research into bionanomaterials is essential because of their immense potential in the future. The further improvement of bionanomaterials as a new class of packaging materials has been developed with increasing interest; the incorporation of nanofillers into the matrix may effectively alter the rate of biopolymer biodegradation, crystallization behavior, and thermal properties [99]. Food and beverage flavors are crucial ingredients. They are essential to ensure customer satisfaction. The majority of flavors are developed either chemically or by extracting them from natural components. They are typically expensive, volatile, and sensitive to heat and light. So it is especially important to keep them in food [100]. Microemulsions and nanoemulsions are frequently employed as flavorings in beverages, preserving flavor quality and reducing the development of undesirable flavors. One of the most significant ways that nanotechnology is used to provide bioactive ingredients to food is through encapsulation. Flavoring ingredients are among these bioactive substances and are crucial for overall product acceptance and the propensity to continue consumption in the future. Flavor alterations, including fragrance loss and off-flavor, are caused by storage and production circumstances and chemical components. Thus, encapsulating these substances before adding them to the food can stop flavor loss during preparation and storage.

2.5.5 Dairy Products Dairy products use nanopackaging to preserve their contents and lengthen their shelf lives. Metals, including copper, zinc oxide, silver, and titanium dioxide, are the most frequently and regularly observed nanoparticles in packaging [101]. In this context, Conte et al. demonstrated innovative copper nanoparticle-embedded

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nanocomposite coatings (CuNPs) as active packaging materials for fresh dairy products [102]. Copper nanoparticles were successfully integrated into the biodegradable polymer matrix polylactic acid (PLA) to composite the bioactivity of CuNPs with it. Picosecond-pulsed laser ablation was used to prepare active films in two separate ways. Both in vitro and in vivo testing were performed to evaluate the antibacterial effects of nanocomposite systems. The films made of active polylactic acid exhibited strong antibacterial activity. Fior di Latte samples were kept at 4 °C for 9 days, which prevented the growth of the main rotting organisms and preserved the sensory qualities. These findings mark a development in the further application of copper in the food packaging sector. In another study, Incoronato et al. assessed the impact of an antimicrobial packaging system with active nanoparticles on the degradation of Fior di Latte cheese quality [103]. Three concentrations of silver montmorillonite embedded in agar were used for this purpose. Throughout a period of chilled storage, cell loads of beneficial and spoiling bacteria were observed. Additionally, a panel test was used to assess the sensory qualities of cheese, including its overall quality, consistency, color, and flavor. The ability of silver cations to inhibit microbial proliferation, as demonstrated by the results, significantly extended the shelf life of Fior di Latte cheese without compromising the functional dairy microbiota or the product’s taste attributes. This study’s active packaging technology may be utilized to increase Fior di Latte’s distribution outside of the confines of the local market and extend its shelf life. Another study also reported an enhancement in the shelf life of Fior di Latte cheese by adding silver nanoparticles (Ag NP) to a bio-based coating together with MAP (50% CO2 , 50% N2 ) packaged with or without the customary covering liquid [104]. Principal microbiological and sensory characteristics were observed at a storage temperature of 8 °C until the product became unacceptable. Fior di Latte’s shelf life was increased to a value of roughly ten days thanks to the active coating and MAP. However, the Fior di Latte has to be preserved in brine in order for these treatments to work. Due to sensory unacceptability, active coating and MAP without brine are combined to produce a shelf life of approximately six days. Regardless of the amount of brine used, the combination of simple coating and MAP resulted in a shorter extension of shelf life (five days) than the control sample (four days). The combination of the coating’s Ag NP, the presence of the covering liquid, and the proper initial headspace conditions may thus represent a viable preservation approach to increase the dissemination of this dairy product outside of the local market, according to the experimental data. Further, “Coalho” cheese shelf life has been enhanced by a layer-by-layer nanolaminate coating [105] (Fig. 2.10). An aminolyzed/charged polyethylene terephthalate (A/C PET) was first constructed with five separate layers of lysozyme and alginate. The shelf life of “Coalho” cheese was then tested for 20 days in terms of titratable acidity, lipid peroxidation, pH, microbiological count, and mass loss using the same technology that had been used to deposit the nanolaminate covering. The deposition of the layers and the successful construction of the nanolaminate coating on the surface of A/C PET were validated by UV/Vis spectroscopy and contact angle investigations. The coating’s water vapor (WVTR) and oxygen (OTR) transmission rate measurements were 1.03 × 10−3 and 1.28 × 10−4 g m−2 s−1 , respectively.

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Fig. 2.10 A (a) pH and (b) titratable acidity (TA) of cheese with and without coating over a 20-day storage period. Each data point represents the mean value of three measurements, and error bars indicate the standard deviation. B Images below illustrate the appearance of coated and uncoated cheese on Day 0 (a, b) and Day 20 (c, d) of storage. Reprinted with permission from Food and Bioprocess Technology, Copyright 2013, Springer Nature [105]

Compared to uncoated cheese, covered cheese displayed decreased lipidic peroxidation, pH, mass loss, microbial proliferation, and higher titratable acidity values after 20 days. These findings imply that the alginate/lysozyme nanocoating’s gas barrier and antibacterial capabilities may be employed to promote the shelf life of “Coalho” cheese. White brined cheese, which is described as being semihard, fresh, and matured in brine, is the most prevalent sort of cheese used in the Middle East [106]. These cheeses have an elevated probability of compromising food since they are manufactured from raw milk, exposed to post-pasteurization contamination during handling, preparation, or storage, or not preheated after brining [107]. Listeriosis outbreaks have been caused by a number of cheese varieties, notably white brined cheese, globally. In a recent study conducted by Olaimat et al., the researchers investigated the inhibitory effects of ZnO nanoparticles on three strains of L. monocytogenes in vitro. The nanoparticles were tested at concentrations ranging from 0.0125 to 0.1% and at temperatures of 10 and 37 °C. Additionally, the team evaluated the antimicrobial properties of a chitosan-based coating containing 1.0% ZnO nanoparticles against L. monocytogenes on the surface and inside vacuum-packed white brine cheese. The study also aimed to determine the extent of ZnO nanoparticles’ penetration from the exterior to the interior of the cheeses. Result showed that ZnO nanoparticles have greater antibacterial activity at 37 °C than they did at 10 °C. Two L. monocytogenes strains had initial counts of 4.0 log CFU/ml that were decreased to undetectable levels, while the third strain had a reduction of 1.2 log CFU/ml at 37 °C. The initial

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L. monocytogenes counts were decreased by 0.4–1.9 log CFU/ml at 10 °C. In vacuumpacked cheese stored at either 10 or 4 °C, a chitosan coating containing 1.0% ZnO nanoparticles reduced L. monocytogenes counts by 1.5 and 3.7 log CFU/g on the surface or by 0.9 and 1.5 log CFU/g in the interior, respectively. The EDX results demonstrated that at the end of storage, ZnO NP levels on the cheese surface were constant, and there was no evidence of their movement into the cheese matrix. Thus, it can be concluded that chitosan and ZnO are antibacterial substances that, when combined in edible coatings, may render foodborne microorganisms inactive. In order to lower the amount of L. monocytogenes in white brined cheese, chitosan coated with ZnO nanoparticles can be employed as an effective active packaging material. Mikicuik et al. conducted a study to investigate the impact of silver nanoparticles on probiotic bacteria derived from fermented milk products. The probiotic bacteria used in the study included Streptococcus thermophilus, Bifidobacterium animalis, and Lactobacillus acidophilus. The researchers aimed to examine the effects of silver nanoparticles on the growth and behavior of these probiotic bacteria [108]. Because of their purported health-promoting qualities, probiotic bacteria are one of the most important bacterial species for the food sector. Studies have revealed that the studied probiotic bacteria, which are beneficial for the digestive system, are significantly affected by the type and concentration of silver nanoparticle solutions. In the study, the growth of Streptococcus thermophilus was found to be significantly inhibited by the dilution method compared to the disk-diffusion method when exposed to various silver nanoparticles. On the other hand, there were no noticeable differences observed between L. acidophilus and B. animalis when comparing the results obtained from the disk-diffusion and dilution procedures. The highest antibacterial activity was observed at concentrations of 2 and 0.25 μg/mL, which had the most detrimental effects on the tested probiotic strains. This research appears to be the first of its kind to investigate the potential antibacterial properties of nanosilver against the probiotic bacteria L. acidophilus, B. animalis, and S. thermophilus isolated from fermented milk products.

2.5.6 Bakery According to the senior consultant for scientific and regulatory affairs at RNI Conseil, nanotechnology to deliver nutrients or flavors into baked goods is still in its infancy. However, this will alter over the coming ten years [109]. Figure 2.11a shows the advantages of active packaging in the bakery industry. In this context, Cozmuta et al. compared the shelf life and microbiological safety of wheat bread stored in an Ag/ TiO2 -P packaging system to bread packed in high density polyethylene (HDP-P) and bread without treated packaging (CS) [110]. In order to prevent contact between the bread and the nanocomposite, Ag/TiO2 -P was developed by adding nanocomposite

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between the polyethylene layers. For six days, the bread’s chemical and microbiological stability was observed toward the total molds, yeasts, fat, lipid hydroperoxides, sugar, protein, and counts of Bacillus cereus and Bacillus subtilis, respectively. Compared to CS and HDP-P, experimental data shows that Ag/TiO2 -P significantly increases the shelf life and microbiological safety of bread. Given the comparable chemical composition of bread and bakery goods, it can be inferred that packaging made of Ag/TiO2 will similarly be beneficial in extending their shelf life. By acquiring more of the water and oxygen molecules in the package’s headspace, the rates of compound breakdown and microbial growth might be further slowed down. This approach would possibly extend the shelf life of bread and ensure its microbiological safety. In order to comply with food safety regulations, this would require using more Ag/TiO2 nanocomposite and optimizing the concentration of Ag in the Ag/ TiO2 matrix. In another study, Peter et al. investigated the microbiological and chemical properties of white bread stored in paper packages modified with Ag/TiO2 -SiO2 , Ag/ N-TiO2 , or Au/TiO2 [111]. The modified packages’ whiteness and water retention were somewhat better than those displayed by the reference sample because the composite had a lighter color. Particularly for the Ag/TiO2 -SiO2 -paper, the water retention was excellent. These gains can be attributed to the higher specific surface area and lower propensity for agglomeration of Ag nanoparticles compared to Au ones. The photoactivity and presence of nano-Ag have a good impact on the preservation ability of the composites for storing bread. When compared to plain paper packaging, the shelf life of bread can be extended by 2 days with packages made of Ag/TiO2 -SiO2 -paper and Ag/N-TiO2 -paper. The shelf life of bread was not seen to be extended by the Au/TiO2 . Thus, result showed that paper that has been modified with Ag/TiO2 -SiO2 has the best properties due to the high specific surface area, while paper that has been modified with Au/TiO2 has the worst properties due to the low specific surface area, high density, and propensity for agglomeration of the Au particles in the composite. The white-colored composite makes the paper package appear even whiter. Due to their density and placement between the cellulose fibers, the examined composites (Ag/TiO2 -SiO2 and Ag/N-TiO2 ) retain water better than the reference paper. Under ambient and cold storage conditions, it has been found that both nanocomposites Ag/TiO2 -SiO2 and Ag/N-TiO2 work well in reducing the amount of acid, yeast, and mold growth in bread. These two nanocomposite materials may extend bread’s shelf life by two days when compared to conventional paper packaging, which is a significant development for the food packaging sector. These composite materials are photoactive, and the silver particles they contain serve as a biocide in food, enhancing food preservation. Agarwal et al. applied the montmorillonite composite nylon 6 (MMT-N6) nanofibers to polypropylene sheets using the electrospinning method (Fig. 2.11b) [113]. By implementing a coating of N6 integrated with montmorillonite, the intrinsic oxygen transfer rate (OTR) of polypropylene was raised to 12.5, while the OTR of polypropylene was raised to 35. OTR for polypropylene increased from 963 to 35 cm3 /m2 /24 h, when treated with N6. The water vapor transfer rate (WVTR) of polypropylene, however, was unaffected by the N6 coating (15.5 g/m2 24 h), which

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Fig. 2.11 a Strategies to extend bread and gluten-free bread shelf life. Adapted from [112]. b Natural flora of the bread has been affected by the MMT-N6 nanofibrous membrane coating on polypropylene packaging. Reprinted with permission from Innovative Food Science & Emerging Technologies, Copyright 2014, Elsevier [113]

was 11.6 g/m2 24 h. However, the WVTR was marginally improved when clay was added to N6 (8.4 g/m2 24 h). Due to the suppression of microbial development, the bread’s shelf life was extended by 2 days when packaged in test films. Result showed that storage for 5 days leads to fungal development on bread packed in control packets but not in test packets. In terms of the microbiological count, bread samples packaged in polypropylene packets revealed 2.9 × 104 CFU/g after 5 days, whereas the microbial count in nanocoated packets was 92 CFU/g at the conclusion of the seventh day of storage. Compared to control bread, which had microbial growth in the range of 7.25 × 104 CFU/g of bread sample, bread packaged in MMT-N6-coated packets had 230 CFU/g of bread sample. Figure 2.11 shows that two out of the three bread samples in the test packet had fungal growth by the end of the seventh day. Therefore, using MMT-N6-coated films allows for an almost 2-day improvement

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in bread shelf life, which is highly significant for both the industry and consumers. To promote the shelf life of items other than bread, montmorillonite has also been used in conjunction with silver nanoparticles. The increased oxygen and moisture permeability barriers provided by the addition of montmorillonite clay in the N6 membranes may be responsible for these results. To increase the shelf life of food goods by limiting lipid peroxidation and microbiological growth, which are inhibited by MMT-N6 nanofibrous membrane coating on polypropylene films and decrease oxygen and moisture transport, these films have been used for the first time in this study.

2.6 Summary This book chapter digs into the numerous prospects given by nanomaterials for functioning as intelligent agents for smart packaging, food preservation, and food processing in the food business. The chapter opens with an introduction that emphasizes the importance of nanomaterials in these applications. The chapter then delves into two fundamental techniques: nanoencapsulation and nanoemulsification. Nanoencapsulation is the development of nanoscale delivery systems that improve the stability, targeted release, and bioavailability of food ingredients. Nanoemulsification, on the other hand, focuses on generating nanoscale emulsions that increase the solubility, dispersibility, and transport of lipophilic substances. Furthermore, the chapter examines the use of nanofiltration, nanoadsorbents, and nanoporous materials in food preparation. Nanofiltration allows for the separation and purification of food components, while nanoadsorbents and nanoporous materials are used to efficiently remove toxins and pollutants from food. The chapter also discusses the function of nanoparticles as active and intelligent packaging materials for several food categories. Fruits and vegetables, meat, fish, seafood goods, poultry, drinks, dairy products, and pastry items receive special attention. Nanomaterials increase food preservation, shelf life, safety, and sensory qualities. Finally, this chapter emphasizes the great potential of nanomaterials in the food business, particularly in smart packaging, food preservation, and food processing. The use of nanoparticles in several food categories opens up new avenues for maintaining food safety, quality, and consumer satisfaction.

References 1. Cerqueira, M.A.P.R., et al., Nanomaterials for Food Packaging: Materials, Processing Technologies, and Safety Issues. 2018. 2. Ashfaq, A., et al., Application of nanotechnology in food packaging: Pros and Cons. Journal of Agriculture and Food Research, 2022. 7: p. 100270. 3. Robertson, G.L., Food packaging: principles and practice. 2016: CRC press.

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Chapter 3

Major Applications of Nanotechnology in Food Industry

Abstract The purpose of this chapter is to investigate the use of nanoparticles as a means of delivering bioactive compounds to specific locations of action, such as tissues and cells, with the intention of lessening the harmful effects of these compounds while simultaneously increasing their potential therapeutic benefit. The encapsulation of bioactive compounds within nanomaterials is one technique that is beneficial. This strategy not only protects the bioactive compounds from cellular metabolism and gastrointestinal digestion, but it also enables regulated the release of the bioactive compounds. Further, nanoparticles also helps in controlling the stress condition in plants. Utilizing nanoparticles enables substantial progress to be made in the examination of several components found in wine. These components include sulfur dioxide, polyphenols, biogenic amines, and organic acids, among others. The use of nanoparticles in wine analysis has exciting new possibilities for enhancing our understanding of and ability to manipulate key wine components, which will ultimately lead to improved quality control and the optimization of winemaking procedures.

3.1 Introduction Nanoscience is becoming increasingly important in today’s society, as it is possible to operate at the nanometer scale. Nanotechnology has become very popular in the food industry, mainly to enhance food safety and prolong shelf life. Its major objective is to control the presence of heavy metals, allergies, and other contaminants and to quickly identify dangerous bacteria so that customers are reminded and food has a longer shelf life [1]. Nanotechnology offers numerous options for enhancing the nutritional value and flavor of foods. Nanoencapsulation techniques are extensively re-utilized for the progressive release of flavor and the preservation of culinary harmony [2]. The bulk of bioactive interactions, primarily proteins, lipids, and carbohydrates, are unstable in a well-acidic duodenum and stomach environment due to enzymatic action. Bioactive multifaceted encapsulation not only enables them to combat this challenging circumstance but also lets them readily integrate into food products [3]. This effect is difficult to achieve with less soluble bioactive chemicals that are not © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_3

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Fig. 3.1 Diagram illustrating the use of nanotechnology in various food sector applications, adapted by [5]

encapsulated. In order to optimize the delivery of vitamins, delicate micronutrients, and drugs, nanoparticle-coated capsules are being employed in daily diets to give favorable health effects [4]. The numerous benefits of nanobiosensors as well as the nanomaterials have now been in wide application in the wine industry processes for a variety of potential use, including the preparation of raw materials, storage condition monitoring, and wine manufacture. These devices are also used as efficient, low-cost tools to ensure food safety and to monitor quality and procedures. Here, in this chapter, we examine the recent state of nanotechnology research work in protecting plants from various pathogens, color additives, flavoring agents, anticake agents, viticulture, and the wine industry, with a particular emphasis on the application of nanomaterials for wine properties such as quality, control, and safety monitoring, including nanobiosensors and nanosensors. We also review the potential development of this technique in enology and provide our opinion on it. Figure 3.1 shows the various aspects of nanotechnology in the food sector.

3.2 Nanomaterial Mediated Protective Effect Under Stress Conditions Today’s environmental issues, such as global warming, salt stress, and water shortage situations, severely limit agricultural production [6]. The interdisciplinary discipline of nanotechnology has produced encouraging results in a number of research studies and extended such new opportunities for the agricultural industry to address issues

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83

related to sustainable agriculture [7]. During the last few years, researchers have paid more attention to the application of nanoparticles as one of the most successful ways for improving growth in plants, particularly under salt stress conditions [8]. Selenium (Se) is an important micronutrient with physiological and antioxidative characteristics. In nanotechnology, the priming of seeds has become more popular as a low-cost, effective, and sustainable means of treating seeds [9]. In the study, El-Badri et al. investigated the promising effects of nanopriming via selenium nanoparticles (SeNPs) on aquaporin gene expression, physiochemical properties, seed microstructure, growth features, seed germination, and mineral uptake in salt stress with two rapeseed cultivars [10]. Authors investigated how bioSeNPs affected the transcription of the aquaporin levels genes (BnPIP1-1 and BnPIP2-1), as well as the uptake of water, throughout seed imbibition (4 and 8 h after priming), and discovered that bioSeNP treatment boosted consumption capability and sprouting stimulation (most active at 150 mol/L). Nanotreatments considerably improved the entire performance index of rapeseed seedlings. Overall, the experimental use of nanomaterials increased photosynthetic efficiency, seed germination, and seed microstructure, all of which were directly associated with higher seedling biomass, particularly when bioSeNP concentrations were higher. The increased levels of free amino acids in nanoprimed seeds led to faster seed germination. Furthermore, bioSeNPs improved the efficacy of the defense system of plants by increasing antioxidant enzyme and non-enzyme activity, thereby increasing the elimination of reactive oxygen species (ROS) in salt exposure. The obtained results may imply that bioSeNPs can improve physiochemical characteristics, seedling growth, and seed vigor. Thus, the results demonstrated that bioSeNPs controlled K+ and Na+ uptake to promote rapeseed development and had a close link with low harmful Na+ ion levels; hence, they avoided oxidative damage caused by salt stress. This extensive data could help researchers better explore the internal working principles underlying plant-bioSeNP interactions and provide relevant evidence for the favorable effects of bioSeNP nanopriming on germination and growth of rapeseed seedlings under salt stress. Zahedi et al. conducted a study to examine the potential positive effects of SeNPs on mitigating the adverse impact of soil salinity on strawberry plants (Fragaria ananassa Duch.). They investigated how SeNPs could manipulate physiological and biochemical pathways to enhance plant growth and yield [11] (Fig. 3.2). Researchers found that adding SeNPs at concentrations of 10 and 20 mg L−1 helped photosynthetic pigments, which led to better growth and yield in strawberry plants grown in both non-saline and saline soils with different levels of NaCl (0, 25, 50, and 75 mM). In the presence of high salinity, strawberry plants treated with SeNPs exhibited higher levels of essential osmolytes such as total soluble carbohydrates and free proline compared to untreated plants. These findings suggest that SeNPs possess the ability to protect photosynthetic pigments and enhance the accumulation of important osmolytes, thereby mitigating the negative effects of soil salinity on strawberry plants. This study highlights the potential of SeNPs as a valuable tool for improving crop performance and tolerance to salinity-induced stress. The foliar use of selenium nanoparticles increased strawberry salt tolerance by lowering stress-induced lipid peroxidation

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and hydrogen peroxide (H2 O2 ) concentration by increasing the activity of antioxidant enzymes such as superoxide dismutase and peroxidase. Furthermore, strawberry plants exposed to selenium nanoparticles collected indole-3-acetic acid and abscisic acid, two essential chemicals that indicate stress and control a plant’s morphological, physiological, and biochemical reactions to salt. Additionally, the application of SeNPs to strawberry plants grown in saline conditions resulted in elevated levels of organic acids such as malic, citric, and succinic acids, as well as increased levels of sugars including glucose, fructose, and sucrose in the fruits. These findings indicate that SeNPs have a positive impact on the fruit quality and nutritional attributes of strawberry plants under saline conditions. By enhancing the accumulation of these beneficial compounds, selenium nanoparticles contribute to the improvement of fruit quality and nutritional value. Thus, observations suggest that selenium nanoparticles play distinct roles in the regulation of soil salinity-induced detrimental impacts on various crops in addition to strawberry plants. Such research could be employed to develop easy, prepackaged nanoprimer materials that could be applied prior to sowing to improve seed germination as well as agricultural yield in challenging circumstances. The hormesis effect of the nanomaterial fullerene against stress conditions has different responses. Agrotechnology is researching the important factors of hormesis on crop quality and productivity. The effect of fullerene exposure at concentrations of 100–250–500 mgL−1 , denoted as FLN1-2–3, respectively, on Zea mays chlorophyll fluorescence kinetics, gas exchange, water management, and growth, as well as cobalt-induced oxidative stress, was investigated by Konakci et al. [12]. Fullerenes

Fig. 3.2 Potential processes of selenium nanoparticles (Se-NPs)-induced salt stress tolerance in strawberry plants. Reprinted with permission from Environmental Pollution, Copyright 2019, Elsevier [11]

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eliminated negative changes in gas exchange, water status, and relative growth rate (RGR). It has been demonstrated that fullerenes can repair the damage caused by cobalt stress to the photosynthetic machinery and maintain the photochemistry of photosystems (PSI-PSII) in energy flux, chlorophyll fluorescence transients, and photosynthesis. Due to insufficient scavenging activity, the accumulation of H2 O2 in maize leaves under cobalt stress was demonstrated by the identification of oxygen that reacts with species-specific fluorescence in protective cells. Under stress conditions, fullerenes are controlled through the gene expression of the tonoplast intrinsic protein 2-1 (TIP2-1), nodulin 26-like intrinsic protein 1-1 (NIP1-1), and ribulose-1,5bisphosphate carboxylase large subunit (RBCL). Fullerenes successfully eliminated the H2 O2 content produced due to enzymatic activities. Ascorbate (AsA) regeneration was accomplished in every use of fullerene applications in conjunction with cobalt stress via elevated monodehydroascorbate reductase and dehydroascorbate reductase. Fullerenes were also used to supplement the induced pool of glutathione (GSH), including the GSH redox state, in a dose-dependent manner. When applied hydroponically, fullerenes removed metabolic and biological process constraints caused by excessive ROS production and lipid peroxidation. Taking into account all available data, modifying application methods and fullerene concentrations in treatment procedures will offer a special platform for enhancing crop stress resistance and agricultural productivity. In a study conducted by Adrees et al., the effects of foliar exposure to zinc oxide nanoparticles (ZnO NPs) on wheat growth, zinc (Zn), and cadmium (Cd) uptake in Cd-contaminated soil under different moisture conditions were investigated [13]. The nanoparticles were applied as a foliar treatment at various concentrations (0, 25, 50, and 100 mg/L) during different stages of wheat growth. Two soil moisture conditions, representing 70 and 35% of water-holding capacity, were maintained from 6 weeks after germination until plant harvesting. The results demonstrated that the application of zinc oxide nanoparticles enhanced wheat growth, with the highest efficacy observed at a concentration of 100 mg/L under normal moisture conditions. Furthermore, when 100 mg/L of nanoparticles were used without water deficit stress, the lowest concentration of cadmium and the highest concentration of zinc were observed. In the presence of ZnO NPs at concentrations of 25, 50, and 100 mg/L, the cadmium concentrations in the grain decreased by 26%, 81%, and 87%, respectively, under normal moisture conditions. Similarly, under water shortage conditions, compared to the control treatment, the cadmium concentrations decreased by 35%, 66%, and 81% when ZnO NPs were used at 25, 50, and 100 mg/L, respectively. Foliar exposure to zinc oxide nanoparticles increased leaf chlorophyll content, enhanced leaf superoxide dismutase and peroxidase activity, and decreased oxidative stress. It is possible that foliar application of ZnO NPs could be an efficient way to increase wheat growth and yield with minimum cadmium and maximum zinc contents under drought stress while reducing the chances of nanoparticle movement to various physical spaces, which may be possible with soil-applied nanoparticles. In another study, Mazhar et al. studied the factors affecting ZnO-NPs on rice and wheat grains under salt stress conditions [14]. To evaluate the comparative effectiveness of ZnO NPs in comparison with alternative bulk Zn sources, two separate pot

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experiments for wheat and rice were carried out, namely zinc sulfate heptahydrate (ZnSO47 H2 O) and zinc oxide. The final work revealed that salt stress had a negative impact on the tested parameters. Zn application via Zn sources resulted in a significant (p < 0.05) improvement in grain Zn concentrations, plant Zn uptake, growth, and salt tolerance. Because of their greater plant absorption and translocation in both regular and stressed conditions of the soil, ZnO NPs improved crop parameters the most when compared to other sources. Thus, under normal and saline conditions, both wheat and rice crops assessed with ZnO NPs showed higher effectiveness for grain zinc fortification. Tables 3.1 and 3.2 show the comparative effect of ZnO NPs compared to other bulk Zn sources on salt tolerance attributes (g kg−1 dry wt) and Zn concentration (mg kg−1 dry wt) of wheat and rice, respectively. Salama et al. conducted a study to examine the effects of foliar applications of curcumin nanoparticles (CuNPs) and glycyrrhizic acid nanoparticles (GANPs) on seedling growth and production, anatomical and chemical parameters, and natural infection with the two-spotted spider mite Tetranychus urticae under drought stress conditions [15]. During the two seasons of the study, the presence of drought stress had a significant impact on the population of T. urticae and led to a decrease in various morphological and yield characteristics. Interestingly, under drought conditions, the application of 3 mM CuNPs resulted in a notable 33.9% reduction in the average population of the mites. Additionally, the highest averages of plant height, branch count, and dry and fresh leaf weights per plant were observed with the application of 1 mM GANPs. Moreover, the foliar spraying of GANPs under water stress conditions led to improvements in seed yield (kg/ha), number of pods, and 100-seed weight. The study also revealed that water scarcity negatively affected stem leaf parameters, which were mitigated by the application of CuNPs or GANPs under drought stress. Furthermore, treatment with these nanoparticles resulted in increased thickness of phloem tissues, xylem, and mid-vein, as well as an improvement in stem diameter primarily due to enhanced cortex, phloem, and xylem tissue thickness as compared to the control group. Plants were sprayed with 1 mM GANPs, which increased the percentages of nitrogen, phosphorus, and potassium in seeds as well as total chlorophyll content. Furthermore, no CuNP or GANP levels tested indicated that the intervention markedly altered the quantity of methionine, tryptophan glutamate, glycine aspartate, tyrosine leucine, lysine, and arginine (p > 0.05), whether under normal or drought conditions. Therefore, investigators could assess the effectiveness of both GANP and CuNP sources as natural nanofertilizers on commercially viable crops.

3.3 Color Additives The use of color additives in the food sector must be approved by the Applied Nutrition, Colors, Center for Food Safety, and Office of Cosmetics of the US FDA. Meanwhile, it should be strictly applied in accordance with the permitted restrictions, specifications, and uses. Based on the development of nanotechnology, numerous

0.41 ± 0.003 (− 30.8)

0.53 ± 0.005 (− 10.85)

0.45 ± 0.023 (− 25.79)

1.42 ± 0.073

T3 = ZnO

T4 = ZnO-NPs

T5 = 10dS m−1 EC

1.25 ± 0.009 (− 12.41)

1.04 ± 0.029 (−27.01)

T7 = 10dS m−1 EC + ZnO

T8 = 10dS m−1 EC + ZnO-NPs

26.9***

4.11*

Zn source

Salinity × Zn source

*p ≤ 0.05 **p ≤ 0.01 *** p ≤ 0.001 ns = not significant

917.72***

Salinity

F-values

1.14 ± 0.036 (− 20.07)

T = 10dS EC + ZnSO4 ·7H2 O

m−1

0.60 ± 0.01

T2 = ZnSO4 7H2 O

Shoot Na+ (g kg−1 dry wt)

T1 = Control

Treatment

12.91**

76.33***

2184***

8.85 ± 0.20 (22.18)

7.7 ± 0.18 (6.22)

8.65 ± 0.26 (19.38)

7.25 ± 0.05

15.2 ± 0.37 (28.34)

14.3 ± 0.07 (20.86)

14.9 ± 0.24 (25.66)

11.86 ± 0.22

Shoot K+ (g kg−1 dry wt)

2.61ns

123.95***

280.06***

34.9 ± 1.05 (121.68)

23.4 ± 0.85 (48.58)

29.5 ± 0.71 (87.35)

15.7 ± 2.03

51 ± 0.74 (97.11)

39 ± 1.07 (50.61)

44.3 ± 1.13 (71.22)

25.9 ± 0.94

Shoot Zn (mg kg−1 dry wt)

0.73ns

63.71***

48.67***

48.3 ± 1.28 (76.14)

36.3 ± 1.36 (32.28)

41.4 ± 0.32 (51.14)

27.4 ± 2.6

54.1 ± 1.6 (59.57)

46.2 ± 3.1 (36.36)

49.6 ± 2.71 (46.27)

33.9 ± 2.7

Root Zn (mg kg−1 dry wt)

2.03ns

149.27***

92.29***

45.7 ± 1.45 (146.45)

26.4 ± 0.8 (42.5)

37 ± 0.59 (99.69)

18.5 ± 1.3

52.9 ± 1.5 (106.43)

39.3 ± 0.19 (53.54)

46.6 ± 1.6 (82.04)

25.6 ± 2.4

Grain Zn (mg kg−1 dry wt)

Table 3.1 Comparative effect of ZnO NPs compared to other bulk Zn sources on salt tolerance attributes (g kg−1 dry wt) and Zn concentration (mg kg−1 dry wt) of wheat plant

3.3 Color Additives 87

0.89 ± 0.041 (− 29.69)

1.05 ± 0.019 (− 16.96)

0.72 ± 0.11 (− 43.04)

2.93 ± 0.08

T3 = ZnO

T4 = ZnO-NPs

T5 = 7dS m−1 EC

2.61 ± 0.07 (− 11.02)

2.23 ± 0.09 (− 23.77)

T7 = 7dS m−1 EC + ZnO

T8 = 7dS m−1 EC + ZnO-NPs

30.58***

0.59ns

Zn source

Salinity × Zn source

*p ≤ 0.05 **p ≤ 0.01 *** p ≤ 0.001 ns = not significant

1049***

Salinity

F-values

2.39 ± 0.014 (− 18.31)

T6 = 7dS EC + ZnSO4 ·7H2 O

m−1

1.26 ± 0.058

T2 = ZnSO4 ·7H2 O

Shoot Na+ (g kg−1 dry wt)

T1 = Control

Treatment

0.19ns

33.96***

1440***

5.8 ± 0.25 (49.69)

4.5 ± 0.31 (16.83)

5.7 ± 0.12 (46)

3.9 ± 0.36

12.2 ± 0.27 (20.29)

10.6 ± 0.16 (4.4)

11.8 ± 0.18 (16.61)

10.2 ± 0.14

Shoot K+ (g kg−1 dry wt)

1.28ns

73.79***

229.93***

25.5 ± 0.92 (64.96)

19.5 ± 0.36 (25.82)

22.8 ± 0.81 (47.45)

15.5 ± 0.57

34.3 ± 0.31 (54.06)

28.3 ± 0.85 (27.06)

32.6 ± 0.67 (46.7)

22.2 ± 1.12

Shoot Zn (mg kg−1 dry wt)

2.59ns

66.86***

637.18***

29.2 ± 0.67 (52.38)

22.1 ± 0.43 (15.1)

26.1 ± 0.84 (36.02)

19.2 ± 0.20

45.5 ± 0.95 (39.68)

38 ± 0.68 (16.65)

44.5 ± 1.53 (36.47)

32.6 ± 0.91

Root Zn (mg kg−1 dry wt)

2.23ns

36.27***

153.6***

31.9 ± 1.05 (36.74)

26.7 ± 1.28 (14.52)

30.8 ± 1.3 (31.98)

23.3 ± 0.67

45 ± 1.3 (47.73)

37.4 ± 1.1 (22.9)

42.7 ± 1.8 (40.2)

30.4 ± 1.5

Grain Zn (mg kg−1 dry wt)

Table 3.2 Comparative effect of ZnO NPs compared to other bulk Zn sources on salt tolerance attributes (g kg−1 dry wt) and Zn concentration (mg kg−1 dry wt) of rice plant

88 3 Major Applications of Nanotechnology in Food Industry

3.5 Flavors

89

nanoscale color additives are being researched and produced. Some nanotechnology products were recently given the go-ahead to be used as food color ingredients, which are crucial for increasing the perceived value of consumer products. The US Food and Drug Administration accepted titanium dioxide (TiO2 ) as a food color addition with the provision that the additive should not exceed 1% w/w [16] and is currently exempt from certification. Color additive combinations for use in food that contains TiO2 may also contain silica (SiO2 ) and/or aluminum oxide (Al2 O3 ) as dispersing aids, but only up to 2% of the overall amount [17]. Unfortunately, carbon black is no longer permitted as a food coloring component.

3.4 Anticaking Agent SiO2 , as an anticaking ingredient to retain flow qualities in powdered products, is mostly used to thicken pastes accordingly. Meanwhile, it can also be a fragrance or flavor carrier in food and non-food products. The substance has a long history in the food industry and was authorized as an EU food additive (E551). Current research indicates that at least a portion of the SiO2 in powdered food items containing E551 is nanosized. In addition, research suggests that when E551-containing meals are consumed, the gut epithelium is likely exposed to nanosized SiO2 [18, 19]. In their work, Athinarayanan et al. demonstrated the effect of the size and morphology of silica (E551) particles in food [19]. The result suggests the detection of 2.74– 14.45 μg/g silica in commercial food products. Moreover, an increase in daily dietary intake has negative health impacts. The shape, crystalline nature, particle size as well as the purity of the silica particles were studied using DLS, XRD, EDX, TEM, and FTIR after E551 was isolated from food products. These tests indicate the existence of roughly 10–50 nm-sized spherical silica nanoparticles (of amorphous origin) in meals. For this, researchers investigated the expression levels of metabolic stressresponsive genes (CAT, GSTA4, TNF, CYP1A, POR, SOD1, GSTM3, GPX1, and GSR1), and the effects of E551 on the viability of human lung fibroblast cells, intracellular ROS levels, cell cycle phase. From the final results, it can be clearly seen that E551 generated dose-dependent cytotoxicity and alterations in ROS levels, as well as changes in gene expression and the cell cycle. WI-38 cells were subjected to a high concentration of E551, which had considerable cytotoxic effects. These discoveries have ramifications for the food industry’s utilization of these nanoparticles.

3.5 Flavors The overall eating experience of food can be enhanced by the good senses of taste and smell. Nanoencapsulation techniques have been well used to enhance taste release and retention and to develop a gastronomic balance. The results also demonstrate

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3 Major Applications of Nanotechnology in Food Industry

that SiO2 nanoparticles can operate as aroma or taste carriers in food and non-food products.

3.6 Nanotechnology in Viticulture Certainly, on the environment, viticulture has an immediate effect as a result of agricultural methods such as the use of agrochemicals, soil management, and water use [20]. There is a significant need for winegrowers to implement more sustainable agricultural practices at present. Nanotechnology is provided as an option within precision agriculture using an ecofriendly methodology [21, 22]. The objective of precision farming is to employ procedures and technology that can respond to interand intrafield crop variability in order to increase production while minimizing the usage of inputs like fertilizers, and herbicides [23–25]. Everywhere in the world, the significant role of viticulture is observed in the social, economic, and cultural spheres. By 2023, it is anticipated that there will be USD 423.59 billion worth of wine sold worldwide [26]. Nevertheless, viticulture and enology are relatively new to the utilization of nanotechnology when compared to other agrifood industries. This late adoption demonstrates how challenging it has become to enter an industry that relies on age-old, conventional methods. In the agriculture sector, nanotechnology has been presented as an efficient technique capable of reducing the amount of applied phytochemicals, like fertilizers, insecticides, and herbicides, in order to increase crop yield and reduce environmental effect [27, 28]. This reduction is achievable because the nanoparticles have a huge surface area [29]. Due to their vast superficial area and potential for regulated release, nanopesticides that target specific plant tissues were used to accomplish the desired results while minimizing the number of phytochemicals normally necessary [25].

3.6.1 Stress Treatment The agriculture industry has utilized engineered nanoparticles extensively to improve the quality and production [30, 31]. Relevant biochemical studies revealed that these particles considerably affect plant gene expression, oxidative stress, photosynthetic processes, and antioxidant enzymatic activities. According to reports, nanoparticles like cerium oxide increase plants’ ability to withstand abiotic stress, primarily by strengthening their antioxidant system. It has been well known that excessive soil salinity poses a serious challenge to global agriculture since it can significantly reduce crop yield and growth across the board [32]. One of the most economically significant fruit crops is the grape (Vitis vinifera L.), a perennial plant grown abundantly worldwide that originates in the Vitaceae family [33]. Abiotic stressors such as drought, salt, extremely high or oxidative stress, chemical toxicity, and

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low temperatures have an impact on grape development [34]. Salinity inhibits the growth of grape biomass, which ultimately culminates in the plant’s death. During saline stress, the grape plant’s biomass of leaves, roots, and shoots was reduced [35]. Engineered nanoparticles have gained recognition in recent years as a possible alternative for overcoming abiotic stress factors, including salt. In this context, Gohari et al. demonstrated the bright future of cerium oxide nanoparticles (CeO2 NPs) in grapevine cuttings for reducing salt stress (Vitis vinifera L. cv. Flame Seedless) [36]. A variety of agronomic characteristics were tested in order to specifically assess the relationship between cerium oxide nanoparticles (25, 50, and 100 mg L−1 ) and salinity (25 and 75 mM NaCl). Results showed that treatment with cerium oxide nanoparticles, in general, considerably improved relevant agronomic parameters of grapevines by reducing the negative impact of salt stress (75 mM NaCl). Additionally, CeO2 NPs also significantly reduce chlorophyll degradation in conditions of high salinity. Also, the presence of CeO NPs mitigated the impacts of salt stress on grapevine damage, malondialdehyde (MDA), and electrolyte leakage; however, no improvement in H2 O2 content has been observed with the appearance of CeO2 NPs. Moreover, in comparison with control plants, salinity-induced significant increases in the enzymatic activity of guaiacol peroxidase, ascorbate peroxidase, and superoxide dismutase (SOD). All concentrations of CeO2 NPs induced ascorbate peroxidase activity, similar to stress conditions, but the highest concentration of cerium oxide nanoparticles markedly increased guaiacol peroxidase activity. However, no significant effect has been observed on SOD activity after cerium oxide nanoparticle exposure. Salinity increased Na and Cl content and even the Na/K ratio when considering the mineral nutrition profile, but it lowered K, P, and Ca amounts. However, the Na, K, and P contents of salt-stressed plants were not significantly changed by the presence of cerium oxide nanoparticles. Together, the data available now points to CeO2 NPs as potentially effective treatments for grapevine salt stress. In addition, it has been observed that TiO2 NPs treatment significantly improved spinach plant development by further activating the photosynthetic process. Comparatively to plants that were only exposed to salinity, broad bean plants supplemented with TiO2 NPs showed a significant increase in soluble sugars, amino acids, and proline concentration, as well as enzymatic antioxidant capacity [37]. Considering the unique physical and chemical attributes and reported favorable effects of proline and carbon quantum dots (CQDs) on plant development and physical characteristics when used separately, their union to generate prolinefunctionalized carbon quantum dot nanoparticles (Pro-CQD NPs) may have a synergistic beneficial effect on plants. In this context, Gohari et al. determine the effects of this cutting-edge nanomaterial (Pro-CQDs NPs), which can be a chemical priming agent in grapevine plants. “Rasha,” [38] (Figs. 3.3 and 3.4). Grapevine plants were subjected to varying concentrations of proline, CQDs, and Pro-CQDs for a period of 48 h before being subjected to salt stress at a concentration of either 0 or 100 mM NaCl. This was done in order to evaluate the effects of these treatments. After three days of salt stress, biochemical tests were performed, and at the end of the stress period, agronomic and physiological indicators were analyzed. The findings revealed that both doses of proline treatment, as well as low-concentration CQDs

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3 Major Applications of Nanotechnology in Food Industry

and Pro-CQDs nanoparticles, had beneficial impacts on grapevine plants under both normal and salt stress conditions. Notably, treatment with 100 mg L−1 proline and 50 mg L−1 Pro-CQDs nanoparticles resulted in ideal performance; however, treatment with 50 mg L−1 Pro-CQDs NPs showed the most promising effect. Under both normal and salt stress conditions, proline administration at 100 mg L−1 enhanced leaf fresh weight (FW), dry weight (DW), chlorophyll a and b levels, proline content, SOD activity, Y (II), carotenoid content, and catalase activity. Treatment with 50 mg L−1 of Pro-CQDs nanoparticles increased carotenoid activity, Y (II), Fv/Fo, catalase activity under salinity, overall Fv/Fo, anthocyanin and phenol levels, as well as ascorbate peroxidase and guaiacol peroxidase activity. In all cases, it decreased the amount of electrolyte leakage, malondialdehyde levels, and hydrogen peroxide levels that were present when the cells were subjected to salt stress. In conclusion, the conjugation of CQDs with proline at a concentration of 50 mg L−1 resulted in an increase in the protective effects of proline administration at a dosage of 100 mg L−1 . Hence, it appears that functionalizing nanoparticles with chemical priming agents is a useful way to maximize plant-priming strategies for effectively ameliorating abiotic stress-related damage to plants. Further, similar authors have investigated the synergistic effect of putrescine (Put) and CQDs in grapevine under salt stress condition [39]. In order to analyze this, Put, CQDs, and Put-CQD nanoparticles were used as chemical priming agents in the “Sultana” grapevine 48 h prior to the imposition of salinity stress (0 and 100 mM NaCl) at concentrations of 5 and 10 mg L−1 . Chlorophyll fluorescence parameters, morphology variables, pigments used for photosynthesis, and the membrane stability index all experienced significant decreases in salinity. The presence of salinity led to elevated levels of malondialdehyde (MDA), proline, H2 O2 , and antioxidant enzyme activity. The study showed that the use of putrescine-conjugated carbon quantum dots nanoparticles (Put-CQD NPs) led to an increase in fresh and dry weight, potassium (K+ ) content, photosynthetic pigment levels, chlorophyll fluorescence, and SPAD parameters. Furthermore, Put-CQD NPs treatment increased proline content, total

Fig. 3.3 Hydrothermal approach a enabling the synthesis of proline-coated carbon quantum dots (Pro-CQDs NPs) and the emission spectra of Pro-CQDs NPs in liquid; inset: photographic images of the fluorescent Pro-CQDs NPs suspended in water in visible and ultraviolet wavelengths b. Reprinted with permission from Environmental Science and Pollution Research, Copyright 2019, Springer [38]

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Fig. 3.4 Impact of Pro (50 and 100 mg L−1 ), CQDs (50 and 100 mg L−1 ), and Pro-CQDs NP (50 and 100 mg L−1 ) regimens on EL a, MDA b, H2 O2 c, and proline d of Vitis vinifera cv. “Rasha” under control (0 mM NaCl) and salt stress (100 mM NaCl) conditions. Due to Duncan’s post hoc evaluation, various letters denote substantial differences at p < 0.05. Reprinted with permission from Environmental Science and Pollution Research, Copyright 2019, Springer [38]

phenolics, and antioxidant enzyme activity, while decreasing sodium ion concentration, MDA, H2 O2 content, and electrolyte leakage. These nanoparticles effectively mitigated the harmful effects of salt stress by reducing MDA and H2 O2 levels. Overall, the application of Put-CQD NPs proved to be an innovative priming technique that successfully enhanced grapevine performance under salinity stress. Several studies have proven salicylic acid’s (SA) ability to help plants withstand environmental stressors. By decreasing the H2 O2 , leaf electrolyte leakage, Na+ /K+ ratio, MDA, as well as enhancing proline and enzyme activity, the grape variety “Sultana’s” salinity tolerance was dramatically boosted [40, 41]. Chitosan has potential as an agricultural stimulant and as a biostimulant. Via secondary signaling, this substance’s non-toxic, biocompatible properties, as well as being biodegradable, lessen the negative impacts of abiotic stressors [42]. In the work, Aazami et al. demonstrated the anti-inflammatory properties of chitosan-based salicylic acid nanocomposite (CS-SA NCs) in grape (V. vinifera cv. “Sultana”) under salinity stress [43]. The two elements, salt stress and chitosan-salicylic acid nanocomposite materials (CSSA NCs), were both investigated with different NaCl levels, including 0, 50, and 100 mM. On the contrary, the application of CS-SA NCs at different levels of NaCl exposure resulted in an increase in proline, H2 O2 , MDA, soluble protein, soluble carbohydrate, overall antioxidant content, and antioxidant enzyme activity. However, the levels of carotenoids, nutritional elements (except for sodium), and chlorophylls (a, b, and total) decreased. Salinity stress negatively impacted the photosynthetic systems, leading to a decrease in Fm' , Fm, and Fv/Fm parameters. Nevertheless,

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3 Major Applications of Nanotechnology in Food Industry

treatment with CS-SA NCs improved these indices during salinity stress. The application of CS-SA NCs enhanced the physiological, biochemical, and nutrient balance features of grapevines under non-stressful conditions. When exposed to salt stress, the examined characteristics of grapevines responded positively to CS-SA NCs at a concentration of 0.5 mM. Therefore, it can be inferred that CS-SA nanoparticles act as biostimulants, enhancing the yield of grape plants under salt-stress conditions.

3.6.2 Disease Control In today’s scenario, several nanoparticles have been studied and proven to manage plant diseases as well as pests in agriculture, but vineyard-specific research is rare. Copper application is one normal method for managing plant pathogens in vineyards [25]. Downy mildew can be efficiently treated with this approach, which is one of the most common diseases of grapevines indicated by Plasmopara viticola infection [44]. Schneider et al. registered a water-based remedy with nanoscale copper particles to inhibit this phytopathogenic bacterium and reduce copper requirements [45]. To ensure the efficacy of the nanoparticles, different formulations were subjected to a biological application. Initially, a copper dose of 150 μg/L was applied to plants with various formulations. Plants was incubated with P. viticola for 7 days. The result showed a reduction in leaf damage when exposed to nanoform. Thus, the nanoform of copper salt proved to be more efficient against plant fungus with a lower copper concentration and was thus considered a suitable alternative in order to stop the pest production in vines. Using nanostructured hydroxyapatite, Battiston et al. demonstrated that the amount of copper employed can be greatly decreased [44]. This study investigated the capability of synthetic hydroxyapatite to provide materials that boost the enzyme activity of copper ions. To determine the most effective formulation, an in vitro antifungal study was carried out using different formulations against Botrytis cinerea, a common grapevine pathogen. Subsequently, greenhouse experiments were conducted to assess the efficacy of these formulations against P. viticola. The treatments included (i) a water-based positive control, (ii) an organic fungicide, (iii) a cupric fungicide, and (iv) hydroxyapatite containing 5.2% copper by weight. The results demonstrated that, in comparison with other formulations, nanostructured hydroxyapatite particles reduced illness severity and incidence with a lower rainwashing impact and a lower copper dosage. Hence, this research has demonstrated that a formulation using hydroxyapatite particles with soluble copper can be used to prevent and treat fungal infections in vineyards. Plants are more susceptible to getting attacked by various fungi during vine pruning, which has been majorly to blame for the development of grapevine trunk disease. Moreover, researchers reported adhesive biodegradable membranes (patches) to prevent fungal assaults at plant trimming sites [46]. Nanofibers made up of soy protein, polyvinyl alcohol, and polyethylene glycol were employed to produce the water-soluble adhesives that were electrospun. Excellent mechanical support has

3.6 Nanotechnology in Viticulture

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been provided by the adhesives, where pore size allows the plants to breathe while physically inhibiting the penetration of fungi. The proposed nano-adhesive here could be chosen and employed for preventing the pruning sites on a vine against fungus assault and the development of diseases such as esca. TiO2 NPs lead to ROS generation that are activated by ultraviolet (UV) radiation, which makes them suitable for efficiently treating a variety of diseases. As ROS are known to have a signaling role in living things, their production by TiO2 NPs has the potential to affect both enzymatic and non-enzymatic defense mechanisms, and the susceptibility of plants to infections. In this context, Korosi et al. investigated how the model plant grapevine (V. vinifera L.) responded to exposure to the photocatalyst Degussa P25 TiO2 nanoparticles under photocatalytic stress [47]. It was verified using electron paramagnetic resonance spectroscopy that the production of photocatalysis-mediated ROS, such as singlet oxygen, hydroxyl radical, and superoxide anion. In a field setting where plants are exposed to natural sunlight with rather high UV radiation (with a maximum of 45 W m−2 ), foliar exposure of five red cultivars was conducted during the blooming phenophase. Researchers carefully evaluated whether photogenerated ROS impacted the major macro- and microelements, capacity for antioxidants, flavonol profile, and overall phenolic content of the leaves after two weeks of exposure. The authors observed that the foliar application of TiO2 NPs led to an increase in the synthesis of leaf flavonols and the overall phenolic content, depending on the grapevine variety. Additionally, analysis using ICP-AES demonstrated that photocatalytically active TiO2 NPs elevated the levels of essential elements such as potassium (K), magnesium (Mg), calcium (Ca), boron (B), and manganese (Mn) in the leaves.

3.6.3 Nanofertilizers Nanoparticles can also be utilized as fertilizer and nutrient carriers for crops, albeit with a lower number of components and a regulated release, which in turn reduces nutrient loss during fertilization, enhances agricultural yield, and decreases pollution [23, 48]. Sabir et al. conducted the first study utilizing nanofertilizer in vineyards [49]. They examined the effect of applying a nanosize calcite product to a “Narince” (V. vinifera L.) vineyard over a two-year period on berry quality and vine growth. In that work, the usage of this nanofertilizer led to improved growth and output per vine, as well as an enhancement in berry weight and Brix levels, with improved production and quality of grapes. In the past decade, Pérez-Lvarez et al. evaluated the application of a special material called amorphous calcium phosphate (ACP) nanoparticles. As nanocarriers of urea in Tempranillo grapevines, the proposed materials utilize the foliar function of three formulations: two formulations consist of different concentrations of free urea (U3 and U6: [N] = 3 kg/ha and 6 kg/ha, respectively), and the third contains urea with nanoparticles at a concentration of 0.4 kg/ha. The study of the grapes’ amino acids revealed that applying the fertilizer with nanoparticles at the same concentrations as the U6 treatment resulted in a 15-fold reduction in the

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amount of urea required for fertilization [50]. The amounts of the amino acid precursors for volatile fermentative substances in grapes (including phenylalanine, leucine, isoleucine, and the amino acids valine, tyrosine, tryptophan, threonine, and glutamate acid) The related information above is depicted in Fig. 3.5. The nanofertilizer treatment yielded the highest glutamic acid concentrations in the musts. Meanwhile, the related concentrations of threonine, tryptophan, and phenylalanine in the must were equivalent to those collected with the U6 samples and greater than those obtained with the U3 and control treatments. U6 samples contained the highest quantities of the remaining amino acids. Furthermore, the application of urea-activated clay particles (U-ACP) on grapevines resulted in increased levels of arginine, an essential amino acid utilized by yeasts during fermentation, while decreasing the concentrations of amino acids that serve as precursors to biogenic amines. This indicates that the use of such nanoparticles could potentially reduce the amount of urea required for fertilization, thereby minimizing its environmental impact and preserving the quality of grapes. However, it should be noted that the utilization of nanofertilizers in vineyard practices is still relatively limited and requires further development.

3.6.4 Antimicrobial Activity of Nanoparticles From both an economic and a social perspective, viticulture plays a significant global role. Sadly, pathogens of numerous types frequently damage vineyards and, in the worst-case scenario, can produce severe epidemics, resulting in major economic losses and potentially destroying the entire crop [52–54]. Although nanoparticles can be employed for pest and insect management, it is vital to understand the metabolic changes that occur during grapevine defense responses. Although nanoparticles can be efficiently employed for pest and insect management, it is very critical to understand the metabolic changes that occur during grapevine defense responses [25]. Further, to apply nanomaterials in agriculture, it is necessary to understand their phytotoxicity and associated ecological concerns [24]. In this context, Teszlák et al. conducted the initial study conducted on vines up to this point [54]. They examined the phytotoxicity of TiO2 NPs in the field on Cabernet Sauvignon (V. vinifera L.) grapevines. TiO2 NPs are well known to exhibit antibacterial characteristics. In the present work, authors have exposed the plant leaves to TiO2 NPs and further examined their effect on the micro- and macro-element content of the leaves, flavanol profile, and photosynthetic function. The results showed that foliar treatment leads to enhanced foliar absorption of nanoparticles, as indicated by increased and selective accumulation of macronutrients. Further, photosynthesis metabolic inhibition was also observed with reduced assimilation of carbon dioxide and enhanced stomatal conductance. TiO2 NPs also affected the photoprotective process, which leads to a reduction in the rate of electron transport as well as non-photochemical quenching. The investigation of flavonoids revealed that certain chemicals may play an active role in the defense system against photocatalytically generated reactive oxygen species.

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Fig. 3.5 Concentration (mg N/L) of several types of essential amino acids in grapes from Tempranillo vines that were left untreated, treated with conventional urea at levels of 3 kg N/ ha (U3) and 6 kg N/ha (U6), and then supplemented with 0.4 kg N/ha of U-ACP nanoparticles. The standard errors of each parameter are provided (n = 3). Substantial differences between treatments are shown by various letters (p ≺ 0.05). Reprinted with permission from Journal of The Science of Food and Agriculture, Copyright 2019, John Wiley and Sons [51]

According to the report recently investigated by Chronopoulou et al., the microfluidic production of poly(lactic-co-glycolic acid) (PLGA) nanocarriers packed using methyl jasmonate (MeJ) can be seen as a novel method for enhancing V. vinifera L.’s natural defenses. The response of V. vinifera cell cultures to the treatment of free MeJ or nanoencapsulated (PLGA nanoparticles; size 40–100 nm) MeJ was assessed in terms of stilbene production. It was noted that the use of PLGA nanoparticles enabled the formation of stilbene to occur sooner and be more stable than when using free MeJ. According to the findings of that research work, the method might be implemented in the field to stimulate the natural fortifications of the grapevines. Downy mildew and powdery mildew, here, are two of the most significant grapevine diseases [55, 56]. According to published data, the earliest grapevine disease recognized by science and agriculture is powdery mold, which is brought on by the pathogen Uncinula necator. It has always existed in North America, its native habitat [57, 58]. The pathogen is a member of the Vitaceae family of holoparasites

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[59] and is capable of infecting all green plant sections. Based on the well-known antimicrobial properties of silver nanoparticles, Vizitiu et al. investigated the effect of Two “green” recipes on grape pathogens: an alcoholic extract of Dryopteris filix-mas (L.) Schott and a dispersion of nanoparticles of silver created from the substance that was extracted [60] (Fig. 3.6). In addition, the effect of several grapevine characteristics (pith/wood ratio, length of young shoots, total water content, total sugars, soluble sugars, starch, and quantity of grapes) was investigated in field trials. The study was also conducted on four different clones grown in vegetation pots within a greenhouse. We utilized a scaled-up technique for the phytosynthesis of silver nanoparticles, which allowed us to acquire vast volumes of nanoparticle-containing solutions. The transmission electron microscopy and X-ray diffraction study of silver nanoparticles validated the production of spherical nanoparticles containing a 17 nm average diameter, which makes them roughly spherical, and a crystallite size of 6.72 nm. Experiments conducted in the field utilizing both natural extracts and phytosynthesized nanoparticles revealed that all four clones responded differently to the treatments. Both formulations protected against the U. necator infection. White wine clones (Feteasca alba 97 St. and Feteasca regala 72 St.) given phytosynthesized nanoparticles exhibited substantial improvements in the pith/wood ratio. Other biochemical studies demonstrated measurable improvements in soluble sugars (Cabernet Sauvignon and Feteasca neagra), starch (Cabernet Sauvignon and Feteasca alba in 2021 for both clones), total sugars (Cabernet Sauvignon and Feteasca alba in 2021 for both clones), and overall water content (Cabernet Sauvignon and Feteasca neagra in 2021 for both clones). The applied treatments also resulted in an increase in the length of young shoots and the number of grapes for all clones compared to the control, indicating that the recipes may have a biostimulant impact. Significant advancements have been achieved in incorporating nutrients or bioactive substances into films and coatings [61]. In this context, strawberries were maintained for several days when chitosan microparticles that included antifungal (Paeonia rockii), were applied to agar-based films [62]. As an alternative to applying bioactive chemicals to the surface of foods, edible coatings have been investigated by Lemes et al. [63]. In that work, transglutaminase was employed to enzymatically crosslink gelatin to create hydrogels, which were subsequently modified further with calcium propionate or zein nanoparticles with curcumin. Benitaka grapes earned the protective coatings (Fig. 3.7), which were then examined after seven days of storage at 25 °C and 50% relative humidity. The nanoparticles containing curcumin were characterized by their spherical shape, broad size distribution, and average diameter of 585 nm. The successful encapsulation of curcumin was confirmed through analysis using FTIR and differential scanning calorimetry (DSC) techniques. Analyses of the gelatin hydrogels’ rheology revealed that the action of transglutaminase enhanced the hydrogels’ pseudoplasticity with increasing temperature. It was verified by a power law model that corresponded to the observed curves. After a week of preservation, palatable coatings on Benitaka grapes failed to result in a rise in the growth of bacteria, nor did they change the grapes’ titratable acidity. With the addition of calcium propionate to the hydrogel, fruit ripening was better controlled. Texture

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◄Fig. 3.6 Changes in the frequency (F), intensity (I), and attack degree (AD) of U. necator were observed during successive treatments in 2020 on different grapevine clones. The clones investigated were as follows: a, b Feteasca alba 97 St, c, d Feteasca neagra 6 St, and e, f Feteasca regala 72 St. The values presented are represented as means ± standard deviation (SD). Statistical analysis using one-way ANOVA and the TUKEY test revealed that means of the same parameter (indicated by the same color) without a common lowercase letter (a–g) exhibited significant differences (p < 0.05). The treatments applied were as follows: V1 = alcoholic extract of D. filix-mas, V2 = alcoholic extract of D. filix-mas with silver nanoparticles, and C = control (chemical pesticide). Notably, no significant pathogen attack was recorded for the Cabernet Sauvignon 131 St. clone, as indicated by null results. The abbreviation N.D. indicates that no pathogen attack was detected in the respective samples, adapted from [60]

profile analysis indicated that the application of the edible coating did not influence the texture properties of the grapes. However, the presence of curcumin-loaded nanoparticles resulted in enhanced color intensity in the grapes. In another study, Silva et al. also determined the influence of the effects of chitosan on the phenolic material, antioxidant capacity, and antimicrobial properties of particular grapevine elements Sousao [64]. Researchers obtained ethanol from the stems, seedlings, and skins of chitosan-treated and untreated grapevines. Total phenolic, anthocyanin, and tannin contents were analyzed, and specific phenolic compounds were identified using HPLC–DAD. The capacity of multidrug-resistant bacteria to be handled by antibiotics was evaluated using the Kirby-Bauer disk diffusion approach. In general, concentrations of phenolic compounds and antioxidant and antibacterial properties increased slightly in grape components treated with chitosan solution. The strongest antioxidant and antibacterial properties were found in seed extracts. Certain components obtained from grapevines treated with chitosan may have greater value due to their enhanced antioxidant and antibacterial properties. Components’ phenolic compounds can be utilized in the pharmaceutical and food industries as natural preservatives and antibiotic adjuvants. According to the above discussion, the future of nanotechnology-based instruments and procedures in contemporary viticulture operations is bright. The employing of nanoparticles for treating and avoiding illnesses and pests and the intelligent distribution of nutrients and fertilizers could be utilized to address the numerous issues of conventional viticulture and to modernize the industry. Yet, in viticulture, there remains a long way to go as it strives to overcome the restrictions associated with traditional food production, adjust to farmer expectations, achieve higher volumes and quality, and encourage environmentally friendly farming.

3.6.5 Entomological Control The attack of the moth Lobesia botrana is another major issue in European vineyards. This pest damages grapes, making them more susceptible to infection by botrytis and

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Fig. 3.7 Photographs of Benitaka grapes were taken immediately after the coating process (day 0) and after a storage period of 7 days at 25 °C and 50% relative humidity. Reprinted with permission from LWT—Food Science and Technology, Copyright 2017, Elsevier [63]

other secondary fungi. In order to protect the plants from this moth, Bansal et al. developed an all-biodegradable, water-resistant nanofiber [65]. To achieve this, biodegradable polyester nanofibers were immobilized with pheromone-releasing oligolactide. Thermogravimetric analyses and in vitro release experiments have shown the slow release of microparticles from nanofibers. For this sort of phytoprotection, the slow release of the pheromone is a really fascinating outcome. Therefore, field experiments are required to observe the plant response.

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3.7 Nanomaterials in Enology Study: Synthesis and Quality Analysis The process of making wine is complicated because it combines knowledge from several fields, including chemistry, biochemistry, and microbiology. The production process of wines is just one of the unit operations that nanotechnology can aid in [66]. Nanotechnology is a relatively new phenomenon in the winemaking industry, with usage for yeast immobilization, wine contaminants removal, and the utilization of nanoparticles as antimicrobial substances being merely a few instances [67]. Yet, one of the most significant applications of nanomaterials in enology is the inclusion of these materials in particular sensors capable of detecting chemicals of various types. All of these nanoparticle uses are currently in the experimental phase. The licensing of this winemaking procedure by the International Organization of Vine and Wine (OIV) is dependent upon the European Food Safety Authority’s (EFSA) and the OIV’s independent group of specialists on hygiene and security (panel number IV) awarding the organization’s favorable assessments [68]. Figure 3.8a shows the various domains of nanotechnology used in a wide range of industries. Incorporating nanoparticles into wine testing equipment not only improves performance but also simplifies methodology, typically enhancing the treatment procedure and lowering or abolishing the requirement for sample pretreatment. With the rapid advancement of nanotechnology, nanoparticles have demonstrated promising uses in numerous biological disciplines, like some kinds of microorganisms (yeast and bacteria). Yeast immobilization and vectorization nanomaterials are a second class of nanomaterials used in winemaking [67]. Originally, yeast lees were separated from sparkling wine bottles by disgorging, a laborious and time-consuming process, owing to the magnetic characteristics of nanoparticles of iron oxide maghemite (γ-Fe2 O3 ). After the time spent on the lees phase, Berovic et al. invented a simple approach for the clean elimination of yeast lees in sparkling wines [69] (Fig. 3.8b). Yeast cells in the presence of magnetic nanoparticles (MNPs) exhibit magnetic sensitivity due to the bonding of MNPs to their surface. The non-toxic nature of iron oxide nanoparticles has been approved by the American Food and Drug Administration (FDA). When utilizing these nanoparticles in winemaking, it is important to adhere to European Union (EU) standards, which restrict the iron content in white wines to a maximum of 10 mg/L. Furthermore, Dusak et al. investigated the application of magnetoresponsive bacteria to effectively control the progression of malolactic fermentation and enable their selective removal from the fermentation medium at the desired timing [70]. Nanoparticles of superparamagnetic amino-functionalized maghemite were used to create the magnetic coating. In addition, fermentation performance has not been affected by this coating of bacteria. Employing chitosan-coated nanoparticles with magnetic properties (CS/Fe3 O4 ) as a support, a fresh and efficient method of paralyzing Saccharomyces cerevisiae’s budding ethanol dehydrogenase (YADH) has been produced successfully [71]. Considering its possible application in producing an assortment of initial components and intermediates, alcohol dehydrogenase which initiates the oxidation of alcohols

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Fig. 3.8 a A summary of the primary applications of nanotechnology in wine production. b Utilization of magnetic nanoparticles in the disgorging method for sparkling wine is demonstrated graphically. Reprinted with permission from European Food Research and Technology, Copyright 2020, Springer [68]

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and the reduction of carbonyl substances including alkaloids and ketones has drawn substantial attention. Chitosan-coated magnetic nanoparticles’ surface functionalization was employed to immobilize alcohol dehydrogenase via covalent binding and electrostatic adsorption. Immobilized alcohol dehydrogenase has been observed to retain 65% of its initial performance in relation to the enzyme in the releasing state, display enhanced thermal stability with excellent durability, and be easily recoverable by magnetic separation.

3.7.1 Odors Removal from Wine The nanofiltration procedure can be utilized as an alternate technique for removing excess acetic acid from wines. Temido et al. tested five different commercial nanomembranes using this technique in white and red wines. The results demonstrated that it is feasible to get rid of ethanol and acetic acid [72]. At present, they have observed a similar problem. When Santos and Ferreira utilized nanofiltration and electrodialysis to remove unwanted chemicals from 28 marketed Portuguese wines [73]. The efficacy of this approach in reducing volatile acidity and eliminating compounds such as ethyl acetate and volatile phenols (4-EP and 4-EG) has been demonstrated. However, it was observed that this method also removed important components, such as organic acids and alcohol, leading to sensory losses in the wine. Therefore, specific operational adjustments are necessary to tailor this production method to the requirements of wine production while minimizing organoleptic drawbacks. More tartaric or malic acids are formed by cold-climate vines that produce grapevines, which may give rise to crystalline deposits (tartrate), a significant issue within the wine business. As a result, wine deacidification is required because, to alter flavor, tartrate salts with potassium or calcium ions might form, which consumers perceive as sensorial flaws [67]. To eliminate tartaric acid (TA) from wines, the conventional technique involves cold stabilization and membrane separation. In an alternative approach, Schramm et al. explored the utilization of dendrimers to remove this compound from both white and red wines [74]. Nanostructures termed dendrimers may contain chemical compounds. In that investigation, dendrimers were used to produce a dendrimer–TA complex, which was then separated through filtration. The two tested dendrimers, poly(amidoamine) and poly(propyleneimine), were able to bind to tartaric acid efficiently. With this approach, the dendrimer-tartaric acid compound can potentially be effortlessly separated from wine samples employing reversed dialysis via ultrafiltration. Other research, with this approach, the dendrimer-tartaric acid compound can potentially be quickly separated from a wine sample employing inverted dialysis via ultrafiltration, like resveratrol and anthocyanins. Catarino and Mendes investigated commercial nanomembranes for the reverse osmosis de-alcoholization process [75]. In addition, the integration of fragrance compounds derived through pervaporation utilizing a polyoctylmethylsiloxane–polyetherimide composite membrane was

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investigated. Three of the four nanomembranes utilized were effective at reducing the alcohol concentration from 14 to 5%, as demonstrated by the results. The procedure of partial de-alcoholization coupled with the inclusion of fragrance compounds acquired through the original wine’s evaporation resulted in the production of low-alcohol wines with great sensory quality. Banvol-gyi et al. also discovered that nanofiltration can lower the alcohol content in wines [76]. In addition, they discovered that this procedure might be used to concentrate key components like resveratrol and anthocyanins, which are employed to recreate wines in addition to other eating habits and medicinal uses. In specific investigations, the use of nanofiltration has been employed to minimize the must’s sugar level before fermentation so as to generate wines with lower alcohol percentages. Salgado and colleagues evaluated a two-stage and singlestage nanofiltration procedure to lower the sugar level in musts of red and white grapes (Garnacha and Verdejo) and analyze the impact on the alcohol percentage of the wines produced [77, 78] (Fig. 3.9). The nanofiltration method effectively reduced the sugar concentration in the musts, resulting in a wine with a low alcohol percentage and no discernible tasting difference compared to normal wines.

Fig. 3.9 For the essentials of the Verdejo varietal, a fermentation flowchart and nanofiltration technologies were utilized: a two-stage and b single-stage nanofiltration processes. Reprinted with permission from Journal of The Science of Food and Agriculture, Copyright 2021, John Wiley and Sons [25]

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3.7.2 Aroma Removal from Wine Moreover, nanotechnology can be utilized to eliminate undesirable aromatic components in wine. In addition, nanomaterials have been utilized to eliminate acetaldehyde, a chemical formed during wine production that has a significant impact on wine quality. The catalytic function of gold nanoparticles (AuNPs) was studied in a few studies on the breakdown of acetaldehyde in alcoholic liquids, such as wine [79, 80]. In this context, Liu et al. demonstrated the application of AuNPs in the reduction of acetaldehyde concentration by 40% in commercial gin, wine, and ethanol solution [79]. The results showed that the generated AuNPs function as catalysts for tearing down 2000 ppm of aldehyde into an ethanol-containing solution at a 40% (v/v) concentration. Aldehyde was degraded by approximately 50% after 10 days of testing in alcohol solutions containing 25 ppm AuNPs and mild stirring. Adding 1 ppm AuNPs to gin wines containing 60 ppm aldehyde and gently swirling for 10 days rendered the aldehyde undetectable. Additional research demonstrated that chitosan-coated gold nanoparticles are more effective at decomposing acetaldehyde [81, 82]. In white wines containing 95 mg L−1 acetaldehydes, treatment with chitosan-coated gold nanoparticles reduced acetaldehydes by 75%, whereas control group has only 26% reduction [82]. In a comparison of gold nanoparticles–chitosan with diameters in the range (10–80 nm), those with a smaller diameter displayed greater catalytic activity. For instance, methoxypyrazine chemicals’ vegetable aroma can prevent wines from discharging the fruity fragrances when their concentration is above the odor threshold, a result that is unfavorable for some types of wines [83]. In this context, Liang et al. investigated the removal of 3-isobutyl-2-methoxypyrazine (IBMP) from Cabernet Sauvignon grape must and wine using magnetic nanoparticles [84]. In this study, three forms of treatment were compared: presumed imprinted magnetic polymer (PIMP), non-imprinted magnetic polymer, and a commercially available polylactic acid (PLA)-based film. Fe3 O4 @SiO2 core–shell nanoparticles were employed to develop PIMP. The PIMP treatment decreased the early levels of IBMP in wines to below or close to the threshold for sensory identification. PIMP’s greater surface area and quicker sorption kinetics made it a more successful remedial therapy than PLA-based films. Without diminishing the overall intensity of others, including fruity aroma, the sensory investigation revealed a significant reduction in the IBMPrelated green aroma feature. According to these experts, additional study is required to enhance selectivity and the printing process. In addition, a method on an industrial scale is required to make the process commercially viable. Teixeira et al. removed undesirable volatile phenols from wines using molecular imprinted extraction of organic molecules from various matrices [85]. MIPs were developed to identify 4-ethylphenol (4-EP) and 4-ethylguaiacol (4-EG). The nanoparticles demonstrated a similar capacity to reduce 4-EP and 4-EG concentrations in wines by approximately 50%. However, other key components, like flavonols, hydroxycinnamic acids, and anthocyanins, were reduced and color loss was seen. This suggests that the specificity and selectivity of the imprinted polymers should

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be enhanced. Certain yeast strains, particularly those belonging to the genus Brettanomyces, can convert cinnamic acids (p-coumaric and ferulic) to volatile phenols during wine aging [83]. The presence of ethylphenols and vinylphenols in wines can be considered undesirable in terms of sensory quality when their concentrations exceed 400 μg L−1 and 725 μg L−1 , respectively [86, 87]. To address this issue, researchers have explored the use of nanomembranes and molecularly imprinted polymers to effectively remove aromatic phenolic compounds from wine.

3.7.3 Protein Removal The specific haze caused by protein synthesis, which consumers view as a flaw, is another issue that frequently arises in the wine industry, particularly in the manufacture of white wines. Traditionally, a bentonite treatment is needed for prevention [88]. Wine losses and challenges with workplace health and safety are only a couple of the drawbacks of this method. In comparison to conventional bentonite treatment, the use of specific mesoporous silica nanoparticles (MSNPs) (average pore diameter: 7–10 nm) for the clarity of white wines has shown efficiency in eliminating protein haze and retaining fragrance components more effectively [89]. Acrylic acid plasma-coated magnetic nanoparticles has also been used in the binding and removal of proteins from wines [90]. These modified magnetic nanoparticles offer a rapid and selective means of separating proteins from white wine while having minimal impact on the phenolic fraction. In a subsequent study, the same researchers investigated the effectiveness of different surface coating agents, including allylamine, acrylic acid, and 2-methyl-2-oxazoline monomers, in removing haze-forming proteins from white wines. They extensively described the characteristics and performance of these coating agents [88]. Interestingly, the researchers observed that white wine proteins could efficiently bind to both negatively and positively charged nanoparticles, allowing for their extraction from the wine using an external magnetic field without leaving behind any nanoparticles. This innovative approach utilizing magnetic nanoparticles provides a simple and rapid method for clarifying and stabilizing wine proteins. Recently, an organization from Australia has been producing nanoparticles and functionalized interfaces for extracting proteins from wine. Mierczynska-Vasilev et al. presented a method to remove proteins from white wines, including chitinases and thaumatin-like proteins, using magnetic nanoparticles coated with acrylic acid plasma polymer [90]. Magnetic nanoparticles coated with acrylic acid plasma were used to collect and extract pathogenesis-related proteins from nine different white wines. To evaluate the effectiveness of the functionalized magnetic nanoparticles, the protein and phenolic content of treated white wines were examined. The investigation revealed that the magnetic nanoparticles with an acrylic acid coating efficiently eliminated proteins while having no effect on the wines’ phenolic content (Fig. 3.10). The standard bentonite treatment, which affects the wine-making process’ economics and sensory quality, may be replaced by this new method. This group further investigated the incorporation of various functional

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groups in the magnetic nanoparticles to improve the prior approach [88] (Fig. 3.11). In this study, plasma polymerization was used to functionalize magnetic nanoparticles having amine, carboxylic acid, and oxazoline groups on their surfaces. The results of zeta potential tests, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy have all demonstrated that allylamine, acrylic acid, and 2-methyl-2oxazoline (POx) make good coating agents for nanoparticles. The protective coatings had no effect on the crystallinity of the nanoparticles with magnetic properties, according to X-ray diffraction data. The effectiveness of removing pathogenesisrelated proteins from Sémillon and Sauvignon wines by fining them with functionalized magnetic nanoparticles was confirmed by high-performance liquid chromatography (HPLC) measurement of residual wine protein. The findings demonstrate that wine proteins are capable of being collected by all three coats during the protein attachment and binding process, with the following order of removal effectiveness COOH > POx > NH2 . The use of magnetic nanoparticles as a rapid, easy, and reliable approach to capture and remove proteins from wine is an additional practical advantage of wine treatment utilizing magnetic separation. Biocompatible magnetic nanoparticles with surface functionalization may also be useful in other beverage production processes that call for the quick, simple, and effective separation of unwanted ingredients and processing aids.

Fig. 3.10 a Illustration depicting the process of (i) plasma deposition of acrylic acid to generate (ii) COOH-rich ppAcrA-coated surfaces; (iii) functionalization of the surface through plasma deposition and subsequent reaction with wine proteins (TLPs = thaumatin-like proteins 1 and CHI = chitinases); (iv) and separation of pathogenesis-related proteins in wine using an external magnetic field. b Images showcasing the magnetic separation procedure: (i) untreated wine, (ii) wine with dispersed magnetic nanoparticles (MNPs), and (iii) wine after the application of a magnet. Reprinted with permission from Food Chemistry, Copyright 2017, Elsevier [90]

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Fig. 3.11 a FTIR absorption spectra showing the difference between bare magnetic nanoparticles (black, spectrum 1) and magnetic nanoparticles coated with plasma-polymerized acrylic acid (red, spectrum 2), allylamine (blue, spectrum 3), and 2-methyl-2-oxazoline (green, spectrum 4). b A proposed mechanism for protein adsorption on magnetic nanoparticles. Reprinted with permission from Food Chemistry, Copyright 2019, Elsevier [88]

3.7.4 Antimicrobial Silver nanoparticles have been popularly known for their antibacterial and antifungal activity against various bacterial species (such as S. aureus and E.coli) and certain types of yeasts [91]. Enologists have historically utilized sulfur dioxide (SO2 ) to regulate the microbial population in wine [92]. There is considerable interest in finding new substitutes for this particular wine component as evidence of the potential health risks associated with it grows [93]. Silver nanoparticles exhibit a broad spectrum of antibacterial activity; therefore, they could be a very promising strategy for lowering SO2 in winemaking [94]. Hence, in comparison with sulfur dioxide, it can also be efficiently utilized in the regulation of microbial populations in musts and wines [67, 95]. Moreover, it has been reported that the kaolin–silver complex appears selective for Brettanomyces yeast species, despite the reality that it appears to be particularly effective at preventing S. cerevisiae from developing [38]. Silver nanoparticles have also

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been demonstrated to have good effects on reducing lactic acid and acetic acid bacterial development in wine [96]. This study primarily focused on the possible application of silver nanoparticles in enology to reduce sulfur dioxide consumption. In order to achieve this objective, two novel silver-based nanomaterials were produced and characterized: polyethylene glycol-stabilized silver nanoparticles (PEG-Ag NPs) and glutathione-stabilized silver nanoparticles (GSH-Ag NPs). Further, authors have assessed their antimicrobial efficacy against S. aureus and E. coli, wine-isolated LAB [Pediococcus pentosaceus, Oenococcus oeni, Lactobacillus plantarum, and Lactobacillus casei], and enological AAB [Gluconobacter oxydans and Acetobacter aceti]. Finally, the antibacterial activity of silver nanoparticles against LAB and AAB was equivalent to the activity of potassium metabisulfite, which is frequently used as a winemaking ingredient. In order to gain a deeper knowledge of the underlying mechanisms, epifluorescence microscopy was used to investigate changes in cell viability following the incubation of bacteria with both synthesized silver nanoparticles. The results showed that PEG-stabilized silver nanoparticles proved to be more effective against gram-negative bacteria in comparison with gram-positive bacteria. However, glutathione-stabilized silver nanoparticles appear to be more effective against O. oeni species. The antimicrobial activity of particles might be attributed to their surface charge and size. The result supports silver nanoparticles’ capacity to regulate the activities of bacteria in winemaking and opens the door to further research into the development and application of antimicrobial-specific silver-based nanoparticles in enology. Another study also confirmed the antimicrobial efficacy of PEG and glutathione-associated silver nanoparticles against bacteria and yeasts, with even better inhibition results than sulfur dioxide [97]. Both types of silver nanoparticles undergo in vitro three-step digestion, as shown in Fig. 3.12, further, their cytotoxicity effect and alteration in the morphology of Caco-2 cells were also investigated. The results showed that both the synthesized silver nanoparticles exhibited antimicrobial effects against various microbes present in wine. The results show that in nanoform, silver nanoparticles can effectively reach the intestine, and the investigation of Caco-2 cells proves the exclusion of the harmful impact of silver nanoparticles on the intestinal epithelium. Nanoparticles were exposed to differentiate and proliferating Caco-2 cells (Fig. 3.13). Caco-2 cells at both growth stages exhibited a significant decrease in viability in all samples containing nanoparticles that had been digested. In contrast, undigested silver nanoparticles had no harmful effects on proliferating or differentiated Caco-2 cells. Although the precise process causing the inhibitory effect is unresolved, it might be explained by the charge difference between the nanoparticles that are positively charged and the negatively charged microbial cells. The food industry has typically used composite substances, including silver nanoparticles, to develop creative containers with antibacterial qualities that enable enhanced preservation of food [98]. When silver nanoparticles were incorporated into packaging supplies, the growth of bacteria was reduced by 99.9%.

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Fig. 3.12 Here, In vitro digestion process, there are actually three stages to the in vitro absorbing process: the first is the incorporation of synthetic saliva into the silver nanoparticles. a, the addition of simulated gastric fluid b, and finally the addition of simulated intestinal fluid c. Reprinted with permission from Innovative Food Science & Emerging Technologies, Copyright 2019, Elsevier [97]

3.8 Summary This chapter explores the major applications of nanotechnology in the food industry. It begins with an introduction to the topic and highlights the potential of nanomaterials to provide protective effects under stress conditions. The chapter then delves into specific applications such as the use of nanomaterials as color additives, anticaking agents, and flavors in food products. In the context of viticulture, the chapter discusses the application of nanotechnology for stress treatment, disease control, and the use of nanofertilizers to enhance crop growth. The antimicrobial activity of nanoparticles and their role in entomological control are also examined. Furthermore, the chapter explores the application of nanomaterials in enology, specifically in the synthesis and quality analysis of wine. It discusses odor and aroma removal from wine, protein removal, and the antimicrobial properties of nanomaterials in wine production. The chapter concludes with a summary of the key points discussed and provides a valuable collection of references for further exploration of the subject. Overall, this chapter provides a comprehensive overview of the diverse applications of nanotechnology in the food industry, with a specific focus on viticulture and enology.

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Fig. 3.13 MTT test was used to determine the cytotoxic effect of primary, digested silver nanoparticles and SIF on proliferative and differentiated Caco-2 cells as measured by cell viability (%). In DMEM medium, samples were diluted (1:2, 1:4, 1:10, and 1:20). Reprinted with permission from Innovative Food Science & Emerging Technologies, Copyright 2019, Elsevier [97]

References 1. Bajpai, V.K., et al., Prospects of using nanotechnology for food preservation, safety, and security. Journal of food and drug analysis, 2018. 26(4): p. 1201–1214. 2. Nakagawa, K., Nano-and microencapsulation of flavor in food systems. Nano-and Microencapsulation for Foods, 2014: p. 249–271. 3. Oehlke, K., et al., Potential bioavailability enhancement of bioactive compounds using foodgrade engineered nanomaterials: a review of the existing evidence. Food & function, 2014. 5(7): p. 1341–1359. 4. Haider, A. and I.-K. Kang, Preparation of silver nanoparticles and their industrial and biomedical applications: a comprehensive review. Advances in materials science and engineering, 2015. 2015: p. 1–16. 5. Singh, T., et al., Application of nanotechnology in food science: perception and overview. Frontiers in microbiology, 2017. 8: p. 1501. 6. Sabagh, A.E., et al., Drought and salinity stress management for higher and sustainable canola (‘Brassica napus’ L.) production: A critical review. Australian Journal of Crop Science, 2019. 13(1): p. 88–96.

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Chapter 4

Intelligent Nano-based Sensor for Quality Detection of Food Products

Abstract Nanomaterials can be successfully utilized in the construction of biosensors, which offer highly sensitive detection of pathogens in food materials, quantification of food constituents, and alerting others to food safety status. These nanosensors indicate an alteration in environmental conditions like humidity or temperature change, microbial contamination, or product degradation. A biosensor is a device attached to biological elements like nucleic acid, antibodies, receptors, or other biorecognition elements that serve as a biosensor by interacting with analytes and producing an electrical signal for detection. The effect and response of these biosensors are rapid, highly specific, and sensitive; they are free from interference but may still be affected by the presence of non-targeted microorganisms. This chapter highlights the effectiveness of nanomaterials in developing biosensors for the detection of pathogens in contaminated food. Nanomaterial-based sensors are efficient, specific, and sensitive in their operation in comparison to traditional biosensors. In order to increase the specificity of the nanosensor, it operated at a similar scale to biological processes.

4.1 Introduction Consumers are becoming increasingly concerned with the purity and safety of the food they consume. In the case of perishable food items such as fruits, vegetables, and dairy products, this concern is of particular significance. Ensuring food quality and safety is of utmost importance in the food industry, as it directly impacts the health and overall welfare of the public [1]. Manufacturers, processors, and distributors of food must ensure that their products are of high quality and secure for human consumption [2]. Consumers are increasingly concerned about the quality and safety of the food they consume for a number of reasons, including: (i) Consumers are aware of the potential health hazards associated with consuming contaminated or low-quality food products. (ii) Food contamination incidents and epidemics are frequently reported in the media, heightening consumer awareness, and concern for food safety. (iii) Governments across the globe have enacted stringent regulations to ensure that food products are safe and of high quality that has increased consumer © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_4

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awareness of these issues. (iv) The expansion of global trade and interconnectedness has significantly complicated the supply chain of the food industry, posing challenges in effectively tracking and ensuring the quality and safety of food products. (v) With the rise of social media and various online platforms, consumers now have a powerful voice to voice their concerns about food quality and safety. As a result, they are calling for increased transparency and accountability from food companies, including producers, processors, and distributors. They want assurances that the food products they ingest are safe, nutritious, and of high quality that has led to an industrywide focus on food quality and safety. Consumers anticipate that food products will be nutrient-dense, free of hazardous substances, and of a certain quality. Food quality refers to the attributes that determine the value and desirability of food products to consumers. These attributes include flavor, texture, color, aroma, nutritional value, and shelf life. On the other hand, food safety refers to the measures taken to prevent the contamination of food products with hazardous substances like bacteria, viruses, and toxins. Consequences of foodborne illnesses caused by contaminated food products can range from moderate discomfort to life-threatening conditions. In addition to the potential health risks, food contamination incidents can have significant economic repercussions, including product recalls, loss of consumer confidence, and brand reputation damage. Consequently, assuring the quality and safety of food is an essential aspect of the food industry. Diverse techniques and technologies have been devised to ensure the high quality and safety of food products [3]. Intelligent nanosensors are increasingly used in the food industry to detect and analyze a variety of food quality parameters [4, 5]. Utilizing intelligent nano-based sensors has enabled food manufacturers and processors to rapidly, accurately, and non-destructively detect and analyze various properties of food products, such as chemical composition, freshness, and contamination [6]. Nanotechnology has revolutionized the food industry in recent years by providing innovative solutions to some of the industry’s most critical problems [7]. Nanotechnology entails the manipulation of materials on the nanoscale that is between 1 and 100 nm in size. This technology has enabled the development of intelligent nanosensors that can detect and analyze the various properties of food products in a rapid, accurate, and nondestructive manner [8]. Nanotechnology has revolutionized food processing in numerous ways [8], including: (i) Intelligent nano-based sensors can detect various food quality parameters, such as freshness, maturity, and nutrient content, with high accuracy and precision, resulting in improved food quality. This technology can assist food manufacturers and processors in ensuring that their products satisfy specific quality standards and are consistently of a high standard. (ii) Intelligent nano-based sensors can detect with high sensitivity and specificity the presence of hazardous substances in food products, such as bacteria, viruses, and toxins. This technology can aid in the prevention of foodborne illness outbreaks and ensure that food products are secure for human consumption. (iii) Nanotechnology can be used to develop food packaging materials that prevent food spoilage and degradation, thereby extending the storage life of food products. The utilization of this technology holds promise in minimizing food waste and improving the accessibility of fresh food items. Nanotechnology has the potential to enhance the nutritional value of food products by improving the

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bioavailability of nutrients and facilitating their digestion in the human body. It can assist in addressing malnutrition and other health issues resulting from nutrient deficiencies. (iv) Nanotechnology has provided significant benefits to the food industry, including enhanced food quality, safety, and shelf life, as well as increased nutritional value [9]. These benefits have contributed to the industry’s ongoing efforts to meet the evolving needs and expectations of consumers all over the globe. Likewise, oligonucleotide-functionalized gold nanoparticles (AuNPs) in combination with immunomagnetic separation technique were used for colorimetric detection of Salmonella species (cause foodborne diseases) in complex matrices. This technique is very sensitive and can detect the as low as 19 bacterial cells which helps in reducing the risk of contamination and foodborne diseases [10, 11]. Further, Pseudomonas aeruginosa was also detected using fluorescence-based biosensor using polydopamine–polyethyleneimine copolymer dots labeled with aptamers [12]. The proposed sensor can detect 1 CFU/mL bacteria with detection time of 1.5 h. It can successfully detect the bacteria in real samples like orange juice, skim milk, and popsicle samples. Significant advancements have been made in recent years in the field of intelligent nanosensors for food quality detection. With the growing demand for high-quality and safe food products, the need for technologies that can detect contaminants, allergens, pollutants, and other quality indicators in food products has increased. Intelligent nanosensors are emerging as a promising technology in this respect, as they offer numerous advantages over conventional sensor technologies. They can detect a broad range of analytes with high sensitivity and selectivity, and they can be incorporated into portable and user-friendly devices. In addition, they can be produced at a lower price, making them an attractive choice for small- and medium-sized businesses. Recent advances in intelligent nanosensors have resulted in the development of sensors with even greater sensitivity and specificity. Scientists have employed nanomaterials such as carbon nanotubes, graphene, and metal nanoparticles to enhance the sensitivity and specificity of sensors, among other applications. It has been demonstrated that these sensors can detect very low concentrations of contaminants and other quality indicators in food products, making them highly effective for ensuring food safety. In addition, recent research has focused on the development of intelligent and multifunctional sensors that can simultaneously detect multiple analytes [13]. These sensors use advanced nanomaterials and nanofabrication techniques to develop complex sensing systems that can detect and distinguish between various analytes in food products [14]. Intelligent nano-based sensors have also been used in the development of anticounterfeiting devices for food products, in addition to their use in food quality detection [15]. These devices employ nanomaterials and other cutting-edge technologies to prevent food product counterfeiting and assure their authenticity. Recent advancements in intelligent nanosensors for food quality detection hold great promise for the food industry as a whole [16]. Figure 4.1 depicts a range of biosensors utilizing nanomaterials for the purpose of detecting foodborne pathogens. These advanced biosensors hold promise in boosting consumer trust by ensuring the quality and authenticity of food items, minimizing food waste, and bolstering overall food safety.

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Fig. 4.1 Biosensors utilizing nanomaterials for the detection of foodborne pathogens, adapted from [16]

Due to their unique physical, chemical, and biological properties, nanomaterials have been extensively utilized in the development of intelligent nanosensors and biosensors. These materials have a high surface-to-volume ratio, tunable surface chemistry, and enhanced sensitivity and selectivity, making them suitable for the development of highly sensitive and selective sensors and biosensors for detecting food quality. As sensing elements, nanomaterials like carbon nanotubes, graphene, AuNPs, quantum dots (QDs), and metal oxides are frequently used in the construction of nanomaterial-based sensors. The nanomaterials are functionalized with specific receptors, such as antibodies, aptamers, enzymes, or DNA strands that recognize the desired target analyte. The presence of the target analyte leads to an interaction with the receptor situated on the surface of the nanomaterial, resulting in the generation of a detectable signal. This signal is subsequently converted into an electrical, optical, or mechanical form to facilitate its detection. Nanomaterial-based biosensors, on the other hand, involve the integration of nanomaterials with biological components such as enzymes, cells, or tissues, forming a hybrid system that exhibits exceptional sensitivity and specificity for the detection of analytes. The biological components serve as the sensor, while the nanomaterials provide signal amplification and transduction.

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Overall, the use of nanomaterials in the construction of sensors and biosensors has revolutionized the field of food quality detection by facilitating the development of highly sensitive, selective, and dependable detection methods [16]. Figure 4.2 illustrates the schematic representation of constructing nanomaterial-based sensors and biosensors. This diagram provides an overview of the process involved in developing these advanced sensing systems using nanomaterials. The objective of this chapter is to present a comprehensive overview of intelligent nanosensors and their diverse applications in the field of food quality detection. The chapter will discuss the fundamentals of intelligent nanosensors, including their operation principles, the nanomaterials utilized in their development, and their design and development. This chapter will also examine the applications of intelligent nano-based sensors in various areas of food quality detection, such as the detection of bacterial and fungal contamination, food adulteration and authenticity, anticounterfeiting devices, food allergens and toxins, and spoilage in food crop grain. In addition, the chapter will explore the challenges and future directions of intelligent nano-based sensors in the food industry, including the need for standardization, regulatory considerations, and ongoing research. This chapter aims to provide readers with an in-depth understanding of the potential of intelligent nanosensors in the food industry and their applications in ensuring the quality and safety of food products. Researchers, food industry professionals, and others interested in the applicability of nanotechnology to the food industry will find this chapter to be of interest.

Fig. 4.2 Diagram depicting the construction of sensors and biosensors using nanomaterials, adapted from [16]

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4.2 Bacterial and Fungal Contamination Detection In this section, we will explore the utilization of intelligent nanosensors for the identification and detection of bacterial and fungal contaminants in various food products. The section will also discuss the varieties of sensors used, their sensitivity and specificity, as well as the advantages of employing these sensors to ensure food safety. In the food industry, bacterial and fungal contamination is a significant concern because it can cause foodborne illnesses and food spoilage. Detecting these contaminants is crucial for ensuring the safety and integrity of food. Intelligent nanosensors have emerged as a potentially useful technology for detecting bacterial and fungal contamination in food products. Using sophisticated nanomaterials and nanofabrication techniques, these sensors are extremely sensitive and selective, allowing them to detect these contaminants at low concentrations. Several varieties of sensors, including electrochemical sensors, optical sensors, and biosensors, have been developed for the detection of bacterial and fungal contamination. Electrochemical sensors rely on the measurement of changes in electrical properties caused by the interaction between the sensor and the analyte of interest. In contrast, optical sensors rely on changes in light transmission or reflection caused by the interaction between the sensor and the target analyte. Biosensors make use of biological elements like antibodies or enzymes to interact with the target analyte, generating a detectable signal. The advancement of nanomaterial synthesis and the creation of highly specific and sensitive biosensors have expanded the possibilities for the development of effective biosensors in the field of agrodefense. It indicates that substantial progress has been made in the development of biosensors for agrodefense applications, but there are still some obstacles to overcome. The assessment of biosensor development and the current challenges in the field can provide future directions for the field. This indicates that sustained research in this area is necessary to meet the needs of modern agriculture and food production. It may be possible to prevent the spread of plant pathogens, reduce crop losses, and improve food safety by developing effective agrodefense biosensors as shown in Fig. 4.3. It has been demonstrated that intelligent nanosensors offer several advantages over conventional sensors for the detection of bacterial and fungal contamination. They can detect these contaminants at much lower concentrations, thereby improving the detection’s accuracy and sensitivity. Moreover, they can be incorporated into portable and user-friendly devices, making them ideal for use in the field or by small and medium-sized businesses. Multiple studies have demonstrated the efficacy of intelligent nanosensors for detecting bacterial and fungal contamination in food products. For instance, scientists have devised biosensors that use antibodies to detect the presence of pathogenic bacteria in food samples, such as E. coli and Salmonella. It has been demonstrated that these biosensors can detect these contaminants at extremely low concentrations, making them extremely useful for ensuring food safety [18]. Similarly, researchers have created electrochemical and optical sensors capable of detecting mycotoxins in food products [19]. By employing nanomaterials like carbon nanotubes and metal nanoparticles, the sensors’ sensitivity and selectivity have been

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Fig. 4.3 Agrodefense: Biosensors for ensuring food safety from disease-free crops and animals. Reprinted with permission from Trends in Food Science & Technology, Copyright 2018, Elsevier [17]

enhanced, allowing for the detection of minute quantities of fungal contaminants in food samples. The utilization of intelligent nanosensors in detecting bacterial and fungal contamination in food products has the capability to greatly enhance the safety and quality of food. These sensors can detect these contaminants at lower concentrations than conventional sensors, and they can be integrated into portable and user-friendly devices, making them ideal for use in the food industry. Figure 4.4 depicts the analytical methods employed for the detection of microorganisms in food samples.

4.2.1 Detection of Bacterial Contamination Recent advances in intelligent nano-based sensors for bacterial detection have centered on enhancing detection sensitivity, selectivity, and speed. The use of nanomaterials such as graphene and AuNPs, the development of multiplexed biosensors, and the use of microfluidic devices for sample preparation and analysis are among the most significant developments in this field. Research has shown that the utilization of nanomaterials such as graphene and AuNPs can enhance the sensitivity and selectivity of bacterial biosensors [21, 22]. For example, researchers have developed biosensors that detect E. coli and Salmonella in food samples using graphene oxide nanoribbons and AuNPs. It has been demonstrated that these sensors are highly sensitive and selective, with low detection limits of 1 CFU/mL [23]. Novel biosensors capable of simultaneously detecting multiple bacterial contaminants in food samples have been successfully developed [24–26]. These biosensors use multiple biological components, such as antibodies or enzymes, to detect and generate a signal for each bacterial contaminant. It has been demonstrated that this method increases the efficiency and precision of bacterial detection in edible products. In

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Fig. 4.4 Methods for detecting microorganisms in food samples using analytical techniques. Reprinted with permission from Current Opinion in Food Science, Copyright 2019, Elsevier [20]

pathogen detection, microfluidic devices have also been used for sample preparation and analysis [27, 28]. These devices enable the quick and effective isolation of bacterial cells from food matrices, and when combined with biosensors, they allow for the on-site detection of bacterial contaminants [29]. For instance, researchers have created a microfluidic biosensor for detecting E. coli in samples of ground beef [25]. Combining microfluidic sample preparation and electrochemical detection, the biosensor exhibited detection limit of 2.5 CFU/g [30]. Recent advances in intelligent nano-based sensors for bacterial detection have centered on enhancing sensitivity, selectivity, and detection speed. These developments have the potential to enhance the efficacy and precision of bacterial detection in food products, thereby enhancing food safety and quality. The articles discuss recent progress in intelligent biosensing technologies applied to the detection of bacterial contamination in food products. These advancements include the utilization of nanomaterials, multiplexed biosensors, and microfluidic devices [31]. Pseudomonas syringae is a pervasive plant pathogen that impacts numerous economically significant plant species. Ralstonia solanacearum is a soil-borne bacterium that results in substantial economic losses, mainly due to the lack of efficient chemical control measures. In the European Union, Xanthomonas campestris Vesicatoria is a quarantine pathogen that can persist in tomatoes and their seeds and has economic significance. The disease symptoms induced by these bacteria on citrus leaves and fruits are depicted in Fig. 4.5.

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Fig. 4.5 Manifestations of bacterial diseases on the leaves and fruits of citrus plants. Reprinted with permission from Trends in Food Science & Technology, Copyright 2018, Elsevier [17]

The majority of biological contaminants in food are caused by photogenic bacteria. S. aureus, S. enterica, E. coli, Cl. Perfringens, L. monocytogenes, and V. cholera, are the most prevalent food-contaminating bacteria.

Escherichia Coli E. coli sensors are widely utilized for the detection of microorganisms in food samples, owing to their high sensitivity and specificity [32]. These sensors rely on E. coli strains engineered genetically to produce fluorescent or luminescent signals in the presence of specific bacterial targets. Measuring the signal’s intensity, the sensor can detect the presence of microorganisms in food samples. In food samples, E. coli-based sensors can detect numerous bacterial pathogens, including Salmonella, Listeria, and E. coli with high accuracy and sensitivity. In addition, they are user-friendly and produce results quickly. However, the need for specialized apparatus and the possibility of false-positive results due to the presence of non-target bacteria are obstacles associated with E. coli-based sensors. Overall, E. coli-based sensors are a promising instrument for the detection of bacteria in food samples, and ongoing research focuses on enhancing their performance and addressing the obstacles associated with their application. Zhu and colleagues devised an expeditious approach to identify and classify lipopolysaccharides (LPS) by employing two distinct types of aptamerfunctionalized AuNPs with varying affinities for binding [33]. In their study, the researchers employed aptamers targeting ethanolamine and E. coli LPS to modify the AuNPs which referred to as the general probe (G-probe), can bind to ethanolamine, which is a component found in all types of LPS. On the other hand, AuNPs that

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were modified with the aptamer specific to the LPS of E. coli have a selective binding affinity to bacteria LPS and are referred to as the specific probe (S-probe). By utilizing these two probes, a logic typing method was established. When both probes are present in the solution, the G-probe can recognize LPS of any type due to its binding affinity with ethanolamine. This leads to the AuNPs aggregation and a visible change of color to blue from red. However, in the presence of the specific LPS, the S-probe selectively binds to it, preventing the AuNPs aggregation while maintaining the red color. The developed method can detect 2.5–20 µg/mL LPS concentrations range, with 1 µg/mL detection limit. This dual aptamer-based colorimetric approach exhibits significant potential for the selective detection of microorganisms, serving as a versatile and sensitive tool for the rapid and specific identification and typing of LPSs. It enables efficient microbial analysis with high precision and speed. In another study, Pandit et al. demonstrated quantitative and qualitative detection of E. coli cells by utilizing superparamagnetic iron oxide nanoparticles (SPIONs) functionalized with E. coli-specific aptamer I [34]. Through magnetic separation, the sludge containing the E. coli-SPION complex was efficiently separated. The confirmation of the presence of E. coli cells was conducted through conventional methods and advanced imaging techniques such as confocal laser scanning microscopy (CLSM). Aptamer II, in conjunction with CdTe-MPA QDs, was utilized for CLSM imaging, enabling precise detection and visualization of E. coli cells. To achieve quantitative and qualitative detection of E. coli, authors developed Aptamer II conjugated CdTe-MPA QDs and a microcontroller-based prototype biosensor. The biosensor demonstrated the ability to detect low bacterial counts, even as low as 1 × 102 CFU, utilizing a photodiode and plano-convex lens. The developed prototype biosensor featured essential components, including a liquid crystal display, ultraviolet light-emitting diode and the microcontroller. This integrated system facilitated the detection of E. coli in water samples directly at the testing site, offering exceptional resolution and sensitivity. Furthermore, this internally developed prototype biosensor shows potential in detecting bacterial contamination in food samples. Its versatility and capabilities make it a valuable tool for rapid and reliable detection of E. coli, both in water and food matrices. By combining SPIONs, aptamers, and QDs, authors have established an effective biosensing platform with promising potential for various applications in the microbial analysis field.

Salmonella Salmonella is a bacterium that can lead to food poisoning in humans. It is frequently found in contaminated food products, especially uncooked or undercooked meat, poultry, and eggs [35]. Detecting Salmonella in food is therefore essential for assuring food safety and preventing foodborne illnesses. Traditional culture-based methods and rapid molecular-based methods, such as polymerase chain reaction (PCR) and DNA microarrays, are available for detecting Salmonella in foods. These techniques are trustworthy, but they require specialized apparatus and knowledge as well as

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time-consuming. Recent advances in nanobiosensor technology have enabled the development of swift and sensitive Salmonella biosensors for use in food safety applications. These biosensors can detect Salmonella in food samples with high specificity and sensitivity in a matter of minutes. They are founded on various detection principles, including electrochemical, optical, and piezoelectric, and can be integrated with microfluidics and nanomaterials to enhance performance. Nanobiosensors have the potential to transform the way food safety is monitored and ensured by providing real-time detection and enabling immediate corrective actions in the event of contamination. However, additional research is required to optimize and validate these biosensors for use in the commercial food industry. Recently, Zheng et al. demonstrated Salmonella typhimurium detection based on highly sensitive optical biosensor [36]. The biosensor utilized porous passive threedimensional (3D) micromixer and gold@platinum nanocatalysts (Au@PtNCs). The detection process involved several steps. First, immunomagnetic nanoparticles were employed to separate the target Salmonella cells, aided by the passive 3D micromixer. Following that, the target cells were labeled with immune Au@PtNCs, which acted as the signal output. The catalytic reaction between the labeled Au@PtNCs and H2 O2 – TMB (Hydrogen peroxide–3,3' ,5,5' -Tetramethylbenzidine) produced a measurable absorbance at 652 nm wavelength, allowing bacterial amount determination. The optical biosensor that was developed exhibited the ability to detect Salmonella within a time frame of 1 h, covering a concentration range of 1.8 × 101 –1.8 × 107 CFU/mL. The calculated detection limit was 17 CFU/mL. In addition, the micromixer enabled the efficient magnetic separation of 99% of the target bacteria from the sample in just 10 min. This biosensor shows promise for detecting other bacteria by making modifications to the antibodies employed. Using Cu(II)-modified reduced graphene oxide nanoparticles (Cu2+ -rGO NPs) with peroxidase-like activity in conjunction with PCR, Wang et al. have developed a novel colorimetric approach to identify Salmonella spp. in milk [37]. Under ideal circumstances, the colorimetric approach showed good specificity and sensitivity for the detection of Salmonella spp. With a linear range from 1.93 × 101 to 1.93 × 105 CFU/mL, the limit of detection for Salmonella spp. was determined to be 0.51 CFU/mL. The approach could distinguish between S. enteritidis and S. typhimurium other foodborne pathogens with accuracy, according to a specificity study. The use of the suggested technique to find Salmonella spp. in milk samples served to further establish its efficacy. S. typhimurium recovery rates in samples of tainted milk varied from 102.84 to 112.25%. This colorimetric sensor presents a promising approach to ensure food safety and quality, offering significant potential for the highly sensitive detection of bacteria in milk samples.

Listeria Listeria monocytogenes is a type of gram-positive bacterium that has the potential to cause severe foodborne infections, particularly in vulnerable groups such as pregnant women, the elderly, and individuals with weakened immune systems [38]. Listeriosis

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is a disease caused by Listeria monocytogenes, which can produce fever, muscle pain, and gastrointestinal symptoms. Traditional culture-based methods, immunological assays, and molecular techniques such as PCR and loop-mediated isothermal amplification (LAMP) can be used to detect Listeria in food products. Typically, these methods entail the detection of L. monocytogenes DNA, RNA, or particular antigens. In recent years, biosensors for the detection of Listeria in consumables have also been developed. These biosensors employ diverse detection mechanisms, including electrochemical, optical, and acoustic, and are intended to be rapid, specific, and sensitive. Some biosensors capture L. monocytogenes using antibodies or aptamers as recognition elements, while others use bacteriophages or other types of specific biological agents. In general, biosensors offer a promising approach for the detection of Listeria in food products. They provide a faster, more reliable, and highly specific method of detection, offering increased sensitivity and specificity compared to traditional methods. Lee et al. demonstrated on-site detection of L. monocytogenes based on electrochemical impedance immunosensor comprised of single-walled carbon nanotubes (SWCNTs) [39]. The sensor utilized a functionalized gold-plated wire coated with bovine serum albumin (BSA), biotinylated L. monocytogenes antibodies, streptavidin, polyethylenimine (PEI), and SWCNTs. In concentration range of 103 – 108 CFU/mL L. monocytogenes, the electron transfer resistance measurements showed a linear relationship (R2 = 0.982). The developed sensor demonstrated exceptional selectivity for the target pathogen, even when other bacterial cells like S. Typhimurium and E. coli were present. In order to address the need for on-site detection, the researchers integrated the sensor into a biosensor platform that can be controlled using a smartphone. This platform consisted of a compact potentiostat device and a smartphone, enabling easy and portable operation. The obtained signals from the proposed platform were compared to those obtained using a conventional potentiostat, employing the immunosensor to interact with L. monocytogenes at concentrations of 103 –105 CFU/mL, and both instruments showed high consistency in the signals obtained. We further evaluated the performance of the portable platform by analyzing recovery percentages L. monocytogenes spiked lettuce homogenate at concentration of 103 , 104 , and 105 CFU/mL. The recovery percentages were found to be 90.21%, 90.44%, and 93.69%, respectively. In summary, the presented immunosensor platform based on SWCNTs exhibits significant promise for on-site applications in the food and agricultural industries. It provides a highly sensitive and selective detection method that can be conveniently utilized in field settings. In another study, Donoso et al. developed a novel nanohybrid compound for optical detection of Listeria [40]. This compound involved the functionalization of polyamidoamine dendrimers with a lipoic acid and fluorescent QDs. The prepared nanohybrid sensor exhibited a low detection limit of viable L. monocytogenes at 5.19 × 103 CFU/mL when observed under epifluorescence microscopy. During testing, the immunosensor exhibited specificity when compared to other pathogens commonly encountered in food samples. Bai et al. developed a rapid and sensitive point-of-care testing (POCT) method for the detection of L. monocytogenes [41]. The method involved the effective synthesis

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of polyethylene glycol (PEG)-mediated ampicillin functionalized magnetic beads (Amp-PEG-MBs), which displayed excellent efficiency (more than 90%) and quick (5 min) capture of L. monocytogenes at room temperature. Unique combination of antibody (Ab), glucose oxidase (GOD), and graphene oxide (GO) was utilized by the author in order to obtain the desired result of specific recognition of L. monocytogenes. Result guarantees the specific binding of L. monocytogenes by creating the antibody Ab@GO@GOD. Amp-PEG-MBs and Ab@GO@GOD were then put together to form a sandwich structure, which was referred to as Amp-PEG-MBs@L. monocytogenes-Ab@GO@GOD in the following step of the process. This structure made the catalysis of glucose easier, and a blood glucose meter (also known as a BGM) was used to record the results of the detection. Within 66 min, the authors were able to successfully detect L. monocytogenes in intentionally contaminated juice by combining magnetic separation (MS) and an enzyme-catalyzed sensor known as MSAb@GO@GOD-BGM. This was accomplished by the integration of these two techniques. It was established that 101 CFU/mL represents the sensor’s lowest possible detection threshold. In addition, by altering particular antibodies, this sensor may also be able to identify other types of infectious agents in the future. In conclusion, the developed POCT method that combines Amp-PEG-MBs with Ab@GO@GOD offers a method that is both quick and sensitive for detecting L. monocytogenes. This sensor exhibits promising applications in the field of pathogen detection due to its capacity to identify other diseases through the utilization of specific antibodies.

Staphylococcus The common bacteria Staphylococcus can induce food poisoning in humans. Staphylococcus aureus is one of the primary species of Staphylococcus associated with food safety concerns [42]. This bacterium is capable of producing enterotoxins, which can lead to gastrointestinal distress in humans. Traditional culture-based methods and molecular techniques such as PCR and ELISA (enzyme-linked immunosorbent assay) can be used to detect Staphylococcus bacteria in food. Biosensors are one of the emerging methods for detecting Staphylococcus. By recognizing specific biomolecules or genetic sequences associated with Staphylococcus bacteria, biosensors are able to detect their presence. Biosensors for detecting Staphylococcus include immunosensors that use antibodies to detect S. aureus in food samples and electrochemical biosensors that detect the DNA of Staphylococcus bacteria by hybridizing with specific DNA probes. These biosensors have the potential to provide rapid and accurate detection of Staphylococcus bacteria in food, thereby aiding in the prevention of outbreaks of contaminated illness. Xie et al. developed unique method for the fabrication of hollow and porous nitrogen-doped carbon nanoballoons loaded with gold nanoparticles (Au-NC-NBs) [43]. The nanoballoons possess notable characteristics, including a substantial specific surface area and elevated levels of nitrogen and gold content. Utilizing these Au-NC-NBs, authors have constructed a surface-enhanced Raman scattering (SERS) aptasensor with improved performance compared to previously reported sensors. The

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SERS aptasensor that is based on the Au-NC-NBs displays both a reduced detection limit (3 cells/mL) and a larger linear range for bacterial detection (10–107 cells/ mL). Additionally, it has improved selectivity when it comes to the detection of germs. Notably, the Au-NC-NBs SERS aptasensor has outstanding performance when it comes to identifying bacteria in real food and biological samples. This study presents a straightforward and adaptable approach for constructing controlled SERS biosensors through the integration of gold nanoparticles and carbon materials. The developed biosensor exhibits significant potential for utilization in the monitoring of food safety and clinical diagnosis. In a separate study, Liu and colleagues successfully developed a dependable colorimetric sensor for the accurate detection of S. aureus. The sensor employs a click chemical reaction in combination with immunomagnetic separation, ensuring reliable and sensitive detection [44]. As separation and signal transduction components, the sensor makes use of aptamer-functionalized Fe3 O4 nanoparticles that are labeled with alkaline phosphatase (ALP). The signal transduction mechanism generates Cu+ ions, which trigger a click chemical reaction, when the experimental conditions are optimized to their full potential. A noticeable shift in color may be seen as a result of this reaction, which brings about the aggregation of azides and alkynefunctionalized gold nanoparticles. The change in color, measured as the net extinction ratio of Δ(A530 /A760 ), exhibits a linear correlation with the concentration of S. aureus in the range of 10–106 CFU/mL. The limit of detection for the sensor is determined to be 2.4 CFU/mL. When applied to the analysis of food and water samples spiked with S. aureus, the sensor demonstrates satisfactory recovery rates ranging from 91.15 to 106.36%, without the need for pre-enrichment steps. The findings from this study indicate that the proposed detection platform presents a straightforward and precise approach for on-site visual detection of S. aureus. This platform shows significant potential for diverse applications that demand swift and dependable S. aureus detection.

Clostridium Clostridium spp. are gram-positive, anaerobic bacteria that are widespread in nature and can be found in soil, water, and the gastrointestinal tracts of humans and animals [45]. Some species of Clostridium are the cause of foodborne infections, such as botulism and tetanus. Clostridium botulinum is one of the most well-known Clostridium species capable of causing food poisoning by producing botulinum toxin. This bacterium is commonly found in sediment and can contaminate food products, such as canned foods that have not been processed or stored properly. Botulism is a deadly disease that can cause paralysis, respiratory failure, and even mortality. Important for assuring food safety is the detection of Clostridium spp. in foods. Traditional culture-based techniques and molecular techniques, such as PCR-based assays, have been devised to detect Clostridium spp. in food samples. Biosensors, which can provide rapid and sensitive detection of bacterial contamination in food samples, are one strategy for detecting Clostridium spp. in foods.

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Biosensors based on immunosensors or nucleic acid sensors have been created for the detection of Clostridium spp. in foods. These biosensors can detect the presence of bacterial organisms or specific nucleic acid sequences in food samples, such as the botulinum toxin gene. The development of sensitive and specific biosensors for detecting Clostridium spp. in food samples can aid in ensuring the safety of food products and preventing outbreaks of infectious illness caused by these bacteria. Qian et al. synthesized two different morphologies of nanoceria by adjusting the concentration of NaOH. Among them, cerium oxide (CeO2 ) nanorods were selected as the sensing material for the efficient detection of the DNA sequence of C. perfringens. The CeO2 nanorods demonstrated a higher affinity for DNA due to their strong adsorption ability compared to CeO2 nanoparticles [46]. To immobilize the DNA probe onto the electrode surface, authors employed a CeO2 /chitosan modified electrode, where the DNA probe was tightly bound through metal coordination. It was determined that the surface density of the DNA that had been immobilized was 2.51 × 10−10 mol/cm2 . The electrochemical impedance biosensor showed great selectivity toward the target DNA when the experimental conditions were optimized. The biosensor also showed low interference from base-mismatched and noncomplementary DNA sequences. The biosensor’s dynamic linear range for detecting C. perfringens oligonucleotide sequence, between 1.0 × 10−14 and 1.0 × 10−7 mol/ L. This range was determined by the dynamic range of the biosensor. The biosensor was able to attain a detection limit of 7.06 × 10−15 mol/L in its testing. Comparatively, the differential pulse voltammetry (DPV) approach demonstrated a detection limit of 1.95 × 10−15 mol/L when it came to determining the concentration of the target DNA. In addition, the authors effectively utilized the DNA biosensor to detect C. perfringens DNA extracted from dairy products, showcasing its potential use in food quality control. This biosensor offers a promising solution for sensitive and selective DNA detection in various fields. Clostridium bacteria produce botulinum neurotoxins (BoNTs) which is potent toxins and can cause the severe illness botulism [47]. Among the BoNT serotypes, BoNT serotype E (BoNT/E) is a common cause of foodborne botulism and requires rapid detection and differentiation to ensure timely treatment and identify toxin sources. However, there are limited methods available for detecting BoNT/E, particularly for serotyping purposes. In this context, study demonstrated Förster resonance energy transfer (FRET)-based novel nanobiosensor between QDs and peptide probes conjugated with a dark quencher [48]. This nanobiosensor enables the detection of biologically active BoNT/E in aqueous environments. The peptide probes used in this sensor feature a specific cleavage site for active BoNT/E. When the peptide probe is cleaved by the toxin, the QDs photoluminescence undergoes intensity changes due to FRET, indicating the presence and quantity of the toxin. Detection of both the BoNT/E light chain (LcE) and holotoxin was achieved within a short period of 3 h. The limits of detection were determined to be 0.02 ng/mL for LcE and 2 ng/ mL for holotoxin. The nanobiosensor exhibits excellent specificity toward the target toxin, even in the presence of other non-target BoNT serotypes. The nanobiosensor presents numerous benefits, such as exceptional sensitivity, ease of use, fast detection time, and compatibility with probes designed for different BoNT serotypes. These

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features make it highly suitable for the rapid detection and serotype discrimination of BoNT/E in food analysis. Overall, the nanobiosensor represents a valuable tool for efficient and accurate detection of BoNT/E, contributing to improved food safety and public health.

Vibrio Parahaemolyticus Vibrio parahaemolyticus, a gram-negative bacterium commonly found in marine environments, is a major cause of foodborne illness associated with the consumption of raw or undercooked seafood [49]. Infections with V. parahaemolyticus can result in gastrointestinal symptoms including abdominal pain, diarrhea, vomiting, and fever. For the detection of V. parahaemolyticus in foods, several methods are available, including culture-based methods, PCR-based methods, immunological methods, and biosensors. Culture-based methods involve the selective enrichment of V. parahaemolyticus from food samples, followed by the organism’s identification based on its distinctive growth and biochemical properties. Using specific primers to amplify the DNA of V. parahaemolyticus, PCR-based methodologies enable sensitive and specific detection. Using antibodies that bound to V. parahaemolyticus antigens, immunological techniques such as ELISA can detect the presence of the organism in food samples. Biosensors for the detection of V. parahaemolyticus are also being developed. These biosensors can provide rapid and sensitive detection of the organism in food samples via electrochemical, optical, and nanotechnologybased sensing mechanisms. Overall, detection and control of V. parahaemolyticus in food are essential for preventing outbreaks of infectious illness and ensuring food safety. Fu et al. demonstrated efficient detection of V. parahaemolyticus based on novel colorimetric immunoassay using AuNPs having 18.1 nm diameter of as a chromogenic substrate [50]. The assay integrates a sandwich immunoassay using magnetic beads with an optical sensing system that utilizes the aggregation of gold nanoparticles facilitated by Mn2+ ions. To target recognition, manganese oxide (MnO2 ) nanoparticles with a diameter of 7.8 nm, coated with polyclonal IgG antibodies, are utilized. These nanoparticles can be etched by ascorbic acid, leading to the generation of manganese ions. Color shifts from red to purple to blue have been observed as the amount of V. parahaemolyticus in the sample increases from 10 to 106 CFU/mL. This corresponds to the range of concentrations that can be found in the sample. This approach has been shown to have very high specificity, and it has a detection threshold of 10 CFU/mL of sample. In addition, it has been used effectively to determine the presence of V. parahaemolyticus in oyster samples without the necessity of pre-enrichment. This was accomplished with great effectiveness. It can be concluded that this method has a lot of potential, not only for the rapid instrumental identification of V. parahaemolyticus but also for the on-site visual detection of the bacteria. In another study, Duan et al. demonstrated a highly sensitive and specific method for the collection and detection of pathogenic bacteria utilizing quantum dots as a

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fluorescence marker and aptamers as the molecular recognition element, coupled with flow cytometry [51]. To achieve this, authors employed a bacterium-based SELEX strategy to select aptamer sequences specifically targeting V. parahaemolyticus and S. typhimurium. By utilizing these aptamers in our method, we can achieve the specific recognition of the bacteria even in complex mixtures such as shrimp samples. The aptamer-modified QDs (QD-apt) were utilized to selectively capture and simultaneously detect the target bacteria with remarkable sensitivity through the fluorescence signal emitted by the labeled QDs. This method offers enhanced sensitivity compared to approaches utilizing individual dye-labeled probes, owing to the high photostability of QDs nanoparticles, which results in amplified signal intensity. Furthermore, this approach holds promise for the sensitive detection of other pathogenic bacteria in various food samples, provided suitable aptamers are selected. Additionally, the utilization of aptamer-conjugated QDs in flow cytometry opens up new possibilities for developing alternative platforms for bacterial detection.

Shigella Shigella is a type of gram-negative bacteria that can induce gastroenteritis in humans. The most prevalent symptoms of shigellosis, the infection caused by Shigella, are diarrhea, fever, and abdominal cramps [52]. Typically, Shigella is transmitted through contaminated food or water, particularly in areas with inadequate sanitation. Shigella detection in food samples is essential for ensuring food safety and preventing shigellosis outbreaks. Diverse techniques for detecting Shigella in food have been devised, including culture-based techniques, immunological techniques, and molecular techniques. The culture-based methods involve isolating and identifying the bacteria from food samples, whereas the immunological methods employ antibodies to detect Shigella antigens specifically. Molecular techniques, including PCR, amplify and detect Shigella-specific DNA sequences in food samples. Recently, biosensors for the rapid and sensitive detection of Shigella in food samples have also been developed. These biosensors utilize antibodies or aptamers that recognize and bind specifically to Shigella and can detect the bacterium in minutes to hours. Some biosensors employ nanomaterials, such as AuNPs or graphene, to improve their sensitivity and selectivity. The creation of these biosensors has the potential to enhance food safety and prevent the spread of shigellosis. Recently, Song et al. demonstrated rapid and specific detection of Shigella using novel nanoplatform (Fig. 4.6). The nanoplatform utilizes biofunctionalized magnetic nanoparticles (MNPs) that have been modified with upconversion nanoparticles (UCNPs). The Shigella aptamer-functionalized horseradish peroxidase (HRP) and complementary strand-modified MNPs@UCNPs are the foundation of the detection method. If Shigella is not present, the HRP that is associated with MNPs@UCNPs can be magnetically isolated resulting in the oxidation of colorless TMB into blue oxTMB. Fluorescence quenching at 545 nm caused due to the overlap between the absorption peak of oxTMB and the emission peak of MNPs@UCNPs. This fluorescence biosensor of MNPs@UCNPs enables the detection of Shigella within 1 h,

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Fig. 4.6 a Different Shigella concentrations ranging from 2.3 × 107 to 2.3 × 101 CFU/mL. The fluorescence spectra of the developed method were recorded at b A calibration curve was created to establish a relationship between the fluorescence intensity at 545 nm of the developed technique and different concentrations of Shigella. c The fluorescence intensity of the MNPs@UCNPs fluorescence sensor was recorded when various bacteria were introduced, adapted from [53]

with a low detection limit of 32 CFU/mL. The results obtained from chicken samples are also exciting, and this study indicates the establishment of a quick and selective sensing platform for the detection of Shigella. Highly sensitive and specific aptamer-based sensor was developed for the detection of Shigella sonnei using SERS analysis [54] (Fig. 4.7). Citrate-stabilized gold nanoparticles (Cit-Au NPs), which acted as both the active substrate and the Raman reporter, were included into the sensor in the form of a composite material. This material was composed of the Raman-active 4-MBA ligand of the Eu-complex and citrate. On the surface of the dual-functional composite material, aptamers that target S. sonnei were changed so that they may be detected specifically. This allowed for the specific identification of S. sonnei. In the presence of S. sonnei, the aptamers were able to attach themselves to the target with a high level of affinity and specificity, which led to the attachment of the dual-functional material onto the bacteria. The SERS intensity response displayed a high positive linear correlation (R = 0.9956) with increasing concentrations of S. sonnei, which ranged from 10 to 106 CFU/mL. This connection was observed over the entire concentration range. The sensor showed a high level of specificity for Shigella species, such as S. dysenteriae, S. flexneri, and S. boydii, in addition to other common bacteria, such as E. coli, S. aureus, and S. typhimurium. When the method was put to the test using actual samples (milk and chicken breast), it achieved good recoveries that ranged from 92.6 to 103.8%. The approach that was devised has a substantial amount of potential for the development of a variety of aptasensors that are capable of providing accurate and convenient detection of numerous food risks.

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Fig. 4.7 Schematic for detection of Shigella sonnei bacteria using SERS-based sensor. Reprinted with permission from Colloids and Surfaces B: Biointerfaces, Copyright 2020, Elsevier [54]

Bacillus Bacillus cereus is a gram-positive, spore-forming bacterium that can induce human foodborne illness [55]. It is present in soil, dust, rice, pasta, meat, vegetables, and milk, among other foods. There are various techniques for detecting B. cereus in foods, such as culture-based techniques, immunological techniques, and molecular techniques. Methods based on culture involve growing microbes in selective media and identifying them based on their distinguishing characteristics. Using antibodies, immunological techniques can detect the presence of B. cereus in food samples. The DNA of microbes can be detected in food samples using molecular techniques such as PCR. In recent advancements, the development of biosensors for the rapid and sensitive detection of B. cereus in food products has emerged. These biosensors offer the potential for on-site testing, enabling quick and efficient detection of microorganisms in edibles. In order to detect B. cereus in milk samples, one type of biosensor employs carbon nanotubes and an aptamer-based recognition element. Within five minutes, the biosensor could detect B. cereus in milk samples with high sensitivity and specificity. With a detection limit of 10 CFU/mL, another biosensor detected B. cereus in food samples using a microfluidic immunosensor. B. cereus detection in foods is crucial for ensuring food safety and preventing infectious illness. The advancement of biosensors for the rapid and sensitive detection of B. cereus holds great promise in improving food safety and reducing the incidence of foodborne illnesses. The quick identification of Bacillus anthracis endospores in contaminated food samples has been made possible by the development of an innovative biosensor that makes use of electrically active polyaniline-coated magnetic (EAPM) nanoparticles [56]. The EAPM nanoparticles, with a diameter of 100 nm, are synthesized by coating gamma iron oxide cores with aniline monomer that is rendered electrically active through acid doping. For the purpose of the biosensing application, the EAPM

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nanoparticles are biofunctionalized so that they can perform the role of immunomagnetic concentrators for B. anthracis spores that are present in samples of lettuce, ground beef, and whole milk. These modified nanoparticles are then placed straight to a biosensor that uses a direct-charge transfer method. The capillary flow of the collected spores on the surface of the biosensor is essential to the detection mechanism of the biosensor. This is combined with the direct-charge transfer that is made possible by the EAPM nanoparticles. The results of the experiments show that the biosensor is able to identify B. anthracis spores in the tested samples at concentrations as low as 4.2 × 102 spores/ml, which is an extremely low level. Importantly, the EAPM-based biosensor system provides a reliable detection method that is quick, with a total detection time of only 16 min. This is a significant advantage. Another group developed Bacillus thuringiensis (Bt) specific gene fragments detection system based on a facile and reusable SERS sensor [57]. Magnetic beads (MBs) made of Fe3 O4 were used in the construction of the sensor with Au–Ag core– shell nanorods (Au@Ag NRs). A hairpin DNA molecule that contained sulfhydryl and biotin groups was linked to the Au@Ag nanorods so that it could act as an indicator. At the same time, the MBs were functionalized with streptavidin (SA) so that they could serve as the capture probe. Target sequences hybridize to the hairpin DNA, revealing the biotin group. Subsequently, the streptavidin-modified MBs capture the Au@Ag NRs, leading to a reduction in suspended NRs and a corresponding change in Raman intensity. Under conditions that were optimized, the SERS intensity had a linear connection with the concentration of Bt transgene fragments, which varied from 0.1 pM to 1 nM. This relationship was observed over the whole concentration range. It was established that the sensor had a detection limit of 0.14 pM when the signal-to-noise ratio was 3. The authors explored the detection of single-base mismatches in the DNA sequences using the SERS assay in order to determine the level of specificity possessed by the sensor. The results demonstrated acceptable sensitivity and accuracy in DNA detection, highlighting the potential of this approach for the specific gene detection of interest. Importantly, the sensor offers simplicity, reusability, and great potential for various applications in gene detection.

4.2.2 Detection of Fungal Contamination Fungi are the next category of biological food contaminants. Fungi, such as yeasts, fungi, and mushrooms, are common eukaryotic organisms. The presence of fungal contamination in food products is a significant issue as it can cause food spoilage, reduce shelf life, and potentially generate harmful toxins that pose health risks to consumers. In recent years, the emergence of intelligent nanosensors has provided a fast and highly sensitive solution for detecting fungal contamination in food, offering an innovative approach compared to traditional detection methods. The use of nanomaterial-based electrochemical biosensors, such as graphene and carbon nanotubes, is a recent advancement in the detection of fungal contamination [58]. Recent study demonstrated the development of a graphene-based biosensor for the

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detection of aflatoxin B1, a potent fungal contaminant commonly found in food products [59]. The biosensor exhibited exceptional sensitivity and specificity, achieving a remarkable detection limit of 0.03 ng/mL [60]. Utilizing biosensors based on molecularly imprinted polymers (MIPs) is another recent advancement in the detection of fungal contamination. MIPs are synthetic materials engineered to selectively recognize and bind to a specific target molecule, such as a fungal toxin. In a recent study, researchers developed a MIP-based biosensor for the detection of zearalenone, a common fungal contaminant in cereals [61]. These and other recent advancements utilizing intelligent nano-based sensors for the detection of fungal contamination in food products represent a promising strategy for confirming safety of food and preventing the contaminated illnesses spreading [62, 63]. Intelligent nanosensors for detecting bacterial and fungal contamination in food products have been extensively studied. Several sensor types, including optical sensors, electrochemical sensors, and biosensors, have been emerged and applied for this purpose. For the detection of bacterial contamination in food products, optical sensors such as surface plasmon resonance (SPR) and fluorescence sensors have been utilized. These sensors detect the presence of microbes through the interaction between light and the sensor’s surface. In recent years, optical sensors, specifically SPR and fluorescence sensors, have garnered considerable interest for detecting bacterial contamination in food products. These sensors function by recognizing specific biomolecules or cells that are present on the bacterial cell surface. SPR sensors are based on the change in refractive index that occurs when target biomolecules attach to the sensor chip’s surface [64]. The sensor chip is typically coated with a thin coating of gold, which serves as a binding surface for bacteria. As the bacteria adhere to the surface, the refractive index of the gold layer changes, which is detected as a change in the angle of reflected light. This change in angle can be used to quantify the sample’s bacteria concentration. Fluorescence sensors, on the other hand, rely on the fluorescent properties of specific biomolecules to function. When excited by a light source, the sensor consists of a fluorophore that emits light. Specific biomolecules bind to the bacterial cells surface and envelope the sensor. While bacterial cells bind to a surface, there is a change in the fluorescence properties of the fluorophore, which is detected by a change in the amount of light emitted. This fluctuation in the amount of light that is emitted can be utilized to quantitatively determine the amount of bacteria present in the sample. The recent advancements that have been made in optical sensors have made it possible for the construction of sensors that are both highly sensitive and specific in order to detect bacterial contamination in food products. Optical sensors, such as SPR and fluorescence sensors, have shown tremendous promise for detecting bacterial contamination in food products due to their high sensitivity and specificity, rapid detection time, and possibility for automation. In addition, these types of sensors also have the ability to be automated. For bacterial detection, electrochemical sensors such as impedimetric and amperometric sensors have also been utilized. These sensors measure alterations in electrical conductivity or current brought on by the presence of microorganisms. For bacterial detection in food products, biosensors containing biological components

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such as enzymes or antibodies have also been developed. Due to their ease of use, high sensitivity, low cost, and capability for real-time detection, electrochemical sensors are widely used for bacterial detection. Impedimetric and amperometric sensors are two categories of electrochemical sensors typically used for bacterial detection. Changes in the electrical impedance of a solution caused by the presence of microorganisms are measured by impedimetric sensors. The bacterial cells function as insulators, decreasing the flow of electrical current and increasing impedance. The change in impedance is proportional to the number of microorganisms present in the solution. Typically, interdigitated electrodes are used by impedimetric sensors to measure impedance changes. In contrast, amperometric sensors detect bacterial cells by measuring the current produced by the electrochemical reaction between bacterial cells and electrodes. In this type of sensor, the bacterial cells function as a catalyst, accelerating the electrochemical reaction and, consequently, the flow of current. For detection, amperometric sensors typically employ screen-printed electrodes or microelectrodes. Recent research has focused on enhancing the sensitivity and specificity of electrochemical sensors for the detection of microorganisms [65]. Due to their high sensitivity, specificity, and real-time detection capability, electrochemical sensors are a promising technology for the detection of bacteria in dietary products. Ongoing research continues to enhance the efficacy and dependability of these sensors for food industry applications. Colorimetric sensors, on the other hand, are able to identify shifts in color or absorbance that are brought about by the interaction of the analyte with the sensor surface. Because of their ease of use, quickness, and relatively low cost, they are suitable for use in applications that are performed at the point of care. Biosensors, electrochemical sensors, and colorimetric sensors are all potentially useful instruments for the detection of fungal contamination in food products; however, each of these sensor types comes with its own set of benefits and drawbacks. It will be necessary to do additional research and development in order to improve the sensitivity, specificity, and robustness of these approaches before they can be used in the food sector for practical applications. Intelligent nanosensors have showed both excellent sensitivity and specificity in the detection of bacterial and fungal contamination in food products. Bhardwaj et al. [66] discuss recent developments and trends in the development of biosensors for the detection of aflatoxin B1 (AFB1), a potent carcinogenic mycotoxin that contaminates a variety of agricultural products. The focus of the work is on paper-based and microspotted array microfluidic biosensors that are inexpensive, transportable, and require minimal sample preparation. The authors describe the working principles and applications of these biosensors and emphasize their advantages over conventional detection methods. In addition, they discuss recent advances in surface functionalization strategies and signal amplification techniques that have improved the sensitivity and selectivity of these biosensors. In conclusion, the authors highlight the potential of these biosensors for on-site, real-time monitoring of AFB1 contamination in food products. These sensors have a high level of sensitivity and specificity, allowing them to detect contaminants even at low concentrations.

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Intelligent nanosensors offer numerous advantages for ensuring food safety. These sensors provide rapid and accurate detection of bacterial and fungal contamination, thereby aiding in the prevention of outbreaks of infectious illness and mitigating the economic losses associated with food contamination. In addition, the use of these sensors can reduce the need for time-consuming and expensive laboratorybased testing methods. With the ability to detect contaminants in real time using portable sensors, food safety can be monitored throughout the food supply chain, from production to distribution and storage. Utilizing intelligent nanomaterial-based sensors for the detection of bacterial and fungal contamination in food products offers numerous advantages over traditional testing techniques. These advantages include enhanced sensitivity and specificity, rapid and precise detection, and the capability to monitor food safety in real time.

4.3 Smart Sensor to Detect Food Adulteration and Authenticity This section will concentrate on the use of nanotechnology-based intelligent sensors to detect food adulteration and authenticity. This section will discuss the varieties of sensors employed, their accuracy and precision, as well as the advantages of using these sensors to detect food fraud. Food adulteration is the deliberate or accidental addition of substandard or hazardous substances to food products. This practice is unethical and hazardous to consumers, posing significant challenges to the food industry, food regulators, and public health officials. Laboratory analysis is timeconsuming, costly, and may not provide real-time results when used to detect food adulteration. Therefore, the development of intelligent sensors to detect food adulteration and ensure food authenticity in real time is necessary. Intelligent sensors are sensors that can detect, process, and transmit data. They are designed to operate independently or in tandem with other devices. In the food industry, intelligent sensors can be used to detect food adulteration and ensure food authenticity. Based on their detection mechanism, intelligent sensors can be categorized as biosensors, electrochemical sensors, or colorimetric sensors. Biosensors are sensors that detect the presence of specific compounds using biological molecules. They are composed of a biological component, such as an enzyme or antibody, and a transducer that converts the biological signal into an electrical signal. Biosensors are highly specific and sensitive, allowing them to detect a vast array of compounds, including food adulterants. Electrochemical sensors detect changes in electrical properties caused by the interaction of a target compound and a receptor element. They consist of two electrodes, a functional electrode and a reference electrode, and a target compoundcontaining solution. When the target molecule interacts with the receptor element on the working electrode, an electrical signal that can be measured is generated. Electrochemical sensors are highly sensitive and can detect food adulterants in real time. Due to their rapid response, enhance sensitivity, and selectivity electrochemical sensors

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have been extensively utilized for detecting food adulteration. These sensors provide quantitative and qualitative information regarding the target analyte based on the electrochemical properties of the analyte. The screen-printed electrode (SPE) sensor is one of the most frequently employed electrochemical sensors for food adulteration detection. These inexpensive, portable, and user-friendly sensors are ideal for onsite testing. To increase their sensitivity and selectivity toward the target analyte, the SPE sensors can be modified with various substances, such as enzymes, antibodies, or nanomaterials. The microfluidic-based sensor is another type of electrochemical sensor that has been utilized for food adulteration detection. These sensors combine microfluidic channels with electrochemical sensors to detect analytes with a high throughput. In addition to reducing the sample volume necessary for analysis and increasing the pace of analysis, microfluidic sensors offer the benefit of a smaller sample volume. In recent times, there has been significant utilization of nanomaterials to enhance the effectiveness of electrochemical sensors in the detection of food adulteration. Among the most commonly employed nanomaterials are AuNPs, carbon nanotubes, graphene, and metal oxide nanoparticles. The nanomaterials can be used to enhance the sensitivity, selectivity, and stability of an electrode’s surface. Due to their high sensitivity, selectivity, and swift response, electrochemical sensors provide a promising solution for the detection of food adulteration. As novel materials and technologies continue to emerge, electrochemical sensors are expected to have an increasingly significant impact on ensuring the safety and authenticity of food products. Colorimetric sensors are sensors that detect color changes caused by the interaction of a target molecule and a receptor molecule. They consist of a colorimetric indicator and a specific receptor element for the target compound. When the target compound interacts with the receptor element, the indicator undergoes a color change, which can be detected visually or with a spectrophotometer. Colorimetric sensors are simple to use and can detect food adulterants rapidly. Colorimetric sensors are a type of sensor that is commonly used to detect food adulteration. When the target analyte is detected, these sensors operate on the principle of a color change. In these sensors, the reaction between the analyte and a specific reagent enables the detection of the analyte. The color change is caused by the formation of a complex or precipitate, which modifies the solution’s optical properties. The change in hue can be detected visually or with a spectrophotometer. The use of AuNPs is a common strategy in the development of colorimetric sensors for food adulteration detection. Due to their unique optical properties, such as localized surface plasmon resonance (LSPR), that is extremely sensitive to changes in the local refractive index, AuNPs are appealing. The surface of the AuNPs is modified with specific ligands that interact with the analyte and cause a color change in the solution. Various colorimetric sensors for detecting food adulteration, such as milk adulteration, honey adulteration, and meat adulteration, have been developed. Using AuNPs functionalized with a melamine-specific aptamer, for instance, a colorimetric sensor for the detection of melamine in milk samples was developed. With a detection limit of 0.1 µM, the sensor was extremely sensitive and selective. The detection of Sudan dyes in chile

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Fig. 4.8 Common immunoassays utilizing optical and electrochemical biosensing for the detection of meat adulteration. Reprinted with permission from Advanced Sensor Technology, Copyright 2023, Elsevier [67]

powder is another example. Sudan dyes are a class of synthetic dyes whose carcinogenic properties prohibit their use in food. Using AuNPs modified with a Sudan I-specific aptamer, a colorimetric sensor was developed. The sensor exhibited high sensitivity and specificity, with a remarkable detection limit of 0.005 µM. Colorimetric sensors, known for their simplicity, affordability, and exceptional sensitivity, hold great promise as a technique for detecting food adulteration. Figure 4.8 provides a visual representation of optical/electrochemical immunosensors designed to detect various types of meat adulteration. In conclusion, intelligent sensors are a promising technology for detecting food adulteration and ensuring the authenticity of food. Biosensors, electrochemical sensors, and colorimetric sensors are some of the most common forms of sensors used for this purpose. These sensors are highly specific, sensitive, and capable of detecting food adulterants in real time. To increase the precision and dependability of these sensors for use in the food industry, additional research is required.

4.4 Nanomaterials in Anticounterfeiting Device This section will discuss the application of nanomaterials to the development of anticounterfeiting devices for culinary products [68]. This section will discuss the types of nanomaterials employed, their properties, and the advantages of employing these materials for preventing food fraud and assuring food safety. In the food industry, counterfeit food products are a major concern because they pose significant health hazards and result in economic losses for companies. The food industry has been

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investigating the use of nanomaterials in anticounterfeiting devices to prevent such problems. Nanomaterials offer several advantages over conventional anticounterfeiting techniques, including their small size, distinctive physical and chemical properties, and ability to be incorporated into a wide range of materials. Figure 4.9 shows the roadmap describing the evolution of the two-dimensional nanomaterials for the development of biosensors. Incorporating nanomaterials into packaging materials is a common method for incorporating them into anticounterfeiting devices. Nanoparticles can be added to ink, paper, and other packaging materials to create distinctive and unreplicable characteristics. These features may consist of holograms, microtext, or invisible pigments that are only visible under certain conditions. Using nanomaterials to create smart labels or tags that can be affixed to food products is another option. These labels may include details such as the product’s origin, manufacturing date, and expiration date. When a food product has been tampered with or exposed to unfavorable conditions, such as high temperatures or excessive moisture, the labels can be designed to change color or emanate a signal. Nanoparticles, including carbon-based nanomaterials, magnetic, quantum dots, metallic, and graphene oxide, can be employed in combination with biological probes to detect analytes. Various transducers, such as voltammetric, amperometric, potentiometric, and optical sensors, including colorimetric, surface plasmon resonance, metallic fluorescence, and optical fiber-based systems, utilize electrochemical or optical signals for detection purposes. For nanosensing applications, various types

Fig. 4.9 Roadmap describing the evolution of the two-dimensional nanomaterials for the development of biosensors. Reprinted with permission from Results in Optics, Copyright 2023, Elsevier [68]

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of sophisticated materials have been utilized to develop nanobiosensors (Fig. 4.10). For the development of nanosensors, SWCNTs and multiwalled carbon nanotubes (MWCNTs) have been utilized as nanomaterials. Nanomaterials based on carbon have proven to be a superior surface for immobilizing biological components in biosensors. Various nanomaterials, including quantum dots, carbon nanotubes, and metal nanoparticles, have been investigated for use in anticounterfeiting devices. For instance, researchers have reported using AuNPs to develop difficult-to-replicate patterns on packaging materials. Emerging as a new area of research in the sector of the food business, the application of nanomaterials in anticounterfeiting devices is worth looking into. By incorporating nanomaterials into packaging materials or creating intelligent labels, it is possible to create unique and distinguishable characteristics that can aid in preventing food product counterfeiting. To fully comprehend the potential benefits and hazards of using nanomaterials in anticounterfeiting devices and to develop effective and practical solutions for the food industry, additional research is required. Figure 4.11 shows the schematic of food degradation and adulteration detection using novel nanomaterial-based sensors.

Fig. 4.10 Nanobiosensor fabrication using advanced functional nanomaterial. Reprinted with permission from Environmental Technology & Innovation, Copyright 2022, Elsevier [69]

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Fig. 4.11 Schematic of food degradation and adulteration detection using novel nanomaterialbased sensors. Reprinted with permission from Advances in Colloid and Interface Science, Copyright 2020, Elsevier [70]

4.5 Nanobiosensor for Detection of Food Allergens and Toxins This section will examine the use of nanobiosensors for detecting allergens and contaminants in food. This section will discuss the different varieties of nanobiosensors, their sensitivity and specificity, as well as the advantages of using these sensors to ensure the safety of food for individuals with food allergies. Food allergens and toxins are a significant concern for public health and safety, as they can cause lifethreatening conditions such as anaphylaxis, allergic reactions, and poisoning. Therefore, procedures that are both effective and sensitive are required in order to identify allergies and pollutants in food. Nanobiosensors are becoming an increasingly viable technique for the detection of allergens and poisons in food as a result of their high levels of sensitivity, selectivity, and speed. Nanobiosensors typically comprise a bioreceptor, responsible for binding to the target analyte, and a transducer, which converts the binding interaction into a detectable signal. The bioreceptor could be an antibody, aptamer, enzyme, or any other biomolecule capable of recognizing the target analyte selectively. The transducer may operate on optical, electrochemical, or mechanical principles. In recent years, numerous nanobiosensors for the detection of food allergens and pollutants have been developed. In the realm of nanobiosensors, a typical setup involves a bioreceptor responsible for specifically binding to the target analyte, accompanied by a transducer that converts the resulting binding event into an observable signal. Zhang et al. [71] present a novel biosensor for the detection of histamine in foods. An optical fiber plasmon sensor that has been functionalized with

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a composite of graphene oxide and multiwalled carbon nanotubes forms the basis of the biosensor. The histamine detector is designed like a humanoid to simulate human anatomy in order to improve its sensitivity and specificity while detecting the presence of histamine. Outstanding performance was demonstrated by the biosensor, which had a sensitivity of 5.5 nm/mM, a detection limit of 59.45 µM in the linear detection range of 0–1000 µM, and a strong selectivity for histamine. In addition, the biosensor exhibited great selectivity for histamine. This study proposes a viable technique for the creation of efficient and sensitive biosensors for the detection of histamine in food products. Such biosensors can help ensure the safety of food and prevent allergic responses in customers. The detection of allergens and contaminants in food is of utmost importance in safeguarding food safety and the well-being of the general public. Notably, substantial advancements have been achieved in recent years toward the creation of highly sensitive and specific detection techniques for identifying food allergens and contaminants. Biosensors are one of the most recent advances in the detection of dietary allergens. Biosensors are analytical devices that detect the presence of a specific analyte using biological molecules. Biosensors based on immunoassay, for instance, utilize antibodies specific to allergenic proteins to detect them selectively in food samples. Aptamer-based biosensors, on the other hand, utilize nucleic acids that can bind to allergenic proteins in a specific manner. In addition, there is a rising interest in the use of nanomaterials to create sensitive and selective methods for identifying allergies and pollutants in food. This interest has been spurred on by recent advancements in the field of nanotechnology. For instance, AuNPs have been used widely in colorimetric assays for the identification of dietary allergies and poisons. These assays have been successful in identifying the substances. AuNPs-based assays are advantageous for on-site testing because they are uncomplicated, rapid, and cost-effective. In addition, advancements in mass spectrometry-based methodologies have substantially enhanced the detection and quantification of allergens and toxins in food. Multiple allergens and contaminants can be identified and quantified using mass spectrometry in a single analysis. The use of artificial intelligence (AI) and machine learning (ML) has tremendous potential for enhancing the precision and speed of allergen and toxin detection in food. AI and ML can be used to analyze large quantities of data, recognize patterns, and make predictions, which can aid in the early detection and prevention of food safety problems. The field of food safety has witnessed significant progress in recent years, particularly in the areas of biosensors, nanomaterials, mass spectrometry, and artificial intelligence/machine learning. These advancements have greatly improved the detection and monitoring of food allergens and contaminants, ultimately leading to enhanced food safety measures and the preservation of public health. Furthermore, the field of nanobiosensors has witnessed the development of innovative approaches for detecting bacterial contaminants in food products. For example, in the case of staphylococcal enterotoxin B (SEB) detection in milk and egg samples, a lateral flow biosensor based on AuNPs was successfully engineered. This demonstrates the potential of nanobiosensors in providing sensitive and specific detection methods for ensuring food safety [72]. Nanobiosensors have demonstrated great

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promise for the food allergens and toxins detection; however, additional research is required to optimize their performance and ensure their practical implementation in the food industry.

4.6 Detection of Spoilage in Food Crop Grain This section will discuss the use of intelligent nanosensors for detecting grain deterioration. This section will discuss the varieties of sensors used, their accuracy and precision, as well as the advantages of utilizing these sensors to ensure food quality and reduce food waste. Food deterioration is a significant problem that can result in significant economic losses. Several food products, including food crops such as cereals, are susceptible to spoilage. Detecting crop deterioration is essential for preventing economic losses and ensuring food safety. Figure 4.12 depicts the agricultural applications of nanobiosensors. In the agriculture sector, nanobiosensors are used to increase productivity, make better use of resources, and detect diseases before their onset, thereby making crop disease management easier. In recent years, intelligent nanosensors for detecting deterioration in food crop grain have been developed. Kpiska-Pacelik et al. [73] discuss the development and applications of microfluidic devices for the detection of mycotoxins, which are toxic compounds produced by certain fungi that can contaminate food and feed. They highlight the benefits of microfluidic technology, such as its capacity to conduct highly sensitive and specific assays, its potential for highthroughput screening, and its capacity to integrate multiple functions into a single device. In addition, the authors provide an overview of the various microfluidic devices used for mycotoxin detection and describe some of the obstacles that must be overcome to enhance their performance and commercial viability. The article provides a valuable overview of the current state of microfluidic-based mycotoxin detection as well as some insights into future research directions. Contamination with fungi is one of the primary causes of grain deterioration. Mycotoxins are hazardous secondary metabolites produced by fungi and can be generated due to fungal contamination. The presence of mycotoxins in food poses significant health risks to both humans and animals if consumed. Therefore, it is essential to detect fungal contamination in food crop grain. Mycotoxins, known as secondary metabolites generated by filamentous fungi, are reviewed by researchers. These toxins are considered toxic substances when they are present in human and animal food and feed, and they are commonly found in cereals, seeds, and other products that can become contaminated during harvest and storage. Mycotoxins present a substantial danger to the health of both humans and animals due to their well-documented toxigenic, nephrotoxic, hepatotoxic, carcinogenic, immunosuppressive, and mutagenic properties, as extensively discussed by researchers [74]. The primary mycotoxins that have been identified, chemically characterized, and are now being researched for their potential toxicity are the primary focus of these studies, this research was published in

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[75]. Recently, Gong et al. provided an overview of current breakthroughs in electrochemical biosensors for the detection of pesticides and mycotoxins in food [75]. The article highlights the advantages of electrochemical biosensors, which encompass their exceptional sensitivity, cost-effectiveness, and straightforward miniaturization. It also discusses the different varieties of electrochemical biosensors, including amperometric, potentiometric, and impedimetric sensors, as well as their operating principles. Subsequently, an extensive overview is provided, examining the recent progress in the field of electrochemical biosensors for the detection of pesticides and mycotoxins. The review emphasizes the existing challenges and explores the potential future prospects of these sensors in various food safety applications. The detection of fungal contamination in food crop grain using nanobiosensors has shown promising results. These sensors recognize specific molecules or biomolecules in the sample. Utilizing nanomaterials in the development of nanobiosensors has resulted in increased sensitivity, selectivity, and precision in detecting fungal contamination in food crop grain. Mondal et al. [76] discuss the present state of development and application of nanobiosensors in sustainable agriculture. The authors emphasize the significance of sustainable agricultural practices and how the application of nanobiosensors can enhance the efficacy of these practices. They discuss the advantages and disadvantages of the various types of nanobiosensors, including electrochemical, optical, and field-effect transistor (FET)-based sensors. The authors also discuss the numerous agricultural applications of nanobiosensors, such as the detection of plant pathogens, monitoring of soil conditions, and evaluation of crop quality. In addition, they provide an exhaustive review of the most recent advances in nanobiosensors for sustainable agriculture, including the use of nanomaterials such as graphene, carbon nanotubes, and nanoparticles. In addition, the authors discuss the difficulties and future potential of nanobiosensors in sustainable agriculture. They emphasize the potential of nanobiosensors in sustainable agriculture and offer valuable insights to researchers and practitioners in this field. Additionally, Mondal et al. [76] discuss the application of aptasensors in sustainable agriculture. Aptasensors are a type of biosensor that employ aptamers, short single-stranded DNA or RNA molecules, as the recognition element instead of antibodies or enzymes. These aptamers exhibit high affinity and specificity, allowing them to selectively bind to specific targets. Using aptasensors in agriculture can provide a rapid and dependable method for detecting various contaminants in soil and water, such as pesticides, heavy metals, and pollutants. Aptasensors can also be used to detect pathogens in plants, allowing plant health to be monitored and disease outbreaks to be prevented. They discuss the different varieties of aptasensors, including electrochemical, optical, and piezoelectric aptasensors. These sensors provide numerous benefits, such as high sensitivity, selectivity, and reproducibility. In addition to being inexpensive and user-friendly, they are ideal for use in the field. The authors discuss recent advances in aptasensor technology, such as the use of nanomaterials and microfluidics to improve sensor performance. In addition, they discuss the potential uses of aptasensors in precision agriculture, where they can be used to monitor soil nutrients and water quality, as well as in food safety and security.

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Fig. 4.12 Applications of nanobiosensor in Agriculture. Reprinted with permission from Environmental Technology & Innovation, Copyright 2022, Elsevier [69]

Overall, aptasensors provide a more sustainable and efficient method for monitoring plant health and ensuring food safety by detecting contaminants in agriculture. Figure 4.13 depicts the various facets of aptamers and their selection through the Systematic Evolution of Ligands by Exponential Enrichment (SELEX) method. Figure 4.13a illustrates how aptamers interact non-covalently with their target of interest. Aptamers are single-stranded oligonucleotides that can recognize specific targets with high affinity and specificity, including proteins, small molecules, and even whole cells. They accomplish this through their three-dimensional structure, that is determined by the nucleotide sequence. Figure 4.13b depicts the various structural motifs that aptamers can adopt, such as hairpin loops, stem-loops, and Gquadruplexes. These structural motifs contribute to the aptamer-target complex’s stability and specificity. Figure 4.13c depicts the SELEX method for selecting aptamers. Starting with a large random pool of oligonucleotides, the SELEX method involves successive cycles of selection and amplification. Isolating and amplifying the oligonucleotides that bound to the target with high affinity and specificity is repeated until a final pool of aptamers is obtained. Positive/negative selection, counterselection, and coselection are some of the SELEX techniques that can be utilized to

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select aptamers, as shown in Fig. 4.13d. These techniques are adaptable to the unique characteristics of the target and the intended aptamer. Overall, Fig. 4.13 provides a comprehensive overview of aptamers and their selection procedure, emphasizing the potential of aptamers as potent recognition elements in biosensors, diagnostics, and therapeutics. The ELISA-based biosensors are one type of nanobiosensor used for detecting fungal contamination in food crop cereal. This biosensor relies on antibodies immobilized on a solid surface to recognize fungal antigens. The antigen–antibody interaction generates a detectable signal that can be detected by an optical or electrochemical transducer. Recent studies have demonstrated the high sensitivity and specificity of ELISA biosensors for detecting fungal contamination in food crop grain.

Fig. 4.13 a The aptamer binds to its target molecule by forming non-covalent interactions. b Various structural motifs can be found in aptamers. c The SELEX technique is employed to select aptamers that specifically bind to the desired target. d Different methodologies are used in SELEX to identify aptamers with high affinity and specificity, adapted from [76]

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DNA biosensors are another form of nanobiosensor used to detect fungal contamination in food crop grain. This biosensor relies on the hybridization of target DNA from fungi with immobilized complementary DNA probes. The interaction between target DNA and DNA probes generates a detectable signal that can be measured using an optical or electrochemical transducer. Recent studies have demonstrated the high sensitivity and specificity of DNA biosensors for detecting fungal contamination in food crop grain. In addition to nanobiosensors, colorimetric nanomaterial-based sensors have been devised for the detection of grain spoilage. In the presence of specific degradation biomolecules, these sensors rely on a change in the color or intensity of the sensor. Recent studies have reported the use of colorimetric sensors based on AuNPs for the detection of grain deterioration with high sensitivity and specificity. AuNP-based colorimetric sensors for pathogen detection are reviewed by Yang et al. [77]. They emphasize the significance of developing low-cost, straightforward, and rapid sensing strategies for detecting pathogens that cause foodborne ailments. It discusses the use of AuNPs as colorimetric sensors as a result of their unique optical properties and high surface area, which enable the detection of minute quantities of target analytes. In addition, they describe the numerous techniques used to functionalize AuNPs with ligands such as antibodies, aptamers, peptides, and nucleic acids for pathogen detection. These strategies offer high selectivity and sensitivity for the analytes of interest, making them attractive for practical applications. The authors discuss the benefits of colorimetric sensors, including their ease of use, low cost, and ability to perform visual detection without specialized apparatus. This article [77] provides examples of successful applications of colorimetric sensors for detecting pathogenic bacteria such as E. coli, Salmonella, and L. monocytogenes. Researchers emphasizes the potential of colorimetric sensors based on AuNPs as a promising technology for rapid and dependable pathogen detection in food and water systems. Overall, the development of intelligent nanosensors has demonstrated tremendous promise for detecting spoilage in food crop grain. Utilizing nanobiosensors and nanomaterial-based colorimetric sensors can improve the sensitivity, selectivity, and precision of detecting fungal contamination and spoilage biomolecules in food crop grain.

4.7 Summary In this chapter, mainly recent advancements in the implementation of intelligent nanosensors to ensure the quality and safety of food products were discussed. The section began with an overview of the different varieties of sensors used for food quality and safety detection. Subsequently, the section discussed the use of electrochemical, optical, and biosensors to detect bacterial and fungal contamination in food products. It highlighted the sensitivity, specificity, and advantages of using these sensors for food safety monitoring. The section then discussed the use of intelligent sensors to detect food adulteration and authenticity, emphasizing the benefits of using

References

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these sensors to combat food fraud and increase consumer confidence. In addition, the section examined the use of nanomaterials in anticounterfeiting devices, emphasizing the role of these devices in enhancing supply chain security and safeguarding the integrity of food products. The section then concentrated on nanobiosensors for the detection of food allergens and pollutants, discussing the principles of these sensors and their potential applications for ensuring the safety of food for consumers with food allergies. The section concluded with a discussion of the detection of spoilage in food crop grain, emphasizing the use of various sensors, such as electronic nostrils and colorimetric sensors, to monitor the quality and shelf life of food products. This chapter concluded by demonstrating the significant potential of intelligent nanosensors for ensuring the quality and safety of food products. This section highlighted the various types of sensors and their applications for detecting bacterial and fungal contamination, food adulteration and authenticity, anticounterfeiting, food allergens and toxins, and grain deterioration.

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Chapter 5

Nanofertilizers and Nanopesticides: Key to Healthier and Safe Food Products

Abstract Nanofertilizers and nanopesticides have recently emerged on the scene as key players in the process of promoting the growth of plants and providing wideranging defense against pests. They make accurate application of fertilizers, insecticides, and herbicides possible, which not only guarantees the safety of food but also lessens the amount of pollutants in the surrounding environment. As a result, the primary focus of this conversation will be on developing novel methods for incorporating nanocarriers into controlled chemical release systems. The investigation of their delivery modalities as well as the fundamental principles that determine their effectiveness will be the primary focus of this work.

5.1 Introduction In the current scenario, the world population will reach 6–9 billion by 2050 and require an enormous food supply in a short phase with extra yield using various novel technologies [1]. Various disease-resistant cultivars, chemical fertilizers, and synthetic peptides have been utilized for decades in order to meet this demand. Pesticides, including herbicides, insecticides, and fungicides, are continuously used in the agriculture sector, but they degrade food and soil quality. It is estimated that a significant portion, approximately 50–70%, of chemicals remain unused as a result of processes such as bioconversion, leaching, and mineralization. Chemical fertilizers and pesticides seem to have adverse effects on human health and the environment, leading to their enhanced accumulation in soil and water, reduction in nitrogen fixation, and ecological imbalance [2, 3] and eutrophication [4]. Additionally, due to non-targeted delivery, conventional methods require repeated application in order to achieve the desired high yield, which in turn increases production costs. Thus, there is an urgent need to upgrade conventional agriculture practices through smart applications. At this point, nanotechnology and nanoscience have drawn interest for their applications in agriculture and crop production. Nanomaterials have been reported to enhance the efficiency and bioavailability of existing fertilizers by reducing mobile nutrient loss toward surrounding media or distributing less bioavailable elements like

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_5

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phosphorous and zinc [5]. To date, several proposed nanopesticides and nanofertilizers consist of reformulated bioactive ingredients in order to enhance the efficacy and overcome the shortcomings of in-practice agrochemicals [6]. Enhanced biointeraction and bioavailability, cost-effectiveness, and reduced loss of nutrients are key factors for the use of nanomaterials in agriculture field [7, 8]. Additionally, targeted delivery, a high surface area-to-volume ratio, and enhanced nutrient efficiency due to their slow release prove them an alternative to conventionally used methods [9]. Nanomaterials like silver [10–12], titanium, silica, molybdenum [13], manganese, iron [14], copper [11, 15], iron, zinc [16, 17] and their oxides, carbon-based nanomaterials and nanoformulations of conventionally used elements like azadiractina, urea, phosphorous, sulfur, tebuconazole, and validamycin can be efficiently transformed into nanofertilizers and nanopesticide forms [18]. Several nanoformulations, nanoencapsulations, and functionalized nanomaterials have been reported for site specific targeted delivery of active ingredients like fertilizers and pest control chemicals to plants [19]. The use of nanopesticides has proven to be effective in treating plant diseases and pests. Thus, in addition to pollution control and high yield, nanoparticles can also efficiently reduce waste in the environment [20]. It also has the ability to accomplish the diagnosis and treatment of several plant diseases via nanofertilizers and nanopesticides. Figure 5.1 shows the different applications of nanotechnology for improving agricultural efficiency.

Fig. 5.1 Primary factors promoting the adoption of nanotechnology to enhance the efficiency of nano-agrochemicals. Reprinted with permission from Chemistry Select, Copyright 2021, Wiley [21]

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5.2 Nanofertilizers Nanofertilizers consist of nutrient fertilizers comprised of nanostructure formulations either in whole or in part and can be delivered to plants for their enhanced uptake or slow release of active ingredients. Conventionally used fertilizers suffer from major limitations like less internalization of phosphorous and nitrogen-based fertilizers in plants, which require large amounts for the desired response. These fertilizers transform into chemical compounds that could be ingested by plants and thus result in the emission of hazardous gases that exert adverse effects on human health and the environment [22]. Due to their small size, nanofertilizers can be easily absorbed by plants with different dynamics than their bulk equivalents and ionic salts, which makes them a potential means of overcoming these restrictions [23, 24]. Additionally, these nanoscale fertilizers also improve the fertility of soil, maintain continuous nutrient supply, reduce toxicity levels, and increase application rates [25, 26]. However, their safety and toxicity assessments need to be considered to prove the biocompatibility of nanofertilizers. Nanofertilizers are usually composed of smaller nanoscale particles derived from larger entities, including bacteria, fungi, different parts of plants, and mineral fertilizers, via different physical and chemical methods. Various micro- and macronutrients that are essential for plant growth, like potassium, magnesium, zinc, manganese, nitrogen, and phosphorous, are included in nanoformulations and used as plant growth enhancers. These can be termed nanofertilizers [27]. A study revealed that the use of potassium, boron, iron, and zinc in nanofertilizer can greatly increase the production of four potato cultivars (Solanum Tuberosum) [28]. According to the type of formulation they contain, nanofertilizers can be divided into the following three categories: (i) Nanoscale fertilizers, also known as conventional fertilizers with a size reduction, typically taking the form of nanoparticles, are the focus of this article. (ii) Conventional fertilizers that have had nanoparticles added to them are what are known as nanoscale additive fertilizers. (iii) Nanoscale coating fertilizers are nutrients that have been encased in nanofilms or absorbed into the nanoscale pores of a host material. These fertilizers have the potential to significantly increase crop yields [29].

5.2.1 Zinc as Nanofertilizer Spraying zinc as a nanofertilizer significantly enhances the tuber number per plant, plant marketable yield, total plant yield, and marketable tuber yield per hectare. Zinc oxide nanofertilizers also enhance the internalization of native nutrients from soil. In this context, Raliya et al. demonstrated the enhanced uptake of phosphorous in mung bean with the use of zinc oxide nanoparticles (ZnO NPs) [30]. The results showed a 10.8% increase in phosphorous uptake in the nanofertilizer-treated

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plant when compared to the control plant. Additionally, the use of ZnO nanoparticles also enhances the phenology of plants, i.e., chlorophyll content, root volume, stem height, and leaf protein. Enhanced root volume and chlorophyll content lead to the accumulation of microbes that improve the soil’s condition. Zinc has been distributed in all plant parts, including seeds, at the dietary recommended concentration. In another study, it was also shown that zinc nanofertilizer with an average size of 15–25 nm exhibited improved phenological growth in Pennisetum americanum L plant (6 weeks old) with high chlorophyll content, plant dry biomass of 12.5%, total soluble lead protein of 38.7% [31]. The results showed a 37.7% increase in crop yield upon crop maturity in foliar zinc nanofertilizer-treated plants. Numerous studies have been conducted to explore the impact and potential of zinc and copper nanoparticles on plant metabolism [32]. In this context, Francis et al. showed the biogenic synthesis of ZnO nanoparticles and copper oxide nanoparticles (CuO NPs) and also demonstrated their combined effect on Amaranthus hybridus seed germination and plant growth [33]. Two different modes, i.e., foliar and hydroponic, have been investigated for various concentrations of ZnO nanoparticles (0.12 μM, 0.24 μM) and CuO nanoparticles (0.06 μM, 0.12 μM). In comparison with the foliar method, hydroponics exhibited better efficiency for plant growth. An important finding of the present study has been the use of low concentrations of ZnO and CuO nanoparticles in comparison with zinc and copper slats present in Hoagland’s medium. Low concentrations can reduce the effective cost as well as avoid their accumulation in the environment. The results also showed the presence of high antioxidant molecules in plants treated with copper oxide and zinc oxide, thus confirming the enhanced plant resistance against pests and infections and also inducing plant growth. No significant accumulation of copper or zinc has been observed in plants treated with nanofertilizers in comparison with control plants. In another study, Abbasifar also demonstrated the combined effect of copper and zinc nanoparticles on basil plants [34]. The results showed a significant improvement in most morphological parameters of the plant at concentrations of 2000 ppm copper and 4000 ppm zinc nanoparticles. Additionally, high flavonoids and phenolic content, as well as enhanced antioxidant activity, have been observed at this concentration. The chlorophyll content of basil plant leaves has also been affected by the treatment with nanoparticles. Superabsorbent hydrogels (SAHs) have emerged as a recent innovation in agricultural fertilizers, offering the ability to control nutrient release and water retention. To create environmentally friendly and cost-effective fertilizers, researchers are focused on utilizing natural polymers such as cellulose, gellan gum, alginates, chitosan, lignin, and their combinations as abundant and affordable raw materials. This emphasis on incorporating natural polymers into fertilizer production has become a key area of interest [35, 36]. In this context, Ekanayake et al. utilized alginic acid to develop the nanofertilizer for slow release of micronutrients for nourishment of surrounding soil [36]. Fertilizer complexes were synthesized by the reaction of nanoparticles with sodium alginate to produce hydrogels by crosslinking zinc and copper with alginate chains. The authors performed the tea bag method to investigate the release of cations in soil, and the results revealed a slow release of ions with an increase in time. The uptake of nutrients in tomato plants has been investigated by leaf analysis for 30

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consecutive days. The results showed that plants treated with nanofertilizer showed reduced uptake of copper, whereas the concentration of zinc in leaves remained undetected. This may be due to the inhibition of zinc uptake by soil phosphorous or the antagonistic behavior of zinc and copper internalization. The findings of the study demonstrate that despite the incorporation of metal oxide nanoparticles into the alginate matrix, they were readily taken up by plant roots even in the presence of an NPK fertilizer. Furthermore, under ambient conditions, these nanoparticles were released into the environment. Based on these observations, the study emphasized the potential of the polymeric fertilizing complex described in the research to be expanded into a versatile micronutrient nanofertilizer. Such a nanofertilizer could enrich the soil with organic matter and simultaneously provide crop plants with various essential micronutrients. Further, Naseem et al. demonstrated the synthesis of zinc aluminosilicate (ZnAl2 Si10 O24 ) nanocomposite via the coprecipitation method and loaded it with urea to provide the plants with both zinc and urea [37]. The authors followed the result for 14 days and found that due to its small particle size and high surface area, ZnAl2 Si10 O24 exhibited a high holding capacity for urea in comparison with its bulk counterparts. The highest release of urea has been found in the first 24 h due to excess adsorption at nanocomposite, and least release has been observed on the 14th day. In comparison with commercially available urea, ZnAl2 Si10 O24 nanocomposite loaded with urea provided a higher yield in the Oryza sativa L plant. The effectiveness of the plant’s ability to use nitrogen was significantly impacted by urea’s prolonged release. Urea-loaded zinc aluminosilicate showed total nitrogen uptake of 1.16 g, higher than that of commercially available urea, i.e., 1.11 g, which in turn affected the final yield. Final yield of urea-loaded nanocomposite has been reported to be 46.02 g, in comparison with commercial urea, which is 43.57 g. Nitrogen recovery efficiency of plants has also been positively affected by the use of nanofertilizers, which proves low wastage of nitrogen, less leaching of nitrogen to the ground and is safe for the environment.

5.2.2 Iron as Nanofertilizer According to the report, iron chlorosis is a common agricultural issue that affects between 30 and 50% of cultivated soils and is one of the main factors limiting crop output in calcareous soils [38]. To treat iron shortages in cash crops, farmers use synthetic iron chelates. Although these fertilizers are expensive, they have a tendency to lixiviate, and chelating agents may prevent precipitation and increase heavy metal mobilization [39]. Many crops, including citrus and fruit trees, are susceptible to iron chlorosis, but soybean (Glycine max L.) is one of the most researched iron strategy plants [40]. Therefore, new methods for treating iron shortages in plants should be developed, and new environmentally friendly fertilizers are required to improve crop environmental quality. In this context, Cieschi et al. demonstrated the synthesis of iron-humic nanofertilizers (57 Fe-NFs) (F, S, and M) from leonardite potassium

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humate [38]. Here, 57 Fe has been used as tracer tool in the form of 57 Fe(NO3 )3 or 57 Fe2 (SO4 )3 . Figure 5.2 shows the distribution of 57 Fe in soybean plants treated with nanofertilizers at different concentrations. Generally, 57 Fe-NFs remain in soil within the range of 80–95%, especially in available soil fractions. The highest amount of 57 Fe has been present in the root of plants treated with S fertilizer, whereas a high content has been found in the shoot of plants treated with fertilizers F and M. Result revealed that synthesized 57 Fe-NFs can effectively transport 57 Fe from root to shoot and finally pods of plants (Fig. 5.3).

Fig. 5.2 Percentage distribution of 57Fe in the shoots, pods, and roots of soybean plants treated with three doses of (1) 35, (2) 75, and (3) 150 μM 57Fe pot-1 using the 57Fe products F, S, and M, as well as in the soluble and accessible fraction of the soil, adapted from [38]

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Fig. 5.3 FeFer (μM pot-1) content in the roots of soybean plants treated with the 57Fe products F, S, and M at three different doses (1) 35, (2) 75, and (3) 150 μM 57Fe pot-1 or 50 μM 57FeEDDHA pot1 (a), as well as the content in the soluble soil fraction (b) and available soil fraction (c) at 48 days after flowering (DAF). Duncan’s Test (p < 0.05) was used to determine significant differences among the treatments, with different letters representing the significant differences. The results are presented as mean values ± standard error, with a sample size of 5, adapted from [38]

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5.2.3 Nitrogen as Nanofertilizer In another study, Mejias et al. demonstrated that nitrogen-based nanofertilizers can effectively enhance nitrogen efficiency in grassland species due to reductions in atmospheric losses as well as targeted delivery to plant sites [41]. Due to the constant and slow release of nutrients, nitrogen nanofertilizers lead to a significant improvement in nitrogen use efficiency (NUE). It has also been reported that nanofertilizers can effectively enhance crop production by 30% when compared to conventional fertilizers [42]. In another piece of research, researchers generated a nitrogen-releasing nanofertilizer by post-synthetically modifying nitrate-doped amorphous calcium phosphate (ACP) nanoparticles with urea [43]. In vivo research conducted on cucumber plants grown in hydroponics revealed that N-doped ACP nanoparticles, which have a lower absolute N content than the conventional urea treatment, stimulate the growth of an equivalent quantity of root and shoot biomass without depleting nitrogen. These nanoparticles have a lower absolute N content than traditional urea therapy. The practical implementation of N-doped ACP as a nanofertilizer is substantiated by its remarkable nitrogen consumption efficiency, reaching as high as 69%. Additionally, the cost-effective fabrication process further enhances its viability as a sustainable solution. It has also been discovered that the amount of nitrogen payloads (up to 8.1 wt%, from the initial level of 2.8 wt%) using the propensity score matching (PSM) method is significantly higher with enhanced efficiency (specifically, use of 16.5 times less urea) and a doubled space–time yield in comparison with an identical one-pot synthesis where urea and nitrate are added together during the synthesis of nanoparticles. The results showed that nano-urea-ACP had a greater NUE than its urea-based traditional fertilizer equivalent (49% NUE). The use of nano-ureaACP with urea that has its nitrogen content lowered by 50% produced shoots and roots with identical biomass and statistically equivalent nitrogen contents. Due to ACP’s high surface reactivity and urea molecules’ high affinity toward Ca2+ ions, nano-urea-ACP demonstrated a still large payload (N content of 6.43 wt%). It is noteworthy that all of the urea utilized in the process was absorbed into the material, preventing unintended losses and, as a result, lowering the operation’s financial cost and environmental concerns. To achieve a more continuous release of urea, further coating with biocompatible, slowly dissolving polymers can be considered, albeit at the expense of a more involved and expensive synthetic work-up. Contrarily, some reports revealed that employing nanofertilizers had no positive effects [44].

5.2.4 Carbon-Based Nanomaterials as Nanofertilizer Nanomaterials that are based on carbon have garnered a lot of interest as potential nanofertilizers due to the fact that they might be used for agricultural reasons. Due to the fact that these substances provide environmentally acceptable and longlasting agents that reduce the amount of fertigation chemicals, and due to the fact

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that their release can be targeted, they are ideal agricultural delivery methods for the next generation of insecticides and fertilizers. The physiology of plants undergoes a variety of shifts when carbon nanostructures are introduced into the plant’s environment. For example, the seedlings grow faster, the seeds germinate better, the roots and shoots get longer, the enzymes work better, the biochemical parameters get better, the plant’s defenses get stronger by turning on defense-related genes, the rate of photosynthesis goes up, oxidative enzymes are turned off, and a number of other metabolic processes are changed to make the plant healthier [45]. Apart from plants, carbon-based nanomaterials also play a crucial role in the maintenance of soil health by enhancing water and nutrients’ retaining capacity, slowing nutrient release, and maintaining soil pH balance [46]. Positive effects of multiwalled carbon nanotubes (MWCNTs) on various crops such as peanuts, wheat, garlic, and corn have been observed [47]. An investigation by Zhai et al. explored the interaction between soybeans and corn plants and different types of MWCNTs, including neutral, positively charged, and negatively charged MWCNTs. The study found that a concentration range of 0–50 ppm of MWCNTs resulted in a significant increase in plant biomass [48]. They found that corn grew better when it was exposed to MWCNTs (10–50 mg/L) for 18 days, but soybeans grew less well in the same conditions. Nardi et al. documented the concentrationdependent effect of carbon nanoparticles on the physiology and morphology of Vigna radiata (Fig. 5.4) [49].

Fig. 5.4 Illustrative diagram depicting the contribution of carbon nanoparticles to enhancing agricultural yield and productivity of crop plants, adapted from [49]

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Plant seeds were exposed to varying concentration of carbon nanoparticles (CNPs), i.e., 25–200 μM in hydroponic medium for 96 h. It has been observed that, exposure of 100–150 μM of CNPs enhances the protein content of plant by 1.14fold, chlorophyll content by 1.9-fold, and plant biomass by 1.14-fold for dry weight and 1.2-fold for fresh weight. Result also showed the increased level of antioxidant molecules like proline, superoxide dismutase, ascorbate peroxidase, and guaiacol peroxidase which in turn reduces the reactive oxygen species level at 100 μM level of CNPs. At the highest concentration of 200 μM, CNPs tend to aggregate at root surface due to direct contact, whereas high concentrations of particles have been found to accumulate in plant tissues. The utilization of CNPs as nanofertilizers offers notable benefits in terms of inhibiting nutrient translocation and absorption, thereby preventing oxidative damage and promoting increased antioxidant concentration in plants. These findings underscore the significance of CNPs as effective nanofertilizers, facilitating prolonged nutrient release and enhancing plant growth. Additionally, CNPs demonstrate their potential for enhancing stress tolerance and the effectiveness of phytoremediation in polluted environments, owing to their remarkable absorption capabilities.

5.2.5 Silicon Nanofertilizer The second-most abundant element on earth, silicon, has the potential to increase agricultural productivity by enhancing photosynthesis, increasing water usage effectiveness, postponing senescence, and increasing tolerance to biotic and abiotic challenges [50]. Traditionally, sodium, potassium, calcium, and magnesium silicates have been employed as silicate fertilizers in agriculture through fertigation, foliar spraying, and soil absorption [51]. Wheat [52] and tomato [53] plants cultivated under salinity stress both benefited from nanosilica’s ability to confer resistance. Additionally, it increased the rate of photosynthetic production, produced more biomass, increased grain yield, and preserved leaf water content. The osmotic adjustments are mechanically provided by a binary film formed by silica nanoparticles (SiO2 NPs) in the cell wall. Additionally, SiO2 nanoparticles promote the activity of antioxidant enzymes, enhancing seedling growth and promoting resilience to biotic and abiotic stressors. Additionally, under salt stress, silicon nanoparticles (SiNPs) increase potassium uptake and translocation while decreasing sodium uptake and translocation [54]. Recently, Kumaraswamy et al. demonstrated the synthesis of chitosan-silicon nanofertilizer, where silicon has been encapsulated in the chitosan-tripolyphosphate nanomatrix [55] (Fig. 5.5). The use of nanofertilizer showed a slow release of silicon with enhancements in yield and growth of the maize crop. Seeds treated with different concentrations of nanofertilizer from 0.04 to 0.12% w/v showed a 3.7-fold increase in seedling vigor index in comparison with silicon oxide. Foliar spray of nanofertilizer significantly enhanced the antioxidant enzymes activity and also maintain homeostasis in plant leaves. Nanofertilizer exposure enhances total chlorophyll concentration and leaf area to enhance the photosynthesis

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Fig. 5.5 Impact of CS-Si nanofertilizer on a growth of seedlings in laboratory conditions and b growth of plants in potted environments. Reprinted with permission from Plant Physiology and Biochemistry, Copyright 2021, Elsevier [55]

process in comparison with silicon dioxide. Result showed that 0.08% exposure of nanofertilizer leads to enhanced yield by 43.4%, whereas 0.04% concentration of nanofertilizer provides 45% increased test weight in comparison with silica alone. Developed nanofertilizer exhibited fecund and myriad effect which may be attributed to gradual release of silicon from nanofertilizer. Foliar application of SiNPs also reported to reduce the severe cadmium stress (20 mg Cd kg−1 soil) in summer savory (Satureja hortensis L.) [56]. Study suggests using 1.5–2.25 mM of SiNPs to help summer savoury plants adapt to cadmium stress by enhancing their physiobiochemical status. The results of the current investigation indicate that developed nanofertilizer can be further customized to expand its use in treating multinutrient insufficiency by encapsulating other significant nutrients in addition to silicon. SiNPs were used to achieve the highest antioxidant capacity in total phenolic content, total flavonoid content (TPC and TFC) and essential oil (EO) content under moderate cadmium stress. Therefore, by varying the drought and Si nanoparticle levels, summer savoury plants with high EO composition variability may be useful in obtaining the desired chemical. Further, cultivation of coriander plants in lead

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contaminated soil has shown favorable effects of SiNPs over polyphenol production [57]. Rice seedlings treated with SiNPs exhibit enhanced TPC by scavenging reactive oxygen species, which enhances plant growth metrics. Further, Hussain et al. investigated the physiological effect of SiNPs on soybean plants under normal light and shade conditions [58]. Two different varieties, i.e., Nandou 12 (shade resistant) and Nan 032-4 (shade sensitive), were cultivated under typical light and shade conditions accordingly. The results showed that plant growth and the net assimilation rate were both significantly reduced under the shading condition. However, foliar silicon treatment in both normal and shaded conditions considerably increased stomatal conductance, transpiration rate, and intercellular carbon dioxide concentration while also improving net photosynthetic rate. In comparison with controls, the net photosynthetic rate of Nandou 12 increased by 46.4% and 33.3% under normal and shading conditions, respectively, with a silicon treatment of 200 mg/kg. Under both light and shading conditions, silicon treatment improved the root length, root surface area, root volume, root–shoot ratio, fresh weight, soluble sugars, chlorophyll content, and root dry weight. The accumulation of certain carbohydrates, such as sucrose and soluble sugar, in stems and leaves was greatly increased by silicon treatment, thus improving stem strength in both situations. By raising the number of effective pods per plant, the number of beans per plant, and the weight of beans per plant, silicon treatment considerably boosted the output. Following silicon treatment, yields under monoculture and intercropping rose by 24.5% and 17.41%, respectively. Silicon works well to reduce the stress caused by shadowing in intercropped soybeans by boosting photosynthetic efficiency and lodging resistance. El-Shetehy et al. conducted a study demonstrating that both SiO2 nanoparticles and soluble Si(OH)4 can effectively induce systemic acquired resistance in Arabidopsis thaliana against the bacterial pathogen Pseudomonas syringae. The induction of resistance was found to be dependent on the dosage of SiO2 nanoparticles and soluble Si(OH)4 and involved the signaling molecule salicylic acid [59]. In their research, the distribution of SiO2 nanoparticles after being taken up through stomata and their impact on the physiology of plant leaves were investigated by ElShetehy et al. [60]. The results revealed that the presence of nanoparticles led to the obstruction of stomatal pores, causing the complete closure of stomata by blocking the space between guard cells.

5.2.6 Nanoclays Nanofertilizers Nanoclays are one of the most popular nanofertilizers consist of silicates with several layers and bidimensional platelets with a nanoscale (1 nm) thickness and several μm in length [61]. The two main characteristics of nanoclays that make them suitable as nutrition transporters are: (1) their structural elements provide physical barriers that allow them to shield nutrition molecules; (2) in the second approach, the incorporation of nutrients into nanoclay structures occurs through processes such as ion exchange or non-electrostatic interactions, such as hydrogen bonding, where the

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nutrients are intercalated between the layers of nanoclays [62]. Given these two qualities, nanoclays are able to withstand nutrients for long periods of time, accelerate plant growth, stabilize nutrient supply, improve nitrogen usage efficiency, and reduce environmental contamination to a minimum level. A report showed that exposure of zincated nanoclay polymer composite to soil exhibited a slow and controlled release of zinc formulation in rhizospheric wheat soil [63]. The usefulness of nanocatalysts in the purification of water was recently demonstrated in 2021. According to Mollamohammada et al., the amount of nitrate and atrazine in water can be significantly reduced when contaminated groundwater is treated using immobilized nanoclay-algae combinations [64].

5.2.7 Hydroxyapatite Nanoparticles as Nanofertilizers Hydroxyapatite nanoparticles are another intriguing class of nanoparticles that are utilized in the development of nano-enabled nutrients. Considering that hydroxyapatite makes up the majority of our bones and other hard tissues, it is regarded as biocompatible. It can transport calcium and phosphorous because of the significant surface-to-volume ratio [65]. Hydroxyapatite nanoparticles with dimensions of 15– 20 nm and lengths of 100–200 nm can combine to form urea, which is resistant to deterioration and has a rapid release into water. By utilizing its amine and carbonyl functional groups, urea establishes a robust interaction with hydroxyapatite, enabling the controlled and gradual release of urea into the plant medium. This mechanism effectively fulfills the essential nutritional needs of plants, promoting their optimal growth and development. Only urea was shown to have a rapid release profile into the plants (within ten minutes), whereas urea-loaded hydroxyapatite nanohybrids had a very lengthy release profile into the aqueous medium (up to one week) [66]. Recently, urea and hydroxyapatite nanohybrids have been proposed as a potential solution for the delivery of nutrients to plants and the improvement of growth-related characteristics. According to Abeywardana et al., a unique nanoseed coating made from zinc-doped urea-hydroxyapatite nanohybrids significantly enhanced the rate of growth and germination in Zea mays seeds (by 69% and 19%, respectively). In addition to serving as a matrix carrier for zinc and urea, hydroxyapatite nanoparticles also serve as a source of phosphorous, an essential nutrient for root formation in the early stages of plant growth. Observation thus supports it as a suitable candidate for delivery of zinc, nitrogen, and phosphorous at the seedling stage. The hydroxyapatite nanoparticles can be an excellent phosphorus fertilizer in improving the shoot length, root length, wet weight, dry weight, and yield above traditional DAP, according to a 50-day analysis of cluster bean growth [67]. Further, Abdelmijid et al. reported the phosphorous containing hydroxyapatite nanoparticles as using an ecofriendly approach via coffee ground extract and pomegranate peel [68]. Different characteristics like carbohydrate level, photosynthetic activity, biocompatibility effect, and metabolite level have been investigated in the Punica granatum L. plant. Authors stated that in order to obtain beneficial results

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and eliminate negative effects, and nHAPs must be used properly. Relying solely on the present detection methods is not sufficient to prove application. The application of hydroxyapatite nanoparticles in crop management should be more careful due to the dose- and time-dependent restrictions seen in experimental conditions.

5.2.8 Polymeric Nanoparticles as Nanofertilizers Recently, polymeric nanoparticles have received great attention due to their benefits, like being inexpensive, environmentally friendly, and biodegradable. Polymeric nanofertilizers offer numerous advantages, including controlled release of nutrients, protection of agrochemicals against adverse environmental conditions, biocompatibility, biodegradability, and the potential to serve as carriers for agrochemicals in delivery systems. In the study conducted by Niu and Li, they demonstrated that incorporating urea fertilizer within a biodegradable starch-g-poly(vinyl acetate) film promoted the gradual release of nitrogen, providing a slow-release mechanism. The polymeric coating caused the decrease in the rate of urea release. Additionally, they also provided an explanation for how water entered the polymeric layer and disintegrated urea. Water will continue to penetrate until the saturation pressure in the penetrating zone and the surface strength are equal. The water stops penetrating at the point of saturation, and the polymeric layer gently allows the release of urea [69]. Polymer nanocarriers, according to Pereira et al., have the ability to control plant development [70]. Their discoveries in this regard have shown the beneficial use of polymeric nanoparticles as nanocarriers in seed treatment. GA3 containing alginate/ chitosan (nano-ALG/CS) exposure to Solanum lycopersicum seeds was reported to improve germination (by 90%), shoot length, and dry weight (by 35–107%). Additionally, seed treatment with these nanoparticles served a practical purpose by enhancing fruit production. As stated by Li et al., the utilization of double-coated polymers is instrumental in achieving controlled fertilizer release. By applying a dual coating consisting of a hydroscopic resin such as sodium polyacrylate as the outer layer and sodium alginate as the inner layer, the release period of urea can be extended, resulting in a prolonged nutrient release profile [71].

5.3 Delivery of Nanofertilizers Nanomaterials can be internalized in plants via several mechanisms. Nanoparticles with sizes smaller than the pore size of the plant cell wall (ranging from 5 to 20 nm) can enter plant cells by traversing through the porous structure of the cell wall [5]. In contrast, larger nanoparticles internalized into plant cells via endocytosis, ABC transporters, ion channels, and binding to carrier proteins [72]. Reports showed that stomata also play an important role in the uptake of nanomaterials during foliar spraying [73]. In addition, the root exudates and mucilage of plant roots are also

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important for the internalization of nanofertilizer in soil solutions. However, the properties of nanofertilizers are important for their foliar delivery, as the size exclusion effect may limit the stomatal delivery pathway. Stomatal delivery of nanofertilizers can be enhanced in combination with aerosol delivery by controlling the particle size. It has been well demonstrated that foliar delivery of magnesium and iron in nanofertilizer form to Vigna unguiculata plants can significantly enhance their growth and development [74]. Further, aerosol-mediated delivery of nanoparticles has also been demonstrated in watermelon [75] and tomato [76] plant via penetration and translocation. The result shows that aerosol-produced nanoparticles with a diameter less than 100 nm can be internalized into the plant leaf via the stomatal pathway and reach the watermelon plant root, traveling through the xylem and phloem. However, internalization of nanoparticles in plant cells can also be enhanced by aerosol-mediated foliar application via evading the plant cell barrier, i.e., the cuticle. The phloem transport channels in the vascular system, which facilitate bidirectional movement along the photosynthetic gradient, are utilized for the transportation of nanoparticles from the shoot to the root. In solution, nanomaterials present in the surrounding plant root result in the release and internalization of nutrients in the form of soluble ions via the hair root. Following internalization, nanoparticles can be transported in plants via two different routes, symplastic or apoplastic, and enter the cytoplasm, which leads to an alteration of organelle functionalization [77]. Symplast pathways facilitate the transportation of smaller particles with sizes less than 50 nm, whereas apoplastic pathways facilitate the transportation of larger particles (~200 nm) [78]. Carbon nanomaterials also moved throughout the plant body via the xylem vessels. Additionally, they entered the plant from the roots through either apoplastic or symplastic routes, and they traveled to a variety of plant locations as a result. Additionally, it has been established that the use of MWCNTs increases water intake as well as the production of new pores that can penetrate the seed coat, leading to an increase in plant biomass [21]. Further studies are required to unravel the uptake, translocation, and fate of nanofertilizers in plant cells. Table 5.1 shows the various nanofertilizers and their impact on plants.

5.4 Mechanism of Action Nanoparticles like ZnO significantly improved the biomass, chlorophyll content, shoot and root length as well as phosphatase enzymatic activity in Raphanus sativus, Cicer arietium, Brassica napus, and Vigna radiate [79, 80]. ZnO nanoparticles with a mean diameter of 25 nm and a 10 ppm concentration have been reported to induce the functionalization of enzymes responsible for phosphorous mobilization like acid and alkaline phosphatase [30]. These enzymes facilitate the transformation of phosphorous complex forms (Al-P, Ca-P, Zn-P, and Fe–P) into plant-available forms. Zn serves as a cofactor for phosphorous solubilizing enzymes like phytase and phosphatase, and the presence of ZnO nanoparticles enhances this activity between 84 and 108%. It has also been reported that the action of ZnO nanoparticles enhances

Concent ration

Different concentration ranging from 0.25–169 g

75, 150, 300 and 600 mgCu/kg

2–1000 mg/kg

500, 60, and 400 mg/kg NPK

62.5–500 mg/kg

75–600 mg/kg

Nanofertilizers

Nano hydroxyapatite

Copper oxide nanoparticles

Iron oxide nanoparticles

Chitosan-encapsulated NPK

Z-Cote HP1 (triethoxycaprylylsilane-coated ZnO)

Copper oxide nanoparticles

Table 5.1 Various nanofertilizer and their impact on plants

Allium fistulosum

Phaseolus vulgaris

Wheat plant

Arachis hypogaea

Brassica rapa

Zea mays L

Plant [91]

Reference

[94]

Treatment of nanoparticles leads to higher copper content in plant root. Treatment with nanoparticles at a dosage of 150 mg/kg resulted in increased levels of calcium (Ca), iron (Fe), bulk calcium, and bulk magnesium (Mg) in the roots. Furthermore, nanoparticle treatment led to elevated levels of allicin in the leaves across all tested concentrations

(continued)

[96]

In comparison with uncoated particles, seeds that were grown [95] in natural soil and treated to nanoparticles with coatings produced 44% more sugar. When compared to seeds from plants grown in natural soil, seeds grown in soil supplemented with organic matter contained significantly higher concentrations of the elements zinc (38%), potassium (64%), sulfur (44%), phosphorus (38%), magnesium (86%), calcium (70%), iron (89%), and manganese (85%)

Maturation time has been accelerated by 40 days. Grain output per plant has been increased by 101.8% in comparison with conventional fertilizer

More chlorophyll, abscisic and gibberellic acids, and total Fe [93] in the roots and shoots, as well as more branches have been observed. There is no analysis of the nutritional value or yield

Nanoparticle treatments resulted in greater Cu uptake in the [92] roots of plants at all concentrations. Rosie variety has higher copper than green. Reductions in chlorophyll and leaf biomass were seen in the Rosie variety. These effects may be attributed to anthocyanins content

Enhanced physiological and development characteristics of the maize plant

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Concent ration

15 kg of N/ha as sprayed

80 and 280 mg Cu/kg

10, 12.5, and 15 mL/L

100, 200, and 300 mg/L

Nanofertilizers

Urea doped calcium phosphate nanoparticles

Copper nanowires

AgNPs

ZnO nanoparticles and Iron oxide nanoparticles

Table 5.1 (continued) Nanoparticles treated plants showed similar yield and quality parameters as of conventional fertilization; however, nanoparticles exposure reduced the nitrogen rate by 40%

Results [97]

Reference

Exposure to nanoparticles leads to an increase in shoot diameter, leaf area, total chlorophyll content, flower percentage, fruit yield, as well as physical and chemical characteristics of the fruits, and also have significant impact on pollen viability

[99]

(continued)

Cucumis sativus Nanoparticles exposure enhanced total chlorophyll content [100] L (15.9–17.3%), seed yield (51.7–52.2%), and concentration of Zn and Fe concentration in the fruit and the seed. Additionally, enhanced concentration of soluble sugars and proteins, starch, and oil content was also observed in the seeds from the nanoparticles treated plants. Nanoparticles exposure also enhanced the germination percent, germination rate, and seedling vigor (59.8–72.6%). A notable enhancement has been observed in the water uptake of seeds and the activity of hydrolytic enzymes (amylase and protease) during seed germination. Seeds from nanoparticle treated plant showed increased activity of reactive oxygen species (superoxide anion and hydrogen peroxide) and antioxidant enzymes (superoxide dismutase, catalase, and peroxidase) in the germination process

Prunus persica L. Batsch

Medicago sativa The presence of nanowires significantly upregulated the [98] expression of leaf-superoxide dismutase, with an approximate 27-fold increase, while rubisco mRNA levels remained unaffected. Furthermore, higher concentrations of iron (Fe) and zinc (Zn) were observed in the roots. Additionally, the nanowires promoted the growth of specific microorganisms involved in the uptake of these elements

Triticum durum

Plant

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10, 25, 50 and 100%

10, 25, 50, 100, 250, 500, 1000, 2000 mg/L

0.01–0.16%

Nano-NPK fertilizer

Copper oxide nanoparticles

Chitosan nanofertilizer

Zea mays

Hordeum vulgare L

Capsicum annum L

15 kg of N/ha of a sprayed Triticum durum aqueous suspension

Calcium phosphate nanoparticles

Plant

Concent ration

Nanofertilizers

Table 5.1 (continued) Reference

[102]

Compared to the control, nanoparticle exposure causes a [104] 1.6-fold increase in the seedling vigor index and a 1.7- to threefold increase in the reserve food mobilizing enzyme activity. It also dramatically raised the activities of antioxidant enzymes, decreased malondialdehyde content, and increased chlorophyll content in leaves by twofold; promoted sucrose translocation in internodes by 2.5–3.5-fold

Result showed the enhancement in seed germination seedling [103] growth parameters at low concentration, whereas concentration higher than 500 mg/L exhibited inhibitory effect

The extent of the effects appeared to vary with concentration. Foliar application revealed that nanocomposite NPK at a concentration of 25% considerably enhanced the growth, yield, and harvest of C. annuum

Allows a 40% reduction in the amount of nitrogen provided to [101] plants compared to standard methods, without compromising the final kernel weight per plant

Results

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Fig. 5.6 Nanoparticles and nanofertilizers promote seed germination by increasing the expression of aquaporin genes, facilitating the absorption of water, nutrients, and reactive oxygen species (ROS) through the seed coat, and stimulating the secretion of α-amylase enzymes from aleurone cells. Reprinted with permission from Advances in Nano-Fertilizers and Nano-Pesticides in Agriculture, Copyright 2021, Elsevier [81]

the dehydrogenase activity by 21% in comparison with the control. This suggests the accumulation of microbes in the rhizosphere, which also facilitates nutrient mobilization and their availability to plants [31]. The mechanism of nanofertilizer has been shown in Figs. 5.6 and 5.7. Other studies demonstrated that plant tissues subjected to magnesium oxide nanoparticles showed a higher magnesium content, indicating that the magnesium was absorbed by the tobacco roots and moved to the shoots and leaves, which were likely the most crucial components for increasing the amount of chlorophyll and promoting growth [82]. Further, titanium dioxide nanoparticles (TiO2 NPs) alone similarly boosted the amount of chlorophyll in Spinacia oleracea. When chlorella pyrenoidosa cells were exposed to anatase TiO2 nanoparticles, they had more pigments that help them make food, like chlorophyll a (Chl a) and phycobiliproteins (PBPs). Additionally, it was found that the genes for chlorophyll a and photosystem II (PS II) were activated in these cells. On the other hand, the photosynthetic activity drastically decreased, which demonstrated that the damage to the PS II reaction center had a negative impact on the process of photosynthesis [83]. Photosynthesis is a vital process in plants where light energy is converted into chemical energy and carbon dioxide is transformed into sugars, playing a crucial role in their metabolism. Several studies have been performed to investigate if nanoparticles and nanotechnology can speed up the photosynthetic rate in plants. In this

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Fig. 5.7 Nanofertilizers stimulate Rubisco activase, leading to enhanced Rubisco carboxylation and increased metabolic activity. Reprinted with permission from Advances in Nanofertilizers and Nanopesticides in Agriculture, Copyright 2021, Elsevier [81]

context, gold and silver nanocrystals have shown positive impacts on hybrid photosystems [84]. The experimental findings revealed the creation of a hybrid system when chlorophyll a in the photosynthetic reaction center interacted with gold and silver nanocrystals, forming a unique composite. In the presence of metal nanoparticles, photosynthetic system’s ability to produce chemical energy can be significantly improved. The efficiency of the photosystem can be modulated by two mechanisms: the amplification of photon fields inside the light-absorbing chlorophyll molecules through plasmon resonance, and the energy transfer from chlorophylls to metallic nanoparticles. In the first step, the amount of light absorbed by chlorophylls can be significantly increased, whereas the second step leads to a reduction in system quantum yield. Due to the plasmon resonance and quick electron–hole separation, the production of excited electrons inside the reaction center has been significantly enhanced. The photocurrent responsiveness can be improved by plasma resonance in phototransport experiments involving photosynthetic reaction centers [84]. Limited studies have focused on elucidating the molecular mechanisms underlying the growth and development of plants exposed to silver nanoparticles (AgNPs) [85]. The results showed the upregulation of genes involved in chloroplast biogenesis, cell division regulation, i.e., carbohydrate metabolism, cell-division-cycle kinase 2 (CDC2), protochlorophyllide oxidoreductase (POR), and fructose 1,6-bisphosphate

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aldolase (FBA) [86]. A study showed the positive impact of AgNPs on biological processes involved in cell division, chloroplast formation, and glucose metabolism. Further, authors have also stated the 1.5-fold overexpression of IAA8 upon exposure of plants to 100 nM decahedral AgNPs, whereas RD22 and NCED3 expression have been enhanced by 3.5 times and 2 times, respectively. Treatment of decahedral AgNPs also induces an enhanced level of root growth promotion. It has also been observed that AgNPs interact with the genes involved in the signaling pathways of auxin and abscisic acid and alter their signal transduction [86]. Nanofertilizers may be able to boost agricultural productivity under currently unfavorable conditions, according to advances in nanomaterial engineering. SiO2 nanoparticles have been reported to enhance the tolerance of plants to abiotic stress by enhancing dry weight, proline accumulation, and freshness in leaves [81]. SiO2 nanoparticles were also reported to enhance the photosynthetic and electron transport rates, gas exchange, PS II activity, and photochemical quenching [87]. Further, rice plants’ ability to withstand lead, copper and cadmium stress has been greatly increased by foliar application of SiNPs at 2.5 mM concentration via controlling cadmium accumulation [88]. The increased enzyme activity observed can be attributed to the molecular mechanism of the nanofertilizer, which is responsible for facilitating this enhanced activity [89]. In addition, the use of nanofertilizers such as nano-SiO2 or nano-ZnO increases the accumulation of free proline and amino acids, as well as nutrient and water uptake, as well as the activity of antioxidant enzymes such as catalase, superoxide dismutase, peroxidase, glutathione reductase, and nitrate reductase, which in turn increases plant tolerance to adverse environmental conditions [89]. A thorough molecular analysis revealed that AgNPs can upregulate and downregulate various genes in Arabidopsis. Genes related to ethylene signaling and auxin regulation were found to be downregulated, while those associated with superoxide dismutase, cytochrome P450-dependent oxidase, peroxidase, and cation exchanger showed upregulation. Oxidative and osmotic stress tolerance in plants can be enhanced by the presence of jasmonic acid. In this context, it has been reported that treatment of chitosanpolyvinyl alcohol and copper nanoparticles (Cs-PVA + Cu nanoparticles) and the Cs-PVA can reduce the gene expression of jasmonic acid by 75% and 66%, respectively [90]. Result thus revealed that Cs-PVA + Cu nanoparticles and the Cs-PVA treatment make up saline stress in plant and regulate the ionic and oxidative stress in plant for improvement of their growth. This finding provided evidence that the jasmonate octadecanoid pathway of the Cs-PVA and the Cu nanoparticles activated the antioxidant defense mechanisms of a plant.

5.5 Nanopesticides All types of pests are mostly deterred by pesticides. They might therefore be developed to combat weeds, fungus, or insects that harm plants. All of these pesticides, however, have also been proven to be highly dangerous. The accumulation of certain

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nanoparticles in soil and water can lead to significant concerns when they enter the food chain [105]. Consequently, nanotechnology is recognized as a promising field for the efficient management of pests, offering advantages such as monitoring flexibility, biodegradability, and specificity toward target pest species while minimizing environmental contamination [106]. Nanomaterials have a significant impact on increasing agricultural productivity by facilitating insect control through optimum pesticide dosage and progressive release [107]. The term “nanopesticides” is used to describe pesticides that have been formulated using nanomaterials specifically designed for agricultural applications. These nanopesticides are often incorporated into hybrid substrates, encapsulated within a matrix, or modified as nanocarriers that respond to environmental or enzyme-mediated triggers. Innovative formulations of nanocarriers based on materials including silica, lipids, polymers, copolymers, ceramic, metal, carbon, and others are anticipated to explore pesticide actions through the combination of their structure and unique features [108]. They are made with the intention of minimizing human exposure to pesticides [109]. When used as herbicides, great penetration ability of nanomaterials helps to get rid of weeds before they become resistant to pesticides, however, overuse of traditional herbicides makes plants resistant to them. In contrast, the antimicrobial activity of bactericides and fungicides begins by attaching a metal nanocomposite to the surface of microbial cells, thereby altering the properties of the cell membrane. The metal plates and the cell walls interact electrostatically and have potential to damage cell structure, increase membrane permeability, cause intracellular substance leakage, produce reactive oxygen species, and ultimately impair microbial essential functions. As a result of their binding to numerous cell organelles, they disrupt metabolic functions and have an impact on the cell’s biochemical processes (Fig. 5.8). There are different types of nanomaterials, including clay, carbon, and metal nanomaterials. Reports showed that iron oxide nanoparticles with cubic morphology and average particle sizes of 56–350 nm were synthesized using leaf extract from S. laureola [111]. Synthesized nanoparticles exhibited strong antibacterial activity against R. solanacearum at all the tested concentrations. In addition to prevent in vitro bacterial growth, iron oxide nanoparticles also prevented tomato bacterial wilt in a pod experiment. The integration of nanoparticles caused the release of intracellular compounds, which in turn caused a degenerative alteration of the exterior morphology. These results show that iron oxide nanoparticles have the ability to inhibit phytopathogens in agricultural settings. AgNPs, being the most widely utilized nanomaterial, exhibit unique physical, chemical, and biological characteristics. These include optical properties, electrical conductivity, thermal stability, catalytic activity, chemical stability, a high surfaceto-volume ratio, and antimicrobial properties. As a result, AgNPs have found diverse applications, particularly as antimicrobial and antifungal agents. Further, due to their versatility, AgNPs are extensively used in the biomedical and agrifood industries [112]. Nilaparvata lugens, often known as the brown planthopper, is a serious pest of rice plants (Oryza sativa L.), particularly in Asia. Although it is often managed chemically, but become resistant to several pesticides [113]. El-ela and colleagues

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Fig. 5.8 Bactericidal mechanisms of AgNPs involve several processes. Initially, AgNPs adhere to the bacterial wall, causing membrane disruption and leakage of cellular contents. Both AgNPs and silver ions (Ag+) have the ability to bind to proteins on the cell membrane, triggering the generation of reactive oxygen species (ROS) and inhibiting adenosine triphosphate (ATP) production. Subsequently, AgNPs penetrate into the cytoplasm, where they interact with various biomolecules such as proteins, enzymes, lipids, and DNA. The elevated levels of ROS induce an apoptosis-like response, lipid peroxidation, and DNA damage. Additionally, AgNPs exhibit sustained release of Ag+ both inside and outside the bacterial membrane, allowing Ag+ to interact with proteins and enzymes, further contributing to the bactericidal effect, adapted from [110]

conducted a study where they successfully synthesized AgNPs by utilizing the exogenous phytohormone gibberellic acid (GA3) as a reducing agent [114]. The effects on the plants and insects were then assessed after we separately applied them to rice plants and BPH. Result showed the synthesis of AgNPs with uniform shape, and spherical and cubical structures having 25–60 nm diameter. Different volatile profiles have been observed by the application of nanoparticles and GA3 on rice plants; the maximum number of these profiles, including the highest emission of linalool, were emitted under AgNPs. Transcriptome analysis revealed that, 24-h exposure of nanoparticles to rice plants displayed different transcriptome profiles in comparison with control. According to the findings of the study, the expression of the linalool synthase gene, in addition to other plant transcription factors including

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WRKY, bHLH, and NAC, was increased as a result of the treatments. In addition to this, the concentration-dependent action of AgNPs led to an increased mortality rate of BPH patients over the course of the study. The use of nanoparticles resulted in a reduction in the total protein concentrations in BPH, as well as an increase in the activity of protecting enzymes (POD, SOD, and CAT), a reduction in the activity of detoxifying enzymes (A-CHE, ACP, and AKP), and a reduction in the activity of detoxifying enzymes. These findings suggest that the environmentally friendly and potentially safer method for managing BPH in rice production may be to synthesize nanoparticles utilizing phytohormones. In general, microorganisms have been extensively investigated for the generation of AgNPs for a variety of purposes. Santos et al. demonstrated the comparison of the biological synthesis of AgNPs by entomopathogenic fungi to that of other filamentous fungi, as well as the potential use of these nanoparticles as antimicrobials and insect pesticides [115]. In another study, Granetto et al. demonstrated a unique nanoformulation to prevent dicamba, a widely used herbicide, from leaking and vaporizing [116] (Fig. 5.9). Due to its remarkable solubility, dicamba is vulnerable to substantial leaching in soils as well as significant volatilization and vapor drift, posing dangers to users and nearby crops. To manage its environmental dispersion, natural, affordable, and biocompatible materials were used. A nanoscale form of natural clay, more precisely K10 montmorillonite, was utilized in this study in order to improve the adsorption of a pesticide. The clay was then covered in carboxymethyl cellulose (CMC), a biodegradable polymer that is frequently discovered in goods intended for consumption. After being diluted to concentrations appropriate for field settings, the nanoformulation demonstrated controlled release properties. The uncoated K10 clay discharged around 45% of the loaded dicamba into the tap water, but this number dropped to less than 30% once

Fig. 5.9 Nanoformulations based on natural clays and biopolymers have shown promising potential for mitigating the environmental dispersion of water-soluble herbicides. Reprinted with permission from Science of The Total Environment, Copyright 2022, Elsevier [117]

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the coating was applied. Additionally, the presence of CMC resulted in a sizeable reduction in the amount of dicamba that was lost as a result of volatilization from treated soils. For example, only 4.5% of the coated nanoformulation and 9.3% of the commercial product were lost in the first 24 h in medium sand. When compared to the uncoated nanoformulation and the commercial formulation, the mobility of the coated nanoformulation was significantly reduced in porous media. Studies conducted in greenhouses demonstrated that the clay-based nanoformulation did not impact the performance of dicamba against the weeds that were being targeted, but variances were detected depending on the species that were being treated. Despite the small scale of the laboratory and greenhouse investigations, these preliminary findings illustrate the potential of the recommended nanoformulation for minimizing the environmental dispersion of dicamba without affecting its effectiveness against target species. This can be accomplished by reducing the amount of dicamba that is released into the environment. Xiang et al. further demonstrated the aldehydemodified sodium alginate (ASA) to develop AgNPs (A-AgNPs) using a two-step process [118]. A-AgNPs has been produced in sizes ranging from 6 to 40 nm with excellent water dispersibility. Additionally, the A-AgNPs displayed improved broadspectrum antimicroorganism efficacy in comparison with naked AgNPs (n-AgNPs). Authors reported that the A-AgNPs primarily exercised their antifungal activity by altering the permeability of cell membranes, influencing the production of soluble proteins, damaging DNA structure, and inhibiting DNA replication. However, germination of rice and N. benthamiana seeds was not inhibited by A-AgNPs. Thus, AAgNPs have the potential to be used in plant protection study due to their high biocompatibility and extremely effective antimicroorganism activity. In other study, Danish et al. synthesized the AgNPs from the leaf extract of Cassia fistula (L.). They then tested the nanopesticidal capacity of these AgNPs against the most significant phytopathogens that affect tomato plants. The research discovered that the particle size of the synthetic nanoparticles ranged from 10 to 20 nm, with a diameter that averaged 16 nm [119]. Result showed that Pseudomonas syringae was inhibited by increasing concentrations of Ag@CfL nanoparticles and 400 μg/ ml of Ag@CfL nanoparticles exposure showed decreased cellular viability, altered bacterial shape, and thus resulted in cellular death. Additionally, Ag@CfL nanoparticles prevented P. syringae from producing exopolysaccharides (EPS) or forming biofilms. Additionally, Ag@CfL nanoparticles also demonstrated strong antifungal action against important fungal infections. Fusarium oxysporum (76%) was the most sensitive of the investigated fungus at 400 μg/mL Ag@CfL nanoparticles, followed by R. solani (65%) and Sarocladium (39%). To enhance the adsorption of a pesticide, a nanoscale natural clay, specifically K10 montmorillonite, was utilized. The clay was coated with CMC, a biodegradable polymer commonly found in food-grade materials. The nanoformulation exhibited controlled release characteristics when diluted to levels relevant to field conditions. In tap water, the uncoated K10 clay released approximately 45% of the loaded dicamba, which decreased to less than 30% after the application of the coating. Furthermore, the presence of CMC significantly reduced dicamba losses due to volatilization from treated soils. For instance, in medium sand, only 4.5% of the coated nanoformulation and 9.3% of the commercial

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product were lost within 24 h. The mobility of the coated nanoformulation in porous media was also notably reduced compared to the uncoated nanoformulation and commercial formulation. Greenhouse studies indicated that the clay-based nanoformulation did not compromise the efficacy of dicamba against target weeds, although variations were observed depending on the treated species. These preliminary findings demonstrate the potential of the suggested nanoformulation in minimizing the environmental dispersion of dicamba without compromising its effectiveness against target species, despite the limited scale of the laboratory and greenhouse studies. This resulted in an overall performance improvement. This work is expected to be a key indicator for the development of effective nanocontrol agents that will help manage deadly phytopathogens that significantly reduce agricultural productivity. Overall, results suggest that Ag@CfL nanoparticles may be employed in green agriculture as nanopesticides to control diseases and enhance plant health in a sustainable manner. The most harmful pathogen that causes the bacterial wilt disease of eggplant is Ralstonia solanacearum. Alamer et al. used native bacterial strain for green production of silver chloride nanoparticles (AgCl NPs) and evaluated their antibacterial activity against R. solanacearum [120]. Authors have used ten different bacterial strains for production of AgCl nanoparticles and found that cell-free aqueous filtrate of strain IMA13 had the best yield out of all of them. The AgCl nanoparticles that were artificially produced have a spherical and oval shape, smooth surfaces and diameters ranging from 5 to 35 nm. The biogenic AgCl nanoparticles displayed considerable antibacterial activity against R. solanacearum at a concentration of 20 μg/mL. This concentration also resulted in a reduction in the swarming and swimming motility of R. solanacearum (61.4 and 55.8%, respectively). The interaction between AgCl nanoparticles and bacterial cells resulted in the disruption of the cell wall and cytoplasmic membranes, leading to the release of nucleic acid materials and ultimately causing the demise of R. solanacearum. These findings hold significant promise for the advancement of an effective nanopesticide targeted at managing phytopathogenic plant diseases. In several agrolivestock application sectors with ecofriendly qualities in the field and greenhouse production, a stimulus light-responsive controlled release (Fig. 5.10) has been deployed as a delivery method. After self-assembling and encapsulating a pesticide, a light-responsive copolymer called Poly(ethylene oxide-b-methacrylic acid) (PEO-PMAA) was developed containing light-sensitive groups. The formulation’s considerable residual activity was then observed [121]. Other than this, a dual pH and ion strength responsive complex system is another approach that focuses on novel materials to reduce the amount of pesticide used in the crop, reduce leaching and decomposition of pesticides, and have a minimal negative impact on the ecosystem [122]. With the stimuli responsive release, early complexation of agrochemicals can be delayed, sulfidation reaction can be inhibited, and the system’s ability to manage pests can be extended. Due to their larger surface area, photocatalysis, and other properties, ZnO nanoparticles are more beneficial in biological systems. Zinc-based nanopesticides have direct and indirect antibacterial effects. Nanomaterials’ participation in antimicrobial activities is the direct strategy, whereas enhancing the nutritional content of

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Fig. 5.10 Diagram depicting a light-triggered mechanism for controlled release of modified pesticides, adapted from [125]

crops can increase secondary metabolic and antibacterial activities through indirect methods [123]. Upon interaction of ZnO nanoparticles with the bacterial cell wall, Zn2+ is released and can enter the cytoplasm, where it interacts with acidic and neutral functional groups. This leads to a disruption in the natural structure of cell membranes, and membrane proteins lose their ability to function normally. Since enzymes directly regulate the bacterial metabolism, Zn2+ -enhanced enzyme suppression will also reduce the physiological activity of the bacteria. Further, Zn2+ can also interact strongly with protein binding sites and have an impact on several proteins’ ability to operate normally [124]. Significant work has been carried out for the development of a method that is both efficient and safe for controlling serious bacterial illnesses in agriculture. An in situ crystal growth approach was used to develop a pH-responsive core–shell nanocarrier (ZnO-Z) using zinc oxide nanospheres and ZIF-8 as the core and shell, respectively [126]. To manage the tomato bacterial wilt disease, the bactericide berberine (Ber) was further loaded to create Ber-loaded ZnO-Z (Ber@ZnO-Z) (Fig. 5.11). The findings showed that Ber@ZnO-Z could rapidly release Ber in an acidic environment, which corresponds to the soil pH where the tomato bacterial wilt disease frequently occurs. In vitro tests revealed that Ber@ZnO-Z had antibacterial activity

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that was roughly 4.5 and 1.8 times greater than that of Ber and ZnO-Z, respectively. Result showed that Ber@ZnO-Z significantly induces ROS generation, which further leads to cytoplasm leakage, DNA damage, and an alteration in membrane permeability in bacterial cells. A wilt index of 45.8% on day 14 following inoculation for Ber@ZnO-Z in pot studies demonstrated a considerable reduction in disease severity compared to 94.4% for commercial berberine aqueous solution. More importantly, ZnO-Z carriers did not accumulate in plants’ aboveground tissues and did not have an immediate impact on plant growth. This research offers recommendations for the development of sustainable agriculture and the efficient management of bacterial infections transmitted through soil. Rice disease pathogens Burkholderia glumae and B. gladioli spread through rice seeds and cause the bacterial panicle blight (BPB) disease, which causes significant yield losses for rice across the globe. In this context, Ahmed et al. used the natural Bacillus cereus RNT6 strain for the biological synthesis of ZnO nanoparticles and investigated their effect on this disease [127]. Synthesized ZnO nanoparticles have a diameter ranging from 21 to 35 nm and a spherical shape. Biogenic ZnO nanoparticles significantly reduced the cell counts (measured by OD600 ) of the two pathogens in broth culture by 71.2% and 68.1%, respectively, at a concentration of 50 μg/mL

Fig. 5.11 a Figure demonstrating the synthesis of Ber@ZnO-Z nanospheres and b their utilization in the combined management of bacterial wilt disease in tomato plants. Adapted from [126]

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Table 5.2 Various nanopesticides and their application to various plant diseases Nanoparticles

Pathogens

Concentration

Result

Reference

Zinc oxide

Fusarium graminearum

100 mM

Significantly reduces the F. graminearum population and deoxynivalenol (DON) formation in the Triticum aestivum L. (wheat plant) at low concentration

[128]

Zinc oxide/ magnesium oxide nanocomposite

Colletotrichum gloeosporioides

625 mg/L

Radial growth test [129] confirms that fungal avocado strain proved to be more susceptible to the nanoparticles than the strain obtained from papaya. Microdilution technique revealed that concentration between 156 and 625 mg L−1 suppressed the spore germination of C. gloeosporioides

Titanium dioxide

Helicoverpa armigera

100 ppm

Treatment exhibited high [130] mortality rate and leads to reduction in β-glucosidase and carboxylesterase enzyme, whereas glutathione S-transferase level increases

Chitosan–silver Colletotrichum nanoparticlecomposite gloeosporioides

1% Chitosan-AgNP composite with Tween-80

Composite decreased the frequency of anthracnose in mango and prevented C. gloeosporioides’ conidial germination

Chitosan copper oxide Fusarium (Ch-CuO) oxysporum f. sp. nanocomposites and ciceri (FOC) chitosan-zinc oxides (Ch-ZnO) nanocomposites

50, 100 and 200 μg/mL

Ch-CuO (46.67%) [132] showed the greatest wilt disease decrease, followed by plants treated with Ch-ZnO (40%) as being somewhat effective

Oligochitosan–silica/ carboxymethyl cellulose

800 mg/L

Inhibited fungal growth with enhanced zone of inhibition and less concentration in comparison with chitosan and silica alone

Phytophthora infestans

[131]

[133]

(continued)

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Table 5.2 (continued) Nanoparticles

Pathogens

β-D-glucan nanoparticles

Pythium 0.1% w/v aphanidermatum

Concentration

Result

Foliar spray of β-d-glucan [134] nanoparticles significantly enhanced the activity of defense enzymes in turmeric plants and provide 77% protection against rhizome rot disease

Reference

Starch derivatives nanoparticles

Phomopsis asparagi, Colletotrichum lagenarium, and Fusarium oxysporum

1.0 mg/mL

Compared to starch, synthetic starch derivatives demonstrated better antifungal efficacy

MoS2 -embedded mesoporous silica

Rhizoctonia solani and Fusarium graminearum

2.0 mg/L

Nanocomposite showed [136] controlled pesticides release and inhibition rate reaches to 76.79% after 48 h incubation

Cerium oxide nanoparticles

Fusarium oxysporum f. sp. lycopersici

50 and 250 mg/ At 250 mg/kg, disease [137] L severity was reduced by 53% with soil application. Foliar application reduced disease severity by 57%

Zinc oxide nanoparticles

Sclerospora graminicola

50 − 500 mg/L Downy mildew [138] sporulation has been inhibited at 150 mg/L concentration. When used as a spray, 200 mg provided 63.73% 3.08 protection from downy mildew

[135]

against B. glumae and B. gladioli which had zone of inhibition of 2.83 cm and 2.18 cm, respectively. Ultrastructure studies showed that in comparison with control, ZnO nanoparticles exposed B. glumae and B. gladioli cells evidenced significant morphological damage. According to the findings, ZnO nanoparticles are a promising class of nanopesticides for preventing BPB illness in rice. Table 5.2 shows the various nanopesticides and their applications to various plant diseases.

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5.6 Summary In the fifth chapter of the book, the topic at hand is the important role that nanofertilizers and nanopesticides play in the process of making food items healthier and safer. It starts off with a brief introduction to the subject matter, focusing on the significance of these nanoparticles in the agricultural industry. The topic of nanofertilizers is discussed in depth in Sect. 5.2, beginning with zinc as a nanofertilizer (5.2.1), then moving on to iron (5.2.2), nitrogen (5.2.3), carbon-based nanomaterials (5.2.4), silicon (5.2.5), nanoclays (5.2.6), hydroxyapatite nanoparticles (5.2.7), and finally polymeric nanoparticles (5.2.8). In each of the subsections, the potential of these nanoparticles as efficient fertilizers and their specific applications in improving plant nutrition and growth are investigated. In addition, the delivery mechanisms of nanofertilizers are covered in this chapter (Sect. 5.3), and the need for controlled release systems for efficient nutrient utilization is emphasized throughout the discussion. In this article, the mechanism of action (Sect. 5.4) that underlies the efficacy of nanofertilizers in boosting plant health and productivity is investigated in additional detail. The last part of this chapter is devoted to discussing nanopesticides (Sect. 5.5), with an emphasis on the role that they play in pest management and crop protection. It demonstrates the benefits of using nanopesticides by demonstrating their ability to provide targeted and controlled releases of pest control chemicals, thereby minimizing environmental pollution and maintaining food safety. In general, this chapter offers a complete overview of nanofertilizers and nanopesticides, as well as their distribution techniques and the action mechanisms that they employ. It is a helpful resource for understanding the possible applications of nanotechnology in agriculture and the impact it has on the production of food items that are healthier and safer.

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Chapter 6

Nanomaterials-Based Nutraceuticals, Nutrigenomics, and Functional Food: Design, Delivery, and Bioavailability

Abstract This book chapter explores the formulation, distribution, and bioavailability of nutraceuticals, nutrigenomics, and functional foods based on nanomaterials. The utilization of nanoparticles in nutraceutical formulations offers several advantages, such as improved stability, bioavailability, and effectiveness. The chapter specifically focuses on the applications of nanoparticles in the nutraceutical field, highlighting their potential to revolutionize the industry. Furthermore, it investigates the noteworthy antibacterial, antifungal, and anticancer properties of nanonutraceuticals, underscoring their promising therapeutic potential. The chapter also addresses the influence of genetically modified foods on genomic changes and provides valuable insights into the emerging field of nutrigenomics. Overall, this chapter provides valuable and up-to-date information on the latest advancements in nanomaterialbased nutraceuticals, nutrigenomics, and functional foods, serving as a catalyst for future research and development in this exciting area of study.

6.1 Introduction In recent years, changes in lifestyle have led to an increase in the frequency of several diseases, like type 2 diabetes and cardiovascular diseases. Meanwhile, people are becoming more aware of the relationship between eating habits and these deadly diseases. As a result, people are paying more attention to the quality of the food they ingest and demonstrating a greater interest in foods that can improve their health and prevent the occurrence of these diseases [1]. These factors prompted research into the potential health benefits of nutraceuticals, nutrigenomics, functional foods, and their mechanisms of action. Concurrently, the industry encouraged to develop novel products that would stimulate the interest of consumers [2]. Nanoformulations are one of the newest methods for administering bioactive chemicals to people and animals. The formulation is frequently employed in the administration of highly potent pharmaceuticals, such as cytostatic agents, due to its ability to facilitate sitespecific drug delivery and regulated drug release, thereby reducing the undesirable impacts of the drug.

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_6

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In the integrated nanotechnology fields of nutraceuticals and nutrigenomics, the most prominent issues are functional food production with therapeutic molecules and their delivery as drug candidates. The present chapter centers on the application of nanotechnology in the domains of nutraceuticals, nutrigenomics, and functional food. Specifically, it explores how these applications can be used to treat serious diseases related to lifestyle factors [3].

6.2 Nanonutraceuticals The term “nutraceutical” (nutrition + pharmaceutical) denotes dietary products or their constituents that provide therapeutic or preventative health benefits. Nutraceuticals are a class of natural compounds that encompass a variety of substances, including antioxidants, prebiotics, probiotics, herbal products, spices, polyunsaturated fatty acids, and other naturally occurring chemicals. These compounds are utilized as a means of achieving therapeutic objectives in a natural and original manner. In contemporary times, there has been a surge in the demand for nutraceuticals due to the growing fascination with naturally occurring chemical compounds. This trend has driven the development of novel functional foods that incorporate nutraceuticals. However, limitations associated with their use have hindered their efficacy due to instability, low solubility, and poor bioavailability following encapsulation. Nanotechnology offers a solution by enabling researchers to overcome these limitations through structures with dimensions in the order of nanometers. Thymoquinone (TQ), found primarily in Nigella sativa, possesses potent anticancer, antioxidant, antibacterial, immunomodulatory, and anti-inflammatory effects, making it an attractive nutraceutical candidate. However, its high instability and quick elimination, coupled with its 99% binding to plasma proteins, limit its clinical efficacy. To maximize TQ’s pharmacological impact while minimizing renal clearance, it requires the protection offered by nanonutraceuticals. Nanonutraceuticals offer ideal delivery mechanisms for TQ as they can be targeted toward specific tissues or organs where they can attain therapeutic concentrations sustained over time. Due to their ability to easily permeate biological membranes and provide prolonged release of TQ throughout various body areas, nanoformulated thymoquinones would increase their bioavailability, making them more effective clinically. Figure 6.1 shows the various advantages of using nanotechnology approaches for the delivery of nutraceuticals. It is of major concern that the high amount of waste produced from the food industry can be considered a major nutraceutical source with a very positive impact on the environment [4]. Likewise, olive pomace, a beneficial byproduct of olive oil manufacturing, exhibited several advantages due to its excessive amount of antioxidants, particularly polyphenolic components including hydroxytyrosol, tyrosol, and oleuropein [5]. They work in tandem to reduce cellular oxidative stress, which has positive effects on the prevention of cancer, cardiovascular diseases, aging, and neurological disorders [6]. In this context, Galic and colleagues employed olive pomace as a means for the ecofriendly synthesis of selenium nanoparticles [7].

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Fig. 6.1 Primary benefits of nanoencapsulation of nutraceuticals within the food industry. “GRAS” is a Food and Drug Administration designation that denotes “Generally Recognized as Safe,” adapted from [2]

The researchers subsequently evaluated the bioaccessibility and biocompatibility of these nanoparticles in an in vitro model. In the present study, olive pomace can be hypothesized to act both as a reducing agent (for selenite reduction) and a functional stabilization agent (for improvement of bioaccessibility and physicochemical properties). The olive pomace functionalization drastically diminished nanoparticle size and zeta potential. The functionalization of olive pomace enhanced the average bioaccessibility, which ranged from 33.57 to 56.93%. The experiments on biocompatibility confirmed the decreased toxicity of the majority of selenium nanoparticles compared to sodium selenite as well as demonstrated that the functionalization of nanoparticles with olive pomace has a substantial effect on the biocompatibility of derived nanosystems, and this depends on the cell lines used.

6.2.1 Cancer Cancer is a primary cause of impairment in human health and has a high mortality rate. The disadvantages of chemotherapeutic drugs include poor solubility, dosedependent toxicity, non-specific targeting, and diminished permeability, resulting in various systemic adverse effects. Multiple chemotherapeutic agents can lead to the development of drug resistance in cancer cells, thereby reducing their effectiveness in combating cancer [8]. Utilizing nutraceuticals of natural origin can mitigate the shortcomings of chemotherapeutic drugs in cancer treatment. The possession of

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antioxidant properties, induction of apoptosis in cancer cells, and inhibition of cell proliferation are indicative of the significance of these substances in the management of cancer [9]. Figure 6.2 shows the mechanism of nutraceuticals in the treatment of cancer. El-far et al. demonstrated the application of costunolide nanonutraceuticals in colon and breast cancer treatment [10]. Costunolide is a sesquiterpene lactone with anticancer properties. Results showed that combining costunolide nanonutraceuticals with doxorubicin dramatically reduced tumor growth in mice implanted with MDA-MB-231-Luc and HCT116 cells. Additionally, oral administration of costunolide nanonutraceuticals drastically reduced the number of viable cells and increased the number of necrotic and apoptotic cells in HCT116 as well as MDA-MB-231-Luc implanted mice. The authors showed that the application of costunolide nanoparticles effectively suppressed the growth of colon and breast tumors when combined with doxorubicin while protecting cardiac muscles from doxorubicin’s adverse effects. Another study reported by El-Ashmawy et al. also showed the inhibition of doxorubicin-induced cardiotoxicity by using TQ loaded into F2 gel (fully acetylated poly-N-acetyl glucosamine nanofiber) nanonutraceuticals [11]. Along with protection from toxicity, the combination of doxorubicin and TQ showed a significant reduction in tumors via upregulation of P53 and downregulation of B-cell lymphoma 2 (Bcl2). TQ nanoparticles also showed a more significant apoptotic effect in breast cancer cells and exhibited a less toxic effect on normal cells. The actin cytoskeleton was downregulated by these nanoparticles, resulting in the inhibition of breast cancer cell migration, which was activated due to the overexpression of miR-34a [12]. Several plants produce polyphenols like resveratrol and 3,5,4' -trihydroxystilbene (1) as a response to injury caused by pathogens. In the last decade, resveratrol has attracted significant attention owing to its widespread use in a vast array of therapeutic purposes, such as chemotherapeutic and chemopreventive applications. Although preclinical studies have shown promising outcomes, the clinical efficacy of resveratrol has been limited due to its inadequate bioavailability and pharmacokinetic properties [14, 15]. To surmount these limitations, Carletto et al. synthesized resveratrol-containing nanocapsules and demonstrated their ability to suppress mouse melanoma tumors [16]. In comparison to free resveratrol, resveratrol-loaded nanocapsules displayed reduced tumor volume, an enlarged necrotic area, and inflammatory infiltration, as well as the avoidance of lung metastasis and bleeding in mice. In addition, in breast cancer cells, the nanoformulation of resveratrol also exhibited antitumor effects. The application of 12-O-tetradecanoylphorbol-13-acetate resulted in the manifestation of anti-invasive characteristics in human breast cancer cells upon exposure to gold nanoparticles that were coated with resveratrol. The aforementioned results were achieved through the inhibition of various cellular components, including nuclear factor kappa-light chain enhancer of activated B cells, matrix metalloproteinase 9 (MMP-9), activator protein 1, phosphatidylinositol 3-kinase/ protein kinase B, cyclooxygenase-2 (COX-2), and extracellular signal-regulated kinase. Additionally, the activation of HO-1 signaling cascades was also observed [17]. Interestingly, Poonia et al. reported that resveratrol has been encapsulated into mimetic folate receptor-targeting nanoparticles with an encapsulation efficiency of

6.2 Nanonutraceuticals

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Fig. 6.2 Molecular targets and mechanisms of action of nutraceuticals in the treatment of prostate cancer, adapted from [13]

approximately 90%. Since MCF-7 cells are known to overexpress folate receptors, the resulting system exhibited promising anticancer activity in vitro against this cell type. Importantly, in comparison to free drugs, whose circulation time period was only 6 h, the circulation period of encapsulated resveratrol supplied intravenously to Wistar rats was greater than 48 h. The discovery has confirmed the nanoparticles’ capability to protect the enclosed medication from external factors. Moreover, the nanoparticles’ in vitro and in vivo properties suggest that they could serve as a viable delivery mechanism for resveratrol, given their resemblance to folate receptors [18]. The utilization of zein nanoparticles for encapsulating resveratrol has been proposed as an alternative approach to augmenting its oral bioavailability. The administration of nanoparticles to human subjects in a liquid medium led to the attainment of plasma concentrations of resveratrol that were commensurate with those reported in prior literature that employed unbound resveratrol. The observed phenomenon can be attributed to the heightened oral bioavailability of resveratrol, which is facilitated by the administration of zein nanoparticles [19]. Further, the synergistic effect of resveratrol with another nutraceutical, i.e., curcumin, has been shown by Zheng et al. in hepatocellular carcinoma (Fig. 6.3) [20]. The utilization of molecular self-assembled nanoparticles, in conjunction with the enhanced permeability and retention (EPR) effect, and surface modification utilizing

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the SP94 peptide moiety that is specific to hepatocellular carcinoma, demonstrated noteworthy effectiveness in the management of liver cancer. The application of hepatocellular carcinoma-targeted nanoparticles resulted in a notable reduction in drug dosage, deceleration of drug release, and enhancement of the bioavailability of the enclosed medications. Elevated levels of medication within the vicinity of the neoplasm were observed, resulting in favorable therapeutic outcomes and the absence of discernible negative consequences. In vivo experiments have proven that the continuous release of medicines from nanoparticles prevents their fast metabolism. This approach not only reduces the necessary drug dosage, but also mitigates the hepatic and renal toxicity resulting from drug metabolism. Moreover, the effectiveness of curcumin in the management of breast cancer has been enhanced through its encapsulation in solid lipid nanoparticles (SLNs) [21]. The Cur-SLNs that were synthesized display a unique spherical morphology with a diameter of around 40 nm and carry a negative surface charge. The results indicate that the SLNs exhibited drug loading and encapsulation efficiencies of 23.38% and 72.48%, respectively. The Curcumin-loaded solid lipid nanoparticles (Cur-SLNs) exhibited a greater level of cytotoxicity toward SKBR3 cells. The in vitro assessment of cellular uptake demonstrated a notable absorption efficacy of Cur-SLNs in SKBR3 cells. Moreover, the Cur-SLNs demonstrated a greater degree of programmed cell death in SKBR3 cells in comparison with the unbound drug. Furthermore, the Western blot analysis has indicated that Cur-SLNs possess the capability to augment the Bax/Bcl-2 ratio and diminish the expression of cyclin D1 and CDK4. The findings of this investigation suggest that Cur-SLNs could potentially be utilized as a feasible chemotherapeutic alternative for the treatment of breast cancer. The authors of a separate study have validated the production of redox-sensitive prodrug nanoparticles utilizing Xyl-SSCur conjugates for the simultaneous administration of curcumin and 5-FU in the treatment of cancer. The Xyl-SS-Cur conjugate was synthesized via the formation of a disulfide (-S-S-) bond between curcumin and xylan, resulting in a covalent linkage between the two molecules. The conjugate of Xyl-SS-Cur demonstrated the capacity to self-assemble into nanoscale particles in an aqueous milieu. The hydrophobic center of the Xyl-SS-Cur nanoparticles was employed to encapsulate the lipophilic prodrug 5-fluorouracil-stearic acid (5-FUSA). The nanoparticles obtained, namely Xyl-SS-Cur/5-FUSA, demonstrated desirable attributes such as a size of 217 2.52 nm, a significant drug loading of curcumin (31.4 wt%) and 5-FUSA (11.4 wt%), and a noteworthy degree of stability. A study was undertaken to investigate the interplay between Xyl-SS-Cur/5-FUSA nanoparticles and blood constituents in the context of hemolysis. The results of the cytotoxicity analysis indicate that XylSS-Cur/5-FUSA nanoparticles exhibit greater cytotoxicity toward human colorectal cancer cells compared to unbound medications (HT-29, HCT-15). The results indicate that the utilization of Xyl-SS-Cur/5-FUSA nanoparticles could serve as a promising approach for delivering medication in cancer treatment. Apart from curcumin, naringenin is another naturally occurring compound that is safe for human use and can be frequently utilized in cancer treatment. Nevertheless, the clinical application of this substance has been restricted owing to its inadequate solubility, absorption, bioavailability, and instability [22]. The combined use of

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Fig. 6.3 Schematic showing combined synergistic effect of resveratrol and curcumin in the treatment of hepatocellular carcinoma, adapted from [20]

naringenin and curcumin has been widely recognized for its ability to impede tumor growth by halting the cell cycle and triggering apoptosis, which is attributed to the heightened production of reactive oxygen species (ROS) [23]. A report showed the suppression of breast cancer by exposure to curcumin-naringenin-magnetic nanoparticles both in vivo and in vitro [24]. Synthesized nanomaterials exhibit excellent biocompatibility and can efficiently inhibit tumor cell proliferation, induce ROS generation, and induce apoptosis. Significantly enhanced tumor suppression with prolonged survival of mice has been achieved via modulation of P21high , CD44low , P53high , ROShigh , and TNF-αlow signaling. The application of poly(lactic-co-glycolic acid) (PLGA) nanoparticles that are loaded with curcumin has been found to exhibit improved encapsulation efficiency and sustained release of the payload. Additionally, the nanoparticles demonstrated a significant decrease in cellular viability, migration, and invasion within MDA-MB231 cells. Trans-retinoic acid (ATRA) is a derivative of vitamin A that is produced through metabolic processes. It is a nutraceutical molecule whose anticancer properties have been extensively explored. To prevent its breakdown, it was encapsulated in liposomes in a recent study with an entrapment efficacy of approximately 82%. Study revealed that the utilization of liposomes for the encapsulation of ATRA provides a protective barrier against photodegradation, which has the potential to impair the drug’s pharmacological efficacy [2]. The liposomal delivery system of ATRA demonstrated a significant decrease in the hypochromic and hypsochromic effects that were induced by the exposure of unencapsulated ATRA to ultraviolet (UV) radiation. Furthermore, liposomes have been

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utilized as a vehicle for delivering all-trans retinoic acid (ATRA), thereby enhancing the anticancer effects of retinoic acid in thyroid carcinoma cell lines, including FRO, PTC-1, and B-CPAP. The intracellular uptake of the vesicular formulation resulted in superior efficacy in vitro against FRO and B-CPAP cell lines in comparison with the unbound drug. As a consequence, there was an increase in the effectiveness of the anticancer properties. Liu and colleagues conducted a recent study that led to the development of a nanogel formulation that is both biodegradable and biocompatible. This formulation is composed of carboxymethylcellulose and lysozyme [25]. This formulation serves as a good carrier for the encapsulation of tea polyphenols. The system developed by Liu et al. demonstrated enhanced anticancer efficacy against the human hepatoblastoma cancer cell line when compared to free tea polyphenols. This is likely due to the fact that encapsulation increases the stability of the polyphenols, revealing that the system exhibits potential for future applications in the food and pharmaceutical industries. Lycopene is a carotenoid pigment that imparts an orange-red hue to various food items. It has been recognized as a potential anticancer therapeutic agent among dietary constituents [26]. The tomato and items made from tomatoes are the primary sources of lycopene in the Western diet, representing roughly 80% of total lycopene consumption. Lycopene possesses distinctive biological characteristics owing to its chemical structure. Its anti-inflammatory and anticancer qualities are directly tied to its antioxidant function, which is the most essential of its many functions. The antitumor effects of these characteristics are exerted through the inhibition of multiple endogenous interleukins and activation of diverse anticancer mechanisms, including the suppression of nitric oxide and inflammatory cytokine production. However, when evaluating the biological impacts of lycopene, one of the primary challenges that must be overcome is the fluctuating and substantially poor bioavailability of the compound [26]. Jain et al. assessed the anticancer efficacy of lycopene-loaded nanoparticles (LYC-SLNs) on MCF-7 human breast adenocarcinoma cells [27]. The cells were cultured in a dish. In comparison with free lycopene, the data obtained by the researchers showed that LYC-SLNs were taken up by MCF-7 cells at a significantly quicker rate, resulting in a significantly lower concentration and a significantly shorter period of cell survival time.

6.2.2 Enhancing Immunity A healthy immune system can also make a substantial contribution to mitigating the adverse impacts on an individual’s health that arise from the escalating levels of environmental pollution and the strains of daily routine. Therefore, it is undeniable that humans require a diet that is both nutritionally sound and contains the necessary quantities of vitamins, antioxidants, and omega-3 fatty acids for optimal health. Consuming a diet that is rich in nanonutraceuticals not only boosts immunity but also has the potential to assist individuals in achieving “a healthy mind in a healthy

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body.” Both of these benefits greatly contribute to living a life that is filled with joy and contentment [28]. Mehrad et al. employed a technique of encapsulation and protection of β-carotene through the formation of a solid shell composed of palmitic acid crystals. This shell was developed on the surface of oil droplets present in the SLNPs that were comprised of palmitic acid, maize oil, and whey protein isolate. The study found that the incorporation of whey protein isolate led to an improvement in the oxidative stability of β-carotene. Additionally, the inclusion of corn oil was observed to decrease the exclusion of β-carotene from the solid lipid matrix toward the surface of SLNPs [29]. The degradation of β-carotene accelerated with rising temperature, ionic strength, and pH. Yogurt containing 5% of these SLNPs (β-carotene or β-carotene and αtocopherol coloaded), which were stabilized using a hydrolyzed soy protein isolate and manufactured using palm stearin as the lipid phase, did not change the product’s physicochemical or rheological features or sensory quality [30]. The β-carotene stabilization by whey protein nanoformulation looks to be the most promising for boosting immunity. Resveratrol possesses the ability to regulate blood pressure, modulate the immune system, and impact energy metabolism, and prevent the growth of EpsteinBarr virus, CMV, human herpesvirus, and influenza viruses. The nanoformulation of α-lactalbumin-resveratrol can be considered a promising nanosystem due to the immunological benefits associated with α-lactalbumin [31, 32]. Spherical αlactalbumin-resveratrol nanoparticles resulted in an enhancement of the chemical stability of resveratrol during storage, particularly under conditions of high temperature and pH 8.0 [32], and demonstrated that the water solubility and in vitro antioxidant activity of the compound under investigation were 32-fold higher than those of free resveratrol. Ovalbumin–carboxymethylcellulose (OVA-CMC) nanoparticles with resveratrol loaded into them were synthesized by heating OVA-CMC nanocomplexes at 90 °C for 30 min. These nanoparticles demonstrated an effective oral absorption rate (EE) of around 70% and a loading capacity of 35 g/mg in addition to increased trans-resveratrol photostability and 80% resveratrol bioavailability. The present study reports on the production of nanoemulsions through spontaneous emulsification, utilizing Tween-80 surfactant and an orange oil to grape seed oil ratio of 1:1 (w/w). The resulting nanoemulsions exhibited a mean droplet size of approximately 100 nm and were utilized for the encapsulation of resveratrol. According to the results, the nanoemulsions demonstrated an improved chemical stability of resveratrol upon exposure to UV light, exhibiting a retention rate of 88% in contrast to the 50% observed in dimethyl sulfoxide [33]. With 150–250 nm particle sizes, a zeta potential of approximately 30 mV, and an EE of 70%, resveratrol-loaded SLNPs and nanostructured lipid carriers exhibited good stability over a two-month period. After being incubated in digestive fluids, the resveratrol remained primarily linked with the lipid nanoparticles, according to research on in vitro simulations of gastrointestinal transit [34]. Yogurt’s textural qualities were unaffected by the addition of niosomes, including resveratrol, which were made using dodecanol as a stabilizer and Span 60 or Maisine 35-1 as surfactants, indicating that they can be employed as additions in this dairy product [35].

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The study conducted by Schroder et al. investigated the effects of emulsifier type and lipid composition on the particle morphology and antioxidant stability of colloidal lipid particles (CLPs) that were loaded with α-tocopherol (Fig. 6.4) [36]. The findings of the study indicate that Tween emulsifiers facilitated the process of tripalmitin crystallization, leading to the formation of well-structured lath-like particles. Conversely, the use of sodium caseinate as an emulsifier resulted in the formation of less organized spherical particles. The swift deterioration of α-tocopherol in CLPs that are based on tripalmitin and stabilized by Tween 40 can be attributed to its displacement toward the surface of the particle, which is caused by the crystallization of lipids. This suggests that in this particular case, the lipid crystallization did not provide adequate protection to the encapsulated vitamin E.

Fig. 6.4 Chemical stability of α-tocopherol, expressed as normalized α-tocopherol amount (%), in CLPs stabilized by a Tween 20, b Tween 40, or c sodium caseinate (NaCas), and prepared with tripalmitin (TP100, red), tripalmitin:tricaprylin 4:1 blend (TP80, blue), or tricaprylin (TP0, green), during storage under oxidative conditions, adapted from [36]

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6.2.3 Inflammation and Oxidative Stress Numerous chemical compounds present in food have been demonstrated to exhibit distinct anti-inflammatory and antioxidant properties. These compounds possess the ability to directly stimulate or hinder diverse cellular signaling pathways. In recent years, nanotechnology has been extensively utilized to circumvent limitations imposed on the pharmacokinetic and stability characteristics of substances. An increasing body of scholarly literature indicates that diverse nanosystems for drug delivery, which contain bioactive compounds derived from plants, exhibit efficacy in mitigating oxidative stress and chronic inflammation that are associated with age-related diseases [37, 38]. The compound known as resveratrol has been documented as having therapeutic properties for various age-related pathological conditions, such as type 2 diabetes, cardiovascular disease, hypertension, stroke, chronic and inflammatory kidney disease, and dementia. The ailments encompass type 2 diabetes, cardiovascular disease, hypertension, stroke, and chronic and inflammatory kidney disease. Several studies have demonstrated that nanoencapsulated resveratrol exhibits antioxidant properties, which is a noteworthy observation. The study conducted by Fan et al. revealed that the utilization of zein nanoparticles loaded with resveratrol, along with bovine serum albumin-caffeic acid conjugate, resulted in a notably enhanced cellular antioxidant activity as compared to the utilization of free resveratrol. This phenomenon can be attributed to the considerably enhanced stability of the resveratrol that was loaded. The results of the study indicate that the bioavailability of resveratrol nanoparticles encapsulated in human serum albumin and conjugated with folate was 5.95 times greater than that of unencapsulated resveratrol, following intravenous administration. The aforementioned approach demonstrated superior localization to the intended site of activity and prolonged duration of drug release, while exhibiting no adverse impact on bodily organs. Numerous instances have been reported wherein various discrete nanoformulations containing curcumin have exhibited anti-inflammatory characteristics. Recent research has investigated the potential anti-inflammatory and therapeutic benefits of nanoformulations containing curcumin in individuals afflicted with mild and severe cases of COVID-19. SinaCurcumin® , a newly developed nanocurcumin product, has been proven to mitigate inflammation and enhance the well-being of individuals afflicted with COVID-19, regardless of the severity of their condition. The aforementioned process is achieved through the upregulation of Treg cell activity and the modulation of inflammatory mediators, namely FoxP3, IL-10, IL-35, and TGF. SinaCurcumin® has been shown to reduce inflammation and improve the health of COVID-19 patients. Additionally, one of the hopeful results of the treatment was a decrease in the overall mortality rate among patients who were given SinaCurcumin® , which highlights the potential therapeutic application of this compound (Fig. 6.5) [37]. Conventional TQ has been shown in a number of studies to be effective as an anti-inflammatory drug in a wide variety of animal models [39, 40]. As discussed

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Fig. 6.5 The number of Treg cells in moderate and severe COVID-19 patients who were treated with nanocurcumin and a placebo. a The proportion of CD4 + CD25 + FoxP3 + (Treg) cells within the total CD4 + T cell population, as measured by flow cytometry in nanocurcumin- and placebo-treated COVID-19 patients with mild and severe disease. b The administration of nanocurcumin to COVID19 patients with modest disease resulted in a significant increase in the frequency of Treg cells in the treatment group compared to the control group (p = 0.0049). c Patients with severe symptoms who received nanocurcumin treatment exhibited a significant increase in Tregs after treatment compared to before treatment (p = 0.0085). With p-values of 0.90 and 0.461, respectively, the placebo-treated group exhibited no significant differences between moderate and severe patients before and after treatment. Mild patient group = 40; severe patient group = 40; Nanocurcumin group = 20; placebo group = 20. Results are presented as the mean SD, and p 0.05 indicates statistical significance. COVID-19, the 2019 Coronavirus disease; Treg, a T-regulatory cell. Reprinted with permission from Life Sciences, Copyright 2021, Elsevier [37]

earlier, thymoquinone’s limited bioavailability can be attributed to both its insufficient solubility in water and its photosensitivity. In this context, Jain et al. [41] produced TQ lipospheres for use as a topical antipsoriatic medication. Lipospheres are an effective method for the delivery of drugs that are also stable and scalable. The authors observed decreases in the levels of nitric oxide, interleukin-2 (IL-2), interleukin-6 (IL-6), interleukin-1 alpha (IL-1), and tumor necrosis factor-α (TNFα) using the murine macrophage cell line RAW 264.7. In contrast, histopathological characteristics of TQ lipospheres decreased IL-17 and TNF in vivo (using BALB/

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c mice). Lipospheres of TQ are a promising antipsoriatic and anti-inflammatory agent. Through nanoformulation, the efficacy and stability of TQ as a topical medication were enhanced. Nanothymoquinone’s anti-inflammatory activity in in vitro and other animal models employing lipopolysaccharides (LPS) or any other chemically induced inflammatory process requires further investigation. As an anti-inflammatory agent, lupeol inhibits pro-inflammatory cytokines, including IL-2, IFN-, and TNF. Unfortunately, lupeol, like all triterpenes, has a relatively low water solubility at 20 °C (0.02 g/mL) [42]. Utilizing nanotechnology is an alternate method for overcoming limited oral bioavailability. Ramirez et al. synthesized lupeol-loaded PLGA nanoparticles and analyzed their physical properties, transport, and modulator effects on NF-κB [43]. The lupeol entrapment efficiency was 64.54%, and it’s in vitro release data fit the Power law and Higuchi equation well (R > 0.84–0.85). Nanonutraceuticals were also observed to strongly modulate NF-κB. However, under the varied experimental conditions, no transmission was observed across the Caco-2 cell type. The anti-inflammatory properties of curcumin are noteworthy; however, its therapeutic application is restricted due to its inadequate water solubility and quick degradation in physiological environments. This limitation is particularly relevant for intravenous drug delivery and disease treatment [44]. Pneumonia, which encompasses acute lung injury (ALI), has traditionally been a lethal ailment due to an unregulated inflammatory reaction and disproportionate generation of reactive oxygen species [45]. The authors, Yuan et al., have documented the creation of Fe-curcumin-based nanoparticles (Fe-Cur NPs) that demonstrate nanozyme characteristics, possess the capacity to eliminate intracellular ROS, and offer anti-inflammatory benefits for the management of ALI [46] (Fig. 6.6). In controlling these biological processes, synthesized nanoformulations are biocompatible and non-cytotoxic. The anti-inflammatory properties of Fe-Cur NPs were investigated through systematic mechanism studies. The results showed that the reduction of intracellular Ca2+ , inhibition of NF-κB signaling pathways, downregulation of key inflammatory cytokines (such as TNF-α, IL-1, and IL-6), inhibition of NLRP3 inflammasomes, and inhibition of NF-κB signaling pathways all helped infected cells and tissues recover. Furthermore, intratracheal and intravenous injections of Fe-Cur NPs were administered to mice with ALI. It was observed that the accumulation of these nanozymes in lung tissue was enhanced compared to that of free curcumin drugs. This finding indicates the potential therapeutic efficacy of Fe-Cur NPs through two different administration routes. In animal studies, we demonstrated that Fe-Cur NPs substantially decreased lung tissue inflammation and scavenged reactive oxygen species. In short, our research shows that giving Fe-Cur nanoparticles to mice can effectively reduce the number of macrophage cells (CD11bloF4/ 80hi) and CD3+ CD45+ T cells, which could be used as a treatment for acute lung injury to ease the cytokine storm it causes. The present investigation developed a plan for utilizing Fe-Cur NPs as nanozymes to eliminate intracellular ROS and as anti-inflammatory nanodrugs to effectively treat ALI in a synergistic manner. This approach holds potential as a therapeutic intervention for the clinical management of this life-threatening ailment. The objective was to employ Fe-Cur NP nanozymes to achieve a reduction in ALI by means of a synergistic approach that involves the

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Fig. 6.6 Synthesis and characterization of Fe-Cur NPs. Schematic of Fe-Cur nanoparticles synthesis and Fe-Cur nanoparticles-based therapy for ALI in mice, adapted from [46]

removal of intracellular ROS and the mitigation of inflammation. The investigation pertains to pertinent cytokines, inflammasomes, and signaling pathways. Lin et al. synthesized acid-labile nanogels with a rod-like morphology using biocompatible and biosafe polymers. These nanogels were intended for intravenous administration in the treatment of systemic inflammation [47]. The polymers comprising the nanogels were synthesized via ester-bonded conjugation of vitamin B6 derivatives, namely pyridoxal and pyridoxamine, to poly(glutamate). Using the solvent evaporation method, rod-shaped nanogels are made by using the aldehyde and amine groups of pyridoxal and pyridoxamine, which are found on the polymers and help crosslinking happen through a Schiff base. This study employs a nanogel system to establish a connection between two derivatives of vitamin B6. It is also the first to construct a nanogel system in the form of rods by evaporating a solvent. The cleavage of imine bonds and subsequent release of cargo occur in acidic environments, specifically within the endosomes and lysosomes of macrophage cells that are associated with systemic inflammation. The production of nanogel polymers was executed efficiently, and the confirmation of the formation and elimination of the Schiff base under both neutral and acidic conditions was achieved through Fourier transform infrared spectroscopy. Upon encapsulation with curcumin, the elongated nanogels exhibited rapid internalization into macrophage cells under static conditions or adhesion to cells during fluxes. Furthermore, they were capable of releasing their payloads in acidic environments, thereby impeding curcumin degradation. The rod-shaped nanogels loaded with curcumin exhibited noteworthy anti-inflammatory

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efficacy in both in vitro and in vivo settings, as evidenced by their ability to significantly decrease the release of pro-inflammatory mediators. The findings indicate the effectiveness of our acid-sensitive, cylindrical nanogels in managing systemic inflammation. Curcumin has been found to offer noteworthy advantages in terms of its antioxidant and anti-inflammatory properties for the treatment of Alzheimer’s disease (AD). The application of curcumin is significantly restricted due to its limited solubility and extreme instability. The study conducted by Zhang et al. involved the development and comparison of intranasal delivery properties of curcumin-encapsulated chitosan-coated poly (lactic-co-glycolic acid) nanoparticles (CUR-CS-PLGA-NPs) and hydroxypropyl-cyclodextrin-encapsulated curcumin complexes (CUR/HP-CD inclusion complexes) [48]. As per the results of in vitro experiments, the stability of curcumin in CUR/HP-CD inclusion complexes was observed to be 95.410.01% for a duration of 72 h under physiological conditions, whereas the stability of curcumin in CUR-CS-PLGA-NPs was found to be 49.663.91%. The inclusion complexes of CUR/HP-CD demonstrated a higher degree of curcumin absorption in SH-SY5Y cells as compared to CUR-CS-PLGA-NPs. Both formulations demonstrated the ability to mitigate the cytotoxic effects of curcumin on cells while displaying comparable antioxidant activity. The results of the study indicate that curcumin exhibited anti-inflammatory properties in BV-2 cells, as evidenced by a reduction of approximately 70% and 40% in TNF-α and IL-6 levels, respectively, when compared to the positive control. The results of in vivo pharmacokinetic studies indicate that the AUC values of curcumin in the plasma and brain of the CUR/HP—CD inclusion complex group were 2.57-fold and 1.05-fold higher, respectively, compared to those of the CUR-CS-PLGA-NP group, subsequent to intranasal administration of 2 mg/kg. To conclude, the study found that CUR/HP-CD inclusion complexes exhibited better potential as carriers for intranasal delivery of curcumin for Alzheimer’s disease therapy in comparison with CUR-CS-PLGA-NPs. Glaucoma is a medical condition characterized by heightened intraocular pressure (IOP) due to compromised drainage of aqueous fluid through either the uveoscleral or trabecular outflow pathways. Latanoprost is known to decrease intraocular pressure by augmenting uveoscleral outflow. The effectiveness of long-term daily usage of the medication may be compromised by the occurrence of undesirable adverse effects. Additionally, a significant number of patients may necessitate the use of multiple medications to regulate intraocular pressure. According to recent studies, the pathogenesis of impaired trabecular outflow capacity is closely linked to oxidative stress in the trabecular meshwork (TM). Cheng and colleagues developed a thermosensitive hydrogel that incorporates latanoprost and nanoparticles loaded with curcumin (CUR NPs). The researchers assessed the hydrogel’s therapeutic potential on human TM cells cultured under oxidative stress, utilizing curcumin’s anti-inflammatory and antioxidant properties (Fig. 6.7) [49]. According to the findings, a concentration of 20 μM CUR-NPs could potentially serve as the most effective concentration for the treatment of TM cells while avoiding any potential cytotoxic effects. The recently developed technique facilitated the observation of a sustained release pattern for both latanoprost, and curcumin nanoparticles. The hydrogel incorporating curcumin nanoparticles demonstrated efficacy in mitigating oxidative stress-induced damage

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Fig. 6.7 Schematic representation of a thermosensitive chitosan–gelatin hydrogel containing nanoparticles laden with curcumin and latanoprost as a dual-drug delivery system for the treatment of glaucoma. Reprinted with permission from Experimental Eye Research, Copyright 2019, Elsevier [49]

in TM cells by reducing inflammation-related gene expression, mitochondrial reactive oxygen stress production, and apoptosis levels. Upon topical application of the hydrogel to rabbits, the in vivo biocompatibility assessment revealed the absence of any indications of inflammation or injury. The results of this study indicate that the utilization of a dual-drug delivery approach holds promise for transforming the treatment of glaucoma by augmenting the outflow of both trabecular and uveoscleral pathways. Table 6.1 provides a comprehensive discussion of various nutraceuticals and their applications based on nanosystems.

6.3 Nutrigenomics Nutrigenomics is primarily concerned with investigating the impact of dietary constituents on the genome, proteome, and metabolome. Nutrigenomics takes into account the impact of bioavailability, maximal ingestion levels, and assessment of the food delivery matrix on the genome [62, 63]. Figure 6.8 shows the various aspects of nutrigenomics in different field. Although it has been discovered that different bioactives can effectively fix aberrant gene expression linked to a variety of illnesses and disorders, their bioavailability restricts their effectiveness. These bioactive substances can be transported by nanotechnology in a way that makes them more accessible to cells, and they have the potential to operate as strong chemical messengers and transcription factors that change how genes are expressed. Nanotechnology also enables the production of synthetic chemicals or the use of biologically generated particles that can change the expression of a particular gene. Various encapsulation platforms, including nanoemulsions, liposomes, and biogenic production of nanoparticles, possess diagnostic and therapeutic potential due to their superior properties in comparison with their bulk counterparts. These platforms can facilitate the creation of a targeted drug

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Table 6.1 Various nutraceuticals and their nanosystem-based applications Nanosystem

Nutraceutical

Observation

Niosomes

Gallic acid, ascorbic acid, curcumin and quercetin

In comparison with [50] formulations containing a solitary antioxidant, co-encapsulations of gallic acid/curcumin and ascorbic acid/quercetin alter their physicochemical properties and entrapment efficiencies. In addition, the antioxidants’ release appears to be enhanced, and their synergistic antioxidant action results in a greater capacity to eliminate free radicals

References

Ufasomes

Oleuropein

Upon comparing the [51] biocompatibility of the system with CaCo-2 cells to that of untreated cells utilized as the control, it was observed that the system exhibited enhanced biocompatibility. The cell survival rate surpassed 70% at lipid concentrations of up to 200 g/mL. Furthermore, the utilization of confocal laser scanning (CLS) microscopy in the conducted experiments revealed that the system under investigation has the potential to engage with and internalize a colon cancer cell line, ultimately leading to an improvement in the bioavailability and antioxidant effectiveness of the administered oleuropein. The MTT and LDH assays provided evidence of enhanced effectiveness in comparison with the unbound active compound

Nanogel

Curcumin

Curcumin was encapsulated by ARPI nanogels with a 95% encapsulation efficiency, considerably increasing its anticancer efficacy against various cancer cell lines

[52]

(continued)

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Table 6.1 (continued) Nanosystem

Nutraceutical

Observation

Gold and silver nanoparticles

Hesperidin and naringin

The silver nanoparticles [53] loaded with hesperidin demonstrated significant antimicrobial efficacy against Staphylococcus aureus and neuropathogenic Escherichia coli K1. Additionally, in vitro testing revealed that these nanoparticles were capable of eliminating two types of brain-eating amoebae, namely Acanthamoeba Castellanii and Naegleria fowleri

References

Poly(d,l-lactide-co-glycolide) (PLGA)

Sclareol

Hyaluronic acid (1.5 MDa) [54] was added to the PLGA nanoparticles to boost their anticancer activity against human breast cancer cells (MCF-7 and MDA-MB468) that express hyaluronan receptors. Human colon carcinoma cells also had a similar pharmacological impact (CaCo-2). After 3 h of incubation, CLSM analysis showed that fluorescent nanosystems were intracellularly localized

Nanostructured lipid carriers

Turmeric extract

The enhanced ability of nanostructured lipid carriers to traverse cell membranes resulted in a system that exhibited superior antioxidant and antibacterial properties in comparison with unbound turmeric extract. Hence, this methodology exhibits prospective applications in the food sector for augmenting the impacts of turmeric

[55]

(continued)

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Table 6.1 (continued) Nanosystem

Nutraceutical

Observation

Nanostructured lipid carriers

Quercetin and linseed oil

Due to the synergistic effects [56] of the two nutraceuticals and the enhancement of their bioavailability, the obtained system exhibited good physicochemical properties and a good in vitro antioxidant activity, supporting its prospective application in the food industry

Nanoemulsions

Tomato extract In comparison with [57] rich in lycopene nanoemulsions that simply and curcumin contained doxorubicin, the suggested nanoemulsions, particularly those that were lycopene-loaded, increased cell viability by 35–40% and decreased the release of IL-1, IL-6, IL-8, nitric oxide, and TNF-α

Nanogels

Tea polyphenols

Polymer capsules and lyotropic Vitamin B12 liquid-crystalline nanosystems

The efficacy of polyphenols in inhibiting the growth of human hepatoblastoma cancer cells was found to be augmented by their encapsulation, as opposed to their free form, owing to the improved stability of the encapsulated polyphenols. The aforementioned methodology exhibits potential prospects for implementation in the domains of food and pharmaceuticals

References

[25]

It was demonstrated that [58] approximately 30% of the vitamin supplied during fabrication of the soft lipid system was encapsulated in cubosomes and that loading had no effect on the structure (continued)

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Table 6.1 (continued) Nanosystem

Nutraceutical

Observation

Chitosan derivatives

Scutellarin

At a dosage of 250 g/mL, it [59] demonstrated significant penetration and little toxicity in Caco-2 cells. Sprague–Dawley rats were used in subsequent in vivo bioavailability experiments, which revealed that the area under the scutellarin nanosystem curve was two to three times bigger than that of bulk scutellarin. Additionally, type 2 diabetic rats’ retinal neovascularization was inhibited by the downregulated expression of angiogenesis proteins

References

Nanoencapsulation in casein nanoparticles

Curcumin and quercetin

Micelle loading has been [60] found to enhance the water solubility of curcumin and quercetin in comparison with isolated polyphenol molecules. The present study observed an increase in the vitality of MCF-7 human breast cancer cells in the following order: free polyphenol molecules, non-digested polyphenol-loaded carriers, and polyphenol-loaded micelles

Poly(vinyl alcohol)-based nanofibers

Lactobacillus reuteri E81

The application of nanosystem to the surface of fish filets resulted in a significant improvement in their antioxidant properties, leading to a noteworthy increase in their free radical scavenging activity when compared to fish filet samples in the control group

[61]

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Fig. 6.8 Nutrigenomics is a multidisciplinary field that encompasses various domains such as genetics, bioinformatics, molecular medicine, molecular nutrition, pharmacogenomics, and molecular biology. Reprinted with permission from Role of Nutrigenomics in Modern-day Healthcare and Drug Discovery, Copyright 2023, Elsevier [63]

delivery system. By increasing their bioavailability, this may potentially assist in overcoming many of the problems caused by hydrophobic molecules. It may also make it possible to provide patients with medicines that are specifically suited to their genetic make-up. This technology has the potential to revolutionize the way pharmaceuticals are targeted and delivered. It can successfully target and transfer nutraceuticals and drugs through obstacles. It has the potential to alter how food is grown, processed, packed, delivered, and eaten, which would potentially have a profound impact on the food sector. The promising future of healthcare that can be realized through the use of nanotechnologies is nutrigenomics. In a diabetic rat model, The study conducted by Polak of and colleagues revealed that consumption of resistant starch in conjunction with a high-fat meal can induce modifications in hyperglycemia, hyperlipidemia, and the genetic expression of pathways that are implicated in hepatic glucose and lipid metabolism [64].

6.3.1 Polymeric Micelles (PICM) Polymeric micelles are supramolecular structures composed of amphiphilic block polymers such as poly(ethylene oxide)-b-poly(propylene oxide), poly(ethylene

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oxide)-b-poly(esters), and poly(ethylene oxide)-b-poly amino acids. The formation of these structures is facilitated by hydrophobic and hydrophilic interactions, including electrostatic interactions, hydrogen bonds, and metal complexation. The utilization of micelles in drug delivery has gained significant attention in the pharmaceutical industry due to their biocompatibility, low toxicity, prolonged blood circulation, and capacity to solubilize a considerable amount of pharmaceuticals within their micellar core. Drug diffusion from intact micelles or micelle disintegration can lead to drug release from polymeric micelles. In any case, micelles should have sufficient thermodynamic and kinetic stability to prevent an uncontrolled drug release at administration [65]. Polymeric micelles have been shown by Nishiyama and Kataoka to be capable of pH-sensitive release. Liu et al. employed a poly(N-isopropyl acrylamideco-acrylamide)-b-poly(D, L-lactide) copolymer for the purpose of administering docetaxel to neoplastic growths. The researchers observed that hyperthermia significantly augmented the targeting efficiency of micelles loaded with drugs and mitigated the drug’s toxicity [66]. A novel drug delivery system containing dexamethasone (DXM) was developed by Sipos et al. utilizing mixed polymeric micelles. The present investigation centered on the advantageous nasal-to-cerebral pathway as a pivotal administration pathway for the management of disorders affecting the central nervous system (CNS) [67]. In comparison with standard formulations, polymeric micelles may offer a better way to deliver medications to the site of action. The polydispersity index, strong surface polarity, and the low Z-average contributed to the large improvement in water solubility (14-fold). In nasal and axonal conditions, the polar brain (porcine) lipid extract exhibited a favorable disintegrating profile with a high in vitro permeability value (14.610–6 cm/s). According to a modified Side-bi-side® type diffusion study, robust mucoadhesive properties contributed to rapid and efficient passive diffusion through the nasal mucosa. The final formulation satisfied all criteria for a rapid-acting nasal drug delivery method, allowing DXM to enter the CNS and exert its therapeutic effects on pathological conditions there.

6.3.2 Carbon Nanotubes (CNTs) A carbon nanotube resembles a graphite sheet that has been coiled into a cylinder and is composed of a hexagonal lattice structure. High structural perfection is present in two fundamental categories of CNTs: A single graphite sheet is flawlessly wound around a cylinder to create a nanotube with a single wall. Multiwalled nanotubes are composed of a series of nanotubes that are arranged in a concentric manner, resembling the structure of tree rings. CNTs can serve as a vehicle for the encapsulation of diverse pharmacological agents, thereby augmenting their therapeutic potential through the utilization of the porous structure or internal cavities of the nanotubes. The impact of functional groups that are affixed to the surface of CNTs on their interactions with cellular machinery is significant. Thus, these concepts can

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be examined and applied to specifically target nutraceuticals and attain efficacious gene modifications [66].

6.3.3 Dendrimers Dendrimers, an emerging class of polymeric architectures with biomolecule-like properties, possess well-defined structures, adaptability in drug administration, and high functionality. Through host–guest interactions and covalent bonding (prodrug method), these nanostructures have demonstrated their ability to entrap and conjugate both hydrophilic and hydrophobic substances of high molecular weight. Due to their exact molecular weight, excellent water solubility, biocompatibility, and polyvalency, dendrimers have attracted far more attention in biological applications in comparison with traditional polymers [66].

6.3.4 Liposomes Liposomes are predominantly constituted by amphiphilic compounds featuring a hydrophilic head and two hydrophobic tails that lack polarity. Liposomes may enclose and safeguard delicate bioactive substances, whether they are hydrophilic or hydrophobic, due to their amphiphilic nature. Targeted delivery of potentially bioactive substances is made possible by this flexibility [68]. In a study, poly(L-histidine)poly(L-lactic acid) micelles conjugated to folate were successful in destroying cancer cells [69]. According to Feng et al., liposomal nanoparticles encapsulating a cancer medication and low-soluble bioactive compounds like curcumin can sensitize cancer cells, like the curcumin and C6 ceramide in the OS cell line [70]. Since liposomes are lipid vesicles that naturally occur in living organisms, they have a wide range of uses. Additionally, their amphiphilic nature makes them ecofriendly and sustainable.

6.3.5 Transferosome Highly deformable vesicles known as transferosomes are used as innovative drug carriers to transport big molecules through intact mammalian skin. The utilization of lipid vesicles as drug delivery systems has gained significant traction in recent times. Nonetheless, a crucial limitation associated with this approach is the localization effect. This challenge can be effectively addressed by employing transferosomes [71]. Therefore, employing transferosomes makes it simple to transport a variety of bioactives derived from food [63].

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6.3.6 Nanoemulsions As per a report, nanoemulsions are submicron emulsions that are thermodynamically stable and exist as a single phase. The ideal size range for these emulsions is between 10 and 100 nm [72]. They possess thermodynamic stability and a single phase. They consist of amphiphilic molecules and emulsions of water and oil. The process of producing nanoemulsions involves the dispersion of a hydrocarbon phase within a water phase, which is subsequently stabilized through the use of surface-active compounds. Nanoemulsions are commonly employed for the delivery of lipophilic drugs and bioactive compounds sourced from food, owing to their superior loading capacity and improved bioavailability. Various methodologies, such as high-pressure homogenization, ultrasonication, self-emulsification, phase inversion, the trimetric method, and microfluidization, have been employed to generate emulsions [63].

6.4 Functional Food Functional foods refer to food items or constituents of the diet that have the potential to offer supplementary health advantages beyond their basic nutritional value. To clarify, functional foods encompass a range of components, both nutritional and non-nutritional, that impact diverse physiological processes linked to well-being and/ or mitigate the likelihood of illness [73]. Typically, a functional meal is a natural, whole food that contains sufficient therapeutic constituents. For example, lycopene in tomatoes, oat fiber, and omega-3 fatty acids in fish are just a few examples of the natural substances that most fruits, vegetables, grains, and fish contain. Special growth circumstances or breeding methods can be used to improve the functional components, like the production of rice that is high in beta-carotene, broccoli that is vitamin-enriched, and soybeans. Diet can affect the composition of meat, poultry, fish, and eggs, for instance, by increasing the quantity of conjugated linoleic acid and omega-3 in meat and dairy products. It is likely that genetic engineering, which consumers have not yet accepted, will be required to provide genuinely exceptional health benefits [73]. Nanoscience and nanotechnology have the potential to provide novel solutions for the development of functional foods, specifically through the integration of bioactive substances without compromising sensory perception and the improvement of ingredient absorption. In contemporary times, there has been a surge in the exploration of nanotechnology as a means to create delivery systems with superior performance for safeguarding and enclosing biologically active foodbased compounds. Nanoparticles that are biocompatible and biodegradable can be furnished with diverse nutrients, bioactive compounds, and phytochemicals to enhance their water solubility, stability, bioavailability, and systemic circulation. The utilization of nanometer-sized delivery systems holds promise for augmenting

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the solubility, bioavailability, controlled release, and precision targeting of encapsulated compounds when compared to micrometer-sized systems generated through traditional microencapsulation methods. Through a precise selection of molecular components, it is possible to generate nanoparticles with varied surface properties, thereby facilitating the targeted delivery of active agents to specific sites. While part of this work requires basic research to adequately characterize the pertinent factors regulating the system, the majority of it is done at the laboratory scale. In numerous ways, food scientists are adapting the pharmaceutical industry’s delivery systems, where platforms for diagnostics and drug administration that are enabled by nanotechnology have been created to address issues with protection and targeted delivery. Figure 6.9 shows the encapsulation of functional food in nanoparticles and their way through the digestive track.

6.4.1 Polysaccharides Starch, a significant provider of carbohydrates in the human diet, is associated with rapid absorption, leading to undesirable spikes in blood glucose levels. There is a prevailing belief that augmenting the intake of carbohydrate-rich foods that possess a low glycemic index can confer significant advantages to one’s overall health. Resistant starch (RS) undergoes fermentation by the microbial flora present in the colon, leading to the production of short-chain fatty acids (SCFAs) that have beneficial effects on health. This is in contrast to its metabolism in the pharynx, stomach, or small intestine. Furthermore, the resistant starch nanoparticles represent a novel form of functional dietary fiber that holds promise for incorporation into health-promoting food products [76, 77]. It has been proven that resistant starch and its nanoparticles have prebiotic effects on human health and resist digestion in the upper intestine but not in the colon. Additionally, resistant starch nanoparticles offer a variety of qualities that are advantageous for their use as functional food additives, including excellent biocompatibility, good water dispersibility, and compact size. In addition, resistant starch nanoparticles are resistant to hydrolysis by upper gastrointestinal tract (GIT) digestive enzymes (such as amylase). Therefore, resistant starch nanoparticles can be used to specifically deliver bioactive compounds to the colon or as prebiotics. Starch with resistance to digestion has the potential to be a novel source of dietary fiber or digestion-controlled food components that can alter glycemic response. Most dietary regimens contained between 6.5 and 74 g/d of resistant starch, which had a positive anti-diabetic effect [78]. According to studies, consuming more than 5 g/ d of RS is sufficient for preventing obesity-related diabetes. Due to the inability of resistant carbohydrates to undergo rapid hydrolysis, they may reduce elevated blood glucose and insulin levels and enhance postprandial glycemic and insulinemic responses. The study involved the administration of 350 g/kg of RS to Otsuka Long-Evans Tokushima obese rats, which are known to be a rat model for obesityassociated diabetes. The results indicated a reduction in plasma insulin concentrations and glycated hemoglobin after a four-week period. The authors postulated

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Fig. 6.9 a Schematic of the differentiation between food additives that are integrated and those that are not integrated. In the case of integrated excipient foods, the bioactive element, whether pharmaceutical or nutraceutical, is dispersed throughout the excipient food matrix. Conversely, non-integrated excipient foods involve the bioactive component being consumed alongside the excipient food in a separate product, adapted from [74]. b Schematic of the construction of pHsensitive, food-grade nanoparticles for the delivery of functional culinary constituents. Reprinted with permission from Trends in Food Science & Technology, Copyright 2020, Elsevier [75]

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that the RS diet’s amelioration of insulin resistance was mediated by a reduction in CD11c expression within adipose tissues, a factor that has been strongly linked to the development of insulin resistance [79]. The ability of RS to promote fat oxidation and prevent fat formation has been examined in a number of studies [80]. Dodevska et al. reported significant reductions in body weight, BMI, and waist circumference following resistant starch intervention during a 12-month period [81]. According to another study, resistant starch intake changed the neuronal activity in the hypothalamic areas that control hunger, causing mice to show signs of satiation. This would cause them to eat less, which would lower their risk of developing obesity and related diseases. Resistant starch thus has significant potential benefits for controlling metabolic syndrome and lowering obesity [82]. Consuming resistant starches has several positive impacts on colon health and is regarded as a preventative measure for those with a high risk of developing colon cancer. According to reports, consuming resistant starch may improve the generation of crypt cells and lessen colon epithelial atrophy, both of which are good for colon health. Additional consequences that affect human health may result from the transformation of resistant starch into nanoparticles. Resistant starch nanoparticles are prone to binding by digestive enzymes owing to their elevated surface-to-volume ratio, thereby altering their interaction with other substrates within the gastrointestinal tract. In addition, after adsorption, digestive enzymes may undergo structural modifications that alter their activity. It has been observed that highly compacted spherical nanoparticles composed of starch have the ability to form complexes with the active domain of α-amylase through hydrogen bonding, leading to a decrease in the enzyme’s activity. Furthermore, the aggregation of polygonal starch nanoparticles, which possess a comparatively delicate internal structure, can result in the entrapment of -amylase, thereby impeding its capacity to catalyze the hydrolysis of the encompassing starch. Thus, it can be inferred that both spherical and polygonal starch nanoparticles exhibit remarkable promise as -amylase inhibitors for the purpose of retarding starch digestion [83]. Similarly, Wang et al. discovered that starch nanoparticles have the ability to form complexes with pepsin and trypsin, resulting in modifications to the enzymatic activity of these digestive enzymes [84]. The potential of utilizing RS nanoparticles as delivery systems targeted toward the colon is being investigated by researchers, owing to their ability to resist digestion in the upper gastrointestinal tract and undergo digestion in the colon [85]. Certain bioactive compounds, including probiotics and nutraceuticals, are highly vulnerable to degradation as a result of the presence of potent acids, bile salts, or digestive enzymes in the gastric and duodenal regions. These compounds may be protected and delivered to their necessary locations of action by being encapsulated within well-designed resistant starch nanoparticles. Examining the pharmaceutical industry’s research can shed light on the potential use of starch nanoparticles for this purpose. As they pass through the GI, RS nanoparticles’ medication release profiles may change at various points. Due to the free drug that is present on the surfaces of the resistant starch nanoparticles, a burst release is frequently seen at the beginning of the process. After that, the release

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slows down and becomes more sustained, which is attributed to the nanoparticle’s slow surface erosion via enzymatic hydrolysis. Finally, the encapsulated medications are completely released once the resistant starch nanoparticles in the colon undergo complete breakdown (Fig. 6.10). The study findings suggest that soybean meal resistant starch nanoparticles may be a viable option for targeted drug delivery to the colon, as less than 30% of the encapsulated drug was released under simulated stomach and small intestine conditions [86]. The present study employed Captopril (CAP) and 5-fluorouracil (5-FU) as model drugs to investigate the release kinetics from nanoparticles of RS. The percentage of CAP released was found to be approximately 18%, 49%, and 92% after 2 h in simulated gastric fluids, 6 h in simulated intestinal fluids, and 12 h in simulated colonic fluids, respectively. The percentage of 5-FU released was approximately 27, 44, and 96 over identical time intervals. The findings indicate that resistant starch nanoparticles have the ability to protect bioactive compounds from degradation in the stomach and small intestine, thereby facilitating their delivery to the colon. The study conducted by Ding and colleagues revealed that the liberation of 5-FU from nanoparticles of RS exhibited a significantly greater magnitude under simulated colon conditions in contrast to those observed in upper GIT settings [87].

Fig. 6.10 Schematic of drug release in the human gastrointestinal tract. Reprinted with permission from Trends in Food Science & Technology, Copyright 2022, Elsevier [77]

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Typically, the ionic gelation method is used to produce pH-sensitive chitosan nanoparticles [88]. Chen and colleagues generated nanoparticles composed of chitosan and heparin with the aim of augmenting the uptake of heparin by intestinal epithelial cells through the paracellular route. The pH dependence of the released heparin from the nanoparticle was observed [89]. Less than 2% of the heparin was released in 2 h at a pH of 1.2, whereas 20% of the heparin was released in 4 h at a pH of 6.6–7.0. The nanoparticle was stable at a pH of 1.2 because of the potent interaction between the chitosan and heparin ions. Some chitosan amino groups deprotonated at pH values of 6.6 or 7.0, which resulted in weaker connections between heparin and chitosan and greater heparin release. The study conducted a transepithelial electrical resistance analysis on Caco-2 cell monolayers. The results indicated that the chitosan coating on the surface of the nanoparticle had a positive charge, which facilitated its interaction with the negatively charged sites present on the cell surfaces and tight junctions. This interaction led to the reversible opening of the tight junctions. The rat model exhibited heightened anticoagulant activity due to the opening of tight junctions. This facilitated the absorption of heparin, which was released and subsequently absorbed via the paracellular pathway, resulting in an absolute bioavailability of 20.5%. One of the most prevalent marine polysaccharides is alginate. It is abundantly accessible to numerous species of algae, and its structure is pH-dependent. However, long-term instability restricts their use in the delivery of bioactive compounds. Alginate nanoparticles disintegrated when Ca2+ was swapped for Na+ in the physiological environment [89]. The curcumin-loaded alginate nanoparticles were combined with a ligand made of folic acid, polyethylene glycol, and polyethylenimine by Anirudhan et al. Ca2+ can be prevented from dissipating by the ligand. The grafted nanoparticles had a surface charge of 4.0 mV and a 442.0 nm particle size. 2% of the curcumin was present in 2 h at pH 1.2, whereas, 10% of the curcumin was released in 4 h at a pH of 7.4 [89]. A naturally occurring polysaccharide, pectin mostly consists of chains of dgalacturonic acid, and its nanoform can be efficiently used for the transportation of various bioactive substances [90]. In an acidic stomach environment, pectin is stable [91]. The hydrophilic nature of pectin can be attributed to the abundance of hydroxyl groups it contains. This property enhances the solubility of the hydrophobic molecules that pectin transports. Liu et al. employed a crosslinking technique to attach Ursolic acid (UA) onto pectin, followed by the generation of UA-loaded pectin nanoparticles via a self-assembly protocol [92]. The nanoparticles exhibited a core– shell configuration, whereby the hydrophilic pectin shells entrapped the hydrophobic UA. The hydrophilic shells were found to increase the solubility of UA. The loading capacity of pectin nanoparticles ranges from 4.1% to 9.2% UA. The size of the pectin nanoparticles that encapsulated UA ranged from 80.0 to 91.0 nm, while their zeta potential was positively charged, measuring between 6.6 and 9.5 mV. The release of UA from the pectin nanoparticles was observed to increase with an increase in pH levels (pH 5.0 < pH 7.4 < pH 8.0), owing to the pH-dependent ester interaction between UA and the crosslinker.

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6.4.2 Lipid-Based The oil phase of a SLNs is composed of a solid substance instead of a liquid one, thereby impeding the sudden release of a lipophilic drug molecule. Numerous SLNs exhibit pseudo-pH sensitivity, akin to nanoemulsions, whereby they are susceptible to degradation by lipase enzymes in alkaline intestinal conditions, while remaining relatively stable in acidic gastric environments. Solid lipids typically exhibit a slower rate of decomposition compared to their liquid counterparts [93]. It is expected that the rate of bioactive chemical release from SLNs will be comparatively lower than that of nanoemulsions. The SLN technique developed by Yang et al. was utilized for the delivery of camptothecin, a natural extract. Camptothecin was solubilized using stearic acid as the solvent, and emulsifying agents such as soybean lecithin and Poloxamer 188 were incorporated. The mixture was subjected to a temperature 10 °C higher than its melting point and subsequently homogenized under high pressure while undergoing sonication to achieve dispersion. Subsequently, the amalgamation was subjected to a cooling process, achieving a temperature of 4 °C. The size of the synthesized SLN was estimated to be around 196.8 nm, while its zeta potential was measured to be 69.3 mV. The encapsulation efficiency of camptothecin was approximately 99.6%. The release of camptothecin was found to be less than 5% after a period of 2 h at a pH of 3.5, whereas a release of 21% was observed within a time frame of five hours at a pH of 7.4 [94]. Typically, a nanoemulsion consists of a hydrocarbon, a surfactant, and water. Without a surfactant, water and oil can form a nanoemulsion. However, nanoemulsions are thermodynamically unstable [95]. A nanoemulsion’s small size has benefits for the loaded lipophilic compounds, including improved bioavailability, optical clarity, and long-term stability [75]. Mehmood et al. demonstrated a nanoemulsion technology for the efficient delivery of beta-carotene [96]. The ultrasonication technique was used to successfully incorporate beta-carotene into nanoemulsions. The droplet size of nanoemulsions containing β-carotene exhibited fluctuations between 112.36 and 147.1 nm at 25 °C and between 112.36 and 133.9 nm at 4 °C over a period of 60 days. The addition of nanoemulsions resulted in a significant enhancement of the oxidation stability of olive oil. The stability of β-carotene nanoemulsions was observed across a spectrum of ionic strengths (50–400 mM), pH levels (2–8), and freeze–thaw cycles. With the passage of time and as the temperature rose, there was a noticeable increase in the levels of turbidity and chromatic aberration. The utilization of nanoemulsions resulted in a significant deceleration of the β-carotene degradation process. Furthermore, the inclusion of antioxidants exhibited a notable enhancement in the preservation of β-carotene within the nanoemulsions. The results indicate that the utilization of ultrasonic homogenization techniques can yield nanoemulsions of β-carotene that possess the intended characteristics. The utilization of nanoemulsions is an effective approach for the incorporation of β-carotene into various food and beverage products. Further, Rachmawati et al. showed the development of a curcumin nanoemulsion for transdermal distribution [97]. The stability and permeability of curcumin

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should be enhanced by its integration inside a nanoglobule. A nanoemulsion was produced through the utilization of the self-nanoemulsification method, employing a blend of glyceryl monooleate, Cremophor RH40, and polyethylene glycol 400. The particle size, polydispersity index, zeta potential, physical stability, Raman spectrum, and morphology of the nanoemulsion were subjected to analysis. Additionally, the viscolam AT 100P gel’s nanoemulsion’s physical performance was investigated. Curcumin’s in vitro permeation was studied using a modified vertical diffusion cell and discarded epidermis from a Python reticulatus. A stable nanoemulsion that is spontaneously formed can accommodate 350 mg of curcumin, while containing 10 g of oil phase. The optimized nanoemulsion exhibited a mean droplet diameter of 85.0 ± 1.5 nm, a polydispersity index of 0.18 ± 0, and a zeta potential of − 5.9 ± 0.3 mV. The stability of curcumin was found to be higher in a nanoemulsion formulation as compared to non-encapsulated curcumin. The application of nanoemulsification resulted in a modification of the release kinetics of curcumin, transitioning from a zero order to a Higuchi release profile. This alteration also led to a noteworthy enhancement in the flux of curcumin permeation from the hydrophilic matrix gel. In general, the nanoemulsion formulation not only augmented the permeability of curcumin but also provided safeguard against its chemical degradation. Ahmad et al. improved transdermal medication delivery by developing curcumin nanoemulsion (Cur-NE) (Fig. 6.11) [98]. In terms of its comparative impact on wound-healing and anti-inflammatory activity, Cur-NE was assessed. The greatest nanoemulsion region and solubility of clove oil (oil), Tween-80 (surfactant), and PEG-400 (co-surfactant) were taken into consideration when choosing these substances. The Cur-NE formulation was synthesized utilizing a method involving aqueous microtitration and high-energy ultrasonication. The substances under consideration are clove oil, Tween-80, and PEG-400. The optimization of Cur-NE has the potential to enhance the skin permeation of curcumin. To summarize, the potential of Cur-NE as a nanoformulation for transdermal delivery that is both safe and non-toxic has been demonstrated. This is evidenced by its significant contribution to wound healing and its display of anti-inflammatory characteristics.

6.4.3 Protein-Based The macromolecules known as proteins are made up of chains of amino acid residues. A few studies have developed pH-sensitive nanoparticles for the delivery of bioactive substances by utilizing the amphoteric characteristics of proteins [75]. Lactoferrin (LF) has several positive effects on human health, including antibacterial and anti-inflammatory properties. The capacity to bind hydrophobic ligands and its durability against low pH makes β-lactoglobulin (BLG) a viable transporter for bioactive chemicals [99]. BLG-dextran nanoparticles were created by Yi et al. using a homogenization-evaporation technique. At a pH between 4.0 and 5.0, BLG glycation via increased steric hindrance, the Maillard reaction between BLG and dextran precluded aggregation and flocculation. Size and zeta potential of BLG-dextran

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Fig. 6.11 Schematic of synthesis of a novel ultrasonicated curcumin nanoemulsion and comparison of its wound-healing and anti-inflammatory properties. Reprinted with permission from RSC Advances, Copyright 2019, Royal Society of Chemistry [98]

nanoparticles produced with beta-carotene were 68.2 nm and 14.0 mV, respectively. The input capacity was 1.1% and the encapsulation efficiency was 98.4%. Within two hours, only 5.4% of the beta-carotene was released in the presence of pepsin at a pH of 2.0. In 2 h in the presence of trypsin and a pH of 7.0, 51.8% of β-carotene was released [100]. Feng et al. developed a nanoparticle composed of amylose, α-linoleic acid, and BLG for the delivery of the flavonoid naringin [101]. The mixture of amylose, αlinoleic acid, and BLG was heated in boiling water for 20 min with constant agitation to produce the ternary nanoparticle, which was then freeze-dried. A ternary interaction between amylase, α-linoleic acid, and BLG resulted in the nanoparticle. The produced nanoparticle had a size of 210 nm. The encapsulation efficiency was 78.7%, while the payload capacity was 14.5%. In 3 h, 16% of the naringin was released in simulated gastric fluid with pepsin, and 50% was released in simulated intestinal fluid with trypsin (pH 6.8) in 4 h.

6.5 Summary This chapter offers a thorough and in-depth analysis of the strategic development, marketing, and bioavailability traits of nutraceuticals and functional meals containing nanomaterials. In the start of the chapter, it is made clear how important nanomaterials are for enhancing the stability, bioavailability, and efficacy of nutraceutical goods. It focuses primarily on examining the particular uses of nanoparticles in the field of nutraceuticals, demonstrating their potential to completely transform the market.

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The chapter goes into greater detail about the different health advantages provided by nanonutraceuticals, such as their anticancer traits, immune-boosting effects, and capacity to reduce inflammation and oxidative stress. In-depth research is done on the potential of nanonutraceuticals. This chapter also discusses nutrigenomics, a new discipline that studies the complex interplay between genes and diet. Nutrigenomics has given substantial consideration to a number of nanocarriers, including polymeric micelles, carbon nanotubes, dendrimers, liposomes, transferosomes, and nanoemulsions. Additionally, the chapter examines the idea of functional foods and their various uses, highlighting the value of polysaccharides, lipid-based formulations, and protein-based formulations in the creation of functional food products. The chapter provides a thorough review of the use of nanomaterials in the fields of functional foods, nutrigenomics, and nutraceuticals. It emphasizes how nutraceuticals based on nanomaterials have the potential to improve stability, bioavailability, and effectiveness. The chapter also analyzes the effect of genetic alterations on the antibacterial, antifungal, and anticancer characteristics of nanonutraceuticals. For researchers, experts, and anyone interested in the design and development of nutraceuticals and functional meals integrating nanomaterials, it is an invaluable resource.

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Chapter 7

Nanocarriers as a Novel Approach for Phytochemical Delivery in Food

Abstract In recent years, there has been a substantial increase in the amount of focus placed on the utilization of nanocarriers as a novel technique for the delivery of phytochemicals in food. The potential of nanocarriers to improve the stability, targeting ability, bioavailability, and therapeutic efficacy of phytochemicals is the primary topic of this chapter. We examined the several nano-based carriers that are used for the onsite delivery of phytochemicals, focusing on their capacity to increase bioavailability and stability. In addition, the metabolic processes of phytochemicals when they are in the presence of nanocarriers are investigated, which sheds light on the possible interactions and changes that take place. In addition, the antimicrobial actions of phytochemicals as well as the health advantages connected with them are investigated, which provides insights into the prospective applications of these compounds. In general, this chapter gives a complete overview regarding nanocarriers application for the efficient delivery of phytochemicals in food and gives prospective pathways for increasing the functional characteristics and health-promoting impacts of these phytochemicals.

7.1 Introduction Phytochemicals are plant-derived compounds and are mostly secondary metabolites consisting of indoles, phenolic acids, isothiocyanates, phytoprostanes and furanes, saponins, phytosterols, and alkaloids [1]. They are typically non-nutritive substances for plants, however, these phytochemicals facilitate fruits, nuts, vegetables, spices, cereals, drinks, and other dietary plant-derived goods with customary flavor and color [2]. In addition to flavor and color, phytochemicals also provide protection to plants from various environmental hazards (stress, pathogenic attack, UV exposure, and pollution) and diseases [3]. Studies show that in addition to plants, phytochemicals also exert similar beneficial effects on humans under stressed conditions, either in metabolite or native form. It involves microtubule and microfilament assembly inhibition, free radical scavenging, chelation of metal, and protease inhibition [4, 5]. This opened up a vast opportunity for important pharmacological uses of phytochemicals

© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_7

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that might help people more effectively than other synthetic medicines. Phytochemicals exhibited various advantageous effects like frequent and easy bioavailability, wide biodiversity, low cost, and preference. However, their wide application has been limited due to their fast metabolism, poor absorption and stability, hydrophobic nature, and lower target specificity. Numerous phytochemicals can be well utilized for their functions as (i) antioxidants (i.e., flavonoids of vegetables and fruits, allyl sulfides from onions, leeks, and garlic; carotenoids from fruits and carrots; tea and grape polyphenols); (ii) DNA replication modulators (beans saponins, hot peppers capsaicin); (iii) enzyme regulatory agents (i.e., soy protease inhibitors; cabbage indoles); (iv) hormones (i.e., isoflavones); and (proanthocyanidins from cranberries). These characteristics offer several opportunities in aesthetic, industrial, medicinal, and nutritional uses [3]. However, it is interesting to note that a number of phytochemicals also have negative side effects that limit their regular applications [6]. Examples include unwanted hypoglycemic effects produced by amylase inhibitors, saponin interactions and lysis of erythrocyte membranes by saponins, infertility and liver disease associations with dietary phytoestrogens, and lignans inducing estrogenic and antifertility effects. To avoid the deleterious effects of metabolizing these compounds at therapeutic doses, nanoencapsulation technology offers a promising approach for effectively delivering bioactive molecules to cells and tissues. By employing nanoparticles as carriers, the transportation of phytochemicals to specific target sites can be achieved, leading to improved bioefficacy. Nanoparticles, characterized by their minute size, are constructed from materials at the atomic or molecular level, making them ideal for this purpose. Consequently, they are more mobile than larger materials throughout the human body [7]. Figure 7.1 displays the extraction, encapsulation, and delivery of phytochemicals by nanoparticles.

Fig. 7.1 Schematic showing the nanotechnology-based phytochemical delivery system. Reprinted with permission from Advanced Drug Delivery Reviews, Copyright 2021, Elsevier [10]

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Nanotechnology is crucial for the delivery of drugs as well as their regulated release and transport to the target site [8, 9]. Through the site- and target-specific administration of medication, this technique offers a broad spectrum of potential benefits for the treatment of chronic human diseases. With comprehensive information at hand, this chapter aims to elucidate the diverse range of nanocarriers utilized for the conjugation of phytochemicals, thereby enhancing their stability and highlighting their primary utility as therapeutic agents.

7.2 Limitations of Phytochemicals Diabetes, neurodegenerative disorders, and cardiovascular diseases can all be treated effectively with phytochemicals. Due to their polar nature and large size, these substances face challenges in traversing the blood–brain barrier (BBB), limiting their ability to penetrate into the brain, blood vessel endothelium, mucosa, and gastrointestinal tract. They can also be degraded enzymatically in the digestive tract. A higher dose of phytochemicals administered causes organ toxicity in the periphery [11].

7.2.1 Condition Optimization The stability of phytochemicals has been influenced by a number of environmental variables. In order to reduce the loss of phytochemicals, it is necessary to construct transportation vehicles, optimize processing procedures, and create storage environments under ideal circumstances. For instance, if degradation can be caused in acidic or alkaline environments, then those conditions ought to be avoided. Similar to this, the processing and packaging of light- and temperature-sensitive phytochemicals can be designed to avoid conditions that may lead to their breakdown.

7.2.2 Stability There is wide variation in the polarities, molecular weights, and functional groups of phytochemicals, which further leads to alteration in their stability and solubility [12]. The stability and bioavailability of phytochemicals are influenced by their exposure to various environmental factors, including humidity, oxygen content, light, and temperature, as well as their interactions with other food components. For example, the stability of flavonoids remains unaffected when incorporated into food products that contain milk proteins, while carotenoids undergo chemical degradation

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when subjected to elevated temperatures, acidic conditions, and exposure to transition metals [13]. For example, flavonoids are stable when added to milk-proteincontaining food products [14]; in contrast, carotenoids undergo chemical degradation when exposed to elevated temperatures, acidic conditions, and transition metals. Enzymes found in various parts of the gastrointestinal tract process the phytochemicals, altering their bioavailability and bioactivity. The rheology of the gastrointestinal contents in the lumen determines how phytochemicals are transported and absorbed in the gastrointestinal tract (GIT). Depending on the quantity and kind of food taken, as well as how those meals are broken down in the GIT, the rheological properties of gastrointestinal fluids can vary, ranging from fluids with low viscosity to solid-like materials with viscoelastic behavior [1].

7.3 Nanomaterials as Nanocarriers for Phytochemicals 7.3.1 Liposomes The most widely studied nanocarrier forms for medication delivery are liposomes. Studies have shown that they can improve the stability of phytotherapeutics, promote their effective distribution in the body, and effectively encapsulate both hydrophilic molecules in the aqueous core and hydrophobic molecules in the non-polar tail region [15]. The liposome’s membrane structure resembles that of a cell membrane. Research findings have demonstrated that they play a stabilizing role for phytotherapeutics, improve their distribution throughout the body, and effectively encapsulate hydrophilic molecules in the aqueous core (e.g., 5-fluoro-deoxyuridine and ampicillin) as well as hydrophobic molecules in the non-polar tail region (such as amphotericin B and indomethacin) [15]. Figure 7.2 shows the delivery of phytochemicals using lipid-based carriers. In order to improve the bioavailability, Narayanan et al. encapsulated curcumin and resveratrol into liposomes and investigated their combined chemo-preventive effect on B6C3F1/J mice (prostate-specific PTEN knockout) [17]. High-performance liquid chromatography (HPLC) analysis results showed an increased level of curcumin in the case of liposomal encapsulated curcumin and resveratrol coadministration. The combined treatment of resveratrol and curcumin significantly reduced the in vivo prostatic adenocarcinoma. Further, in vivo studies revealed that exposure to curcumin and resveratrol induces apoptosis and inhibits cell growth. Further, the action of these formulations downregulated the expression of cyclin D1 and pAkt, which were enhanced due to the loss of PTEN. The results of this study offer concrete proof that the combination of phytochemicals can improve the effectiveness of chemoprevention in prostate cancer. These results strongly imply that the loss of the tumor suppressor gene PTEN is caused by the combination of phytochemicals, which may lower the incidence of prostate cancer. Moreover, Huang and colleagues also exhibited the utilization of liposomal encapsulation techniques for curcumin and

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Fig. 7.2 Lipid-based approach for delivery of phytochemicals, adapted from [16]

resveratrol to amplify their antioxidant efficacy [18]. The encapsulation of curcumin and resveratrol together led to a reduction in particle size, a lessening of the polydispersity index, and an increase in the efficiency of the encapsulation process. The liposome formulation that had a ratio of 5:1 curcumin to resveratrol displayed the smallest particle size (77.50 nm), the lowest polydispersity index (PDI) (0.193), the highest encapsulation efficiency (80.42%), and the most potent antioxidant properties. These properties included the scavenging of 2,2-diphenyl-1-picrylhydrazyl, the inhibition of lipid peroxidation, and high reducing power. Liposomes that contained both curcumin and resveratrol displayed greater performance throughout the various stages, including preparation, storage, heating, and exposure to surfactant stress, in comparison to liposomes that contained only one of the polyphenols. This was the case regardless of which polyphenol was contained within the liposomes. Fluorescence and infrared spectroscopy techniques were used to analyze the distribution of curcumin and resveratrol within liposomes. The results indicated that curcumin is primarily located in the hydrophobic acyl-chain region of the liposomes, while resveratrol is aligned with the polar head groups. This distinctive arrangement of the two compounds may contribute to the enhanced stability of the liposomes, suggesting a synergistic effect between their orientations. Malekar et al. investigated the location and effect on colloidal stability of five chemically distinct phenolic compounds (raloxifene, garcinol, quercetin, transresveratrol, and bisphenol A) in a liposomal bilayer containing dipalmitoylphosphatidylcholine [19]. According to the authors, the centrally located phenolic compounds (resveratrol and quercetin) had a negative impact on liposomal colloidal stability because they had less contact with phosphate head groups. In contrast, phytochemicals in the glycerol region of acyl chains (raloxifene, garcinol, and bisphenol A) were more stable when exposed to phosphate head groups or electrostatic repulsion forces. Wogonin is an O-methylated flavone that can be isolated from Chinese herbal

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plants and is used as an anticancer agent [20]. Using the film dispersion method, Wogonin liposomes have been created and have demonstrated improved entrapment efficiency. It can also be used as an antitumor agent with enhanced accumulation, therapeutic effect, and biodistribution [21].

7.3.2 Niosomes Niosomes are colloidal aggregates composed of non-ionic surfactants, with or without cholesterol, that closely resemble the appearance of liposomes. They possess biocompatible properties and are considered safe for biomedical applications due to their non-toxic nature. To encapsulate non-polar and polar pharmaceuticals, lipid bilayers and micelles can coexist. Niosomes facilitate sustained drug delivery with longer shelf life, biodegradability, stability, and non-immunogenicity [22]. Elagic acid had been encapsulated into noisome to enhance its pharmaceutical properties and overcome its limitations like low solubility and permeability [23]. In a similar context, the antineuropathic potential and anti-inflammatory properties of the alkaloid fraction from Fumaria officinalis have been enhanced by encapsulating it in niososme. It can significantly improve the pharmacokinetic properties of the alkaloid fraction by enhancing entrapment efficiency, stability, and rapid degradation in simulated gastrointestinal conditions [24]. The primary determinants of antinociceptive and anti-inflammatory activities are anti-inflammatory factor IL-10 increased expression, expression of interleukin 6 and tumor necrosis factor-alpha (TNF-alpha) reduced expression and decreased in vivo oxidative stress. Diosgenin is another phytochemical with anticancer properties, but its application has been hampered by its poor water solubility, instability in biological environments, low permeability, and bioavailability [25]. To overcome these limitations of diosgenin, Hajizadeh et al. encapsulated it in the nucleus, which enhanced its solubility and improved its efficacy in a liver cancer cell line (Fig. 7.3) [26]. The loading efficiency of diosgenin in niosomes resulted in a sustained release profile with an 89% loading efficiency, whereas free diosgenin exhibited a faster release (40% in 720 min compared to 100% in 240 min). Cytotoxicity assessment using the MTT assay revealed minimal cytotoxicity of free diosgenin (60% cell viability), whereas diosgenin niosomes demonstrated significant inhibition of growth in the HepG2 cancer cell line (28% cell viability). As a result, this approach has been promised as a sustainable, reliable, and controlled delivery method for phytochemicals. Further, the phytochemical thymoquinone from Carum carvil seeds has also found wide application in cancer therapy [27]. To overcome its hydrophobic nature limitation, Barani et al. designed a carum-loaded niosome for their application in breast cancer therapy [28]. Results showed that loaded niosomes exhibited enhanced anticancer activity against MCF-7 cancer cells in comparison to free thymoquinone. It showed decreased migration of cancer cells with a G2/M arrest in cell cycle progression. These findings indicate the presence of effective novel carriers capable of efficiently

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Fig. 7.3 Schematic representation of the diosgenin-encapsulated niosome. Reprinted with permission from DARU Journal of Pharmaceutical Sciences, Copyright 2019, Springer Nature [26]

encapsulating poorly soluble phytochemicals, which could offer significant benefits in the context of breast cancer treatment. Myrtus communis (myrtle) herb acts as an antiseptic and serves as a remedy for wounds, burns, nosebleeds, and mouth ulcers. However, factors like poor solubility and permeability as well as low biopharmaceutical activity limit their application, which can be overcome by their niosomal formulation [29, 30]. The study depicts that niosomal formulations with 4% myrtle extract form multilamellar vesicles and exhibit optimal in vitro release and entrapment efficiency. Encapsulation also reduces the release rate and increases the action duration of the extract, with lower toxicity toward 3T3 cells. In comparison to free myrtle, the formulation also exhibited enhanced antibacterial activity, as depicted by a high inhibition zone and a lower minimum inhibitory concentration.

7.3.3 Bilosomes Niosomes and liposomes have been successfully utilized to transport drugs to their target sites, but instability in the gastrointestinal tract has made it clear that new delivery methods are required. This leads to the development of bile salts, which also consist of bile salts in addition to lipids [31]. This facilitates low degradation in the gastrointestinal tract with high penetrability to the mucosal lining. The majority of bilosome research is conducted for oral vaccination purposes, but a few recent studies have used bilosomes for phytochemical delivery. To investigate the application of bilosomes, a pharmacologically active polysaccharide isolated from Enteromorpha intestinalis, in drug delivery against hepatocellular carcinoma [32].

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The results showed the formation of spherical vesicles with controlled release and optimum entrapment efficiency (71.60%). In vivo results showed reduced serum fetoprotein, heat shock protein 70, lipocalin-2, and endoglin in bilosome-exposed mice in comparison to the control group. Furthermore, histological examination of the tissue sample demonstrated a localized area characterized by degenerated pleomorphic hepatocytes and the presence of fine fibrosis originating from the portal region. The optimized bilosomal formulation shows great promise as a potential therapeutic approach for hepatocellular carcinoma, as it exhibits potent anticancer and antiangiogenic properties. In another study, tripterine from Tripterygium wilfordii was encapsulated in hyaluronic acid (HA)-functionalized bilosomes for targeted delivery to inflamed joints [33]. Result showed the bilosome-encapsulated tripterine exhibited enhanced cellular uptake with high targeted efficiency, which resulted in prolonged circulation time and increased intraarthritic bioavailability in comparison to free tripterine. The in vivo antiarthritic efficacy of HA@Tri-BLs was also noticeably greater than that of uncoated Tri-BLs, which resulted in a clear remission of inflammation. Our results imply that bilosomes functionalized with HA are a viable delivery system for articular administration of antiphlogistic medicines to enhance their efficacy.

7.3.4 Archaeosomes Archaeosomes consist of caldarchaeol lipids (forming a monolayer) and/or archaeol lipids (forming a bilayer). These lipid components exhibit exceptional stability and versatility in diverse biological and physical conditions. Like other lipid-based nanocarriers, archaeosomes have the capability to effectively deliver both hydrophilic and hydrophobic drugs to the desired target site. It exhibited enhanced stability in a wide pH and temperature range due to saturated alkyl side chains and ether bonds.

7.3.5 Solid Lipid Nanoparticles Solid lipid nanoparticles (SLN) application in drug delivery is a relatively recent development. They use additional emulsifiers in addition to drug encapsulation in the lipid core to add stability [34]. Due to its exceedingly low bioavailability and volatility, the isolated phytochemical epigallocatechin-3-gallate (EGCG) from green tea leaves was not fully exploited despite its potent anticancer and anti-inflammatory properties. On the other hand, SLN loaded with EGCG displayed a prolonged and sustained release of EGCG without demonstrating any acute or chronic toxicity [35]. In addition to fatty acids, other types of lipids such as glycerides, steroids, and wax are also utilized in the manufacturing process of SLN. The synthesis of SLN is improved both in terms of its bioactivity and its safety when physiological lipids are incorporated into the process. Combining the advantages of lipid nanoemulsions and

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Fig. 7.4 Schematic of EGCG encapsulation in solid lipid nanoparticles. Reprinted with permission from Chemistry and Physics of Lipids, Copyright 2016, Elsevier [37]

polymeric nanocarrier systems, SLNs can range in size from 10 to 1000 nm and have a range of sizes in between. Notably, SLN is the only nanocarrier technology that can be sterilized by autoclaving and used for both intravenous and topical administration of drugs [36]. Further to boost EGCG’s stability and test for anticancer activity, Radhakrishnan et al. have encapsulated it in SLN (Fig. 7.4) [37]. A stealthy method of effective drug distribution is made possible by the lipid core of nanoparticles, which also serves as an extra structural reinforcement for the nanoparticle assembly. EGCG-SLN was found to be 8.1 times more toxic to MDA-MB 231 human breast cancer cell lines and 3.8 times more toxic to DU-145 human prostate cancer cell lines than unadulterated EGCG. The use of EGCG-loaded EGCG-SLN greatly improved the stability of encapsulated EGCG, which is known to be unstable under physiological conditions and prone to complete degradation in its native form. During colloidal stability experiments, EGCG-SLN demonstrated remarkable resistance to electrolyte-induced aggregation and stability in both serum and phosphate buffer saline (PBS). Thus, EGCG-SLN is a prospective delivery method for EGCG as a potential chemotherapeutic drug. Eugenol is a naturally occurring substance that is present in a variety of aromatic plant species, such as clove, holy basil, and betel vine. By reducing the inflammatory response brought on by P. acnes, it has demonstrated antiacne effectiveness [38]. In a study conducted by Garg et al., the permeation of eugenol-loaded SLNs incorporated in a hydrogel formulation was investigated in human cadaver skin. The results demonstrated that the SLNs significantly enhanced the penetration of eugenol into the epidermal layer compared to the conventional hydrogel alone. Moreover, the eugenol-loaded SLNs exhibited superior occlusive and hydrating effects on the skin compared to eugenol oil and the ordinary hydrogel formulation [39]. Since their tiny size facilitates their entry through the skin, curcumin (Cur) is amenable to topical administration when it is encapsulated in SLNs. Precirol ATO5 and Tween-80 were used to manufacture Cur-SLNs utilizing the probe ultrasonication method [40]. Additionally, Cur-SLNs were added to Carbopol gel, and their effects

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on ex vivo skin permeability, skin deposition, and skin irritation were investigated. By inhibiting tyrosinase, the anti-hyperpigmentation potential of Cur-SLN gel was evaluated. Using BALB/c mice, its prospective effects on irritant contact dermatitis were investigated further. The improved Cur-SLN displayed 51 nm and 93% EE particle sizes. Experiments on drug deposition in vitro also suggested the possibility of skin targeting, whereas ex vivo penetration of Cur-SLN gel revealed regulated drug release for up to 24 h. An in vitro tyrosinase inhibition assay demonstrates the gel’s potential for cutaneous depigmentation. In BALB/c mice, the gel effectively reduced cutaneous water content and suppressed auditory edema. The Cur-SLN gel would be a secure and effective alternative to conventional treatments for Irritant contact dermatitis (ICD) and pigmentation. Tetrahydrocurcumin (THC), commonly known as “white curcumin,” is a stable and colorless derivative of curcumin known for its enhanced antiinflammatory and antioxidant properties. Kakkar et al. aimed to improve the topical bioavailability of THC by incorporating it into a nanocarrier system with a hydrogel as the final dosage form. The THC-SLNs exhibited an ellipsoidal shape and had an average particle size of 96.6 nm, as observed through transmission electron microscopy (TEM). The zeta potential of the THC-SLNs was measured to be 22 mV. The THC-SLNs showed high drug content (94.51% ± 2.15%) and encapsulation efficiency (69.56% ± 1.35%). In vitro drug release experiments revealed that the THC-SLN gel’s drug release followed Higuchi’s equation, demonstrating Fickian diffusion. Ex vivo permeation experiments revealed that the THC-SLNs gel had a skin penetration rate approximately 17 times greater than the pure THC gel. Studies on skin irritation, occlusion, and formulation stability revealed that the product was non-irritating, had the necessary occlusivity, and was stable. This activity was substantiated by biochemical and histological analyses. It is important to highlight that THC-SLNs gel had noticeably better action than free THC gel. The created substance opens up new therapy paths for a number of skin ailments because inflammation is inherent to all skin problems. To the best of our knowledge, this study presents the first investigation into the therapeutic potential of lipidic nanoparticles loaded with white curcumin for the treatment of cutaneous inflammation.

7.3.6 Carbon Nanotubes Multiple-walled carbon nanotubes (MWCNTs) and single-walled carbon nanotubes (SWCNTs) are two general categories for carbon-based nanomaterials. Due to their special physicochemical characteristics, which enable them to pass through cell membranes, and their incredibly adaptable materials as well as vast potential for biomedical applications, these CNTs have generated a great deal of interest [41, 42]. Li et al. showed that the amorphous structure of curcumin in SWCNT-Cur allowed for quick release. SWCNT-Cur was more efficacious than native curcumin at inhibiting the proliferation of PC-3 cells. In addition to serving as scaffolds, the SWCNTs in SWCNT-Cur were also thermal ablation agents, which significantly

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reduced PC-3 cell growth [43] (Fig. 7.5a). The conjugates’ improved solubility and dispersibility, as well as the slower degradation rate of curcumin in the formulation, all contribute to the mechanism underpinning SWCNT-Cur’s higher antitumor effectiveness when compared to curcumin alone. A growing number of studies have also demonstrated that SWCNTs have the extraordinary ability to be rapidly incorporated by mammalian cells through endocytosis [44], phagocytosis, and/or diffusion. Their cargo is also absorbed during SWCNT internalization. Furthermore, phosphatidylcholine is easily incorporated into the phospholipid bilayer that builds up mammalian cell membranes, which improves the distribution of curcumin from the outside to the inside of the cell in the SWCNT-Cur. In addition, the rapid release of curcumin when SWCNT-Cur is internalized in the cell may aid in achieving a high drug concentration. Li et al. further evaluated the in vitro and in vivo properties of SWCNTCur (Fig. 7.5b) [45]. In mice, SWCNT-Cur dramatically boosted the blood level of curcumin by up to 18-fold. Additionally, SWCNT-Cur showed no overt damage in the major organs and a considerably greater inhibitory efficacy on tumor growth in a mouse S180 tumor model. Additionally, SWCNT-photothermal Cur’s therapy under near-infrared radiation made it easier for it to stop the growth of the tumor in vivo. Additionally, the amount of solvent left in the SWCNT-Cur formulation is minimal, and gas chromatography and infrared spectra both showed that hydrogen bonds were established between the void carriers and the curcumin. Moreover, investigations employing confocal microscopy and spectrofluorometry demonstrated that SWCNT-Cur exhibited a sixfold higher curcumin absorption rate in human prostate cancer PC-3 cells compared to unmodified curcumin. This enhanced cellular uptake and increased curcumin concentration in the bloodstream indicate that the modification of curcumin’s physicochemical properties through functionalized SWCNT, along with the combination of phototherapy and chemotherapy effects, presents a promising approach for improving the anticancer effectiveness of curcumin in vivo. Additionally, Yanagi et al. proposed the β-carotene encapsulation in SWCNTs [46]. Authors have shown that β-carotene can be shielded from radical species reactions and its isomerization by being enclosed inside a nanotube. Thus, the protection aspect can open new avenues for their application for biomedical purposes. It is remarkable that β-carotene can be easily encapsulated in carbon nanotubes and that these tubes can act as nanocontainers. It is well-established that carotenoids can be functionalized by attaching various organic groups. It can be anticipated that functionalized carotenoids will be able to penetrate SWCNTs with ease as well. Also, Yallappa et al. used bark extracts from Terminalia arjuna to turn Cu(NO3 )2 and AgNO3 precursors into copper nanoparticles (CuNPs) and silver nanoparticles (AgNPs) using microwave irradiation in the presence of well-dispersed MWCNTs in an aqueous medium [47]. Every indication pointed to the synthesis of CuNPs or AgNPs and their MWCNTs functionalization. The bactericidal activity of CuMWCNT and Ag-MWCNT nanomaterials that were modified phytochemically was enhanced, Furthermore, it was observed that the inhibitory activity against bacteria was more pronounced compared to its activity against fungi. In addition, these nanomaterials have no cytotoxic effect on normal epithelial cells (Vero), However, they exhibited significant toxicity toward MDA-MB-231, HeLa, SiHa, and HepG2

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Fig. 7.5 a Loading of curcumin onto SWCNTs is thought to happen through adsorption, complexation with the benzene ring, hydrogen bonding between the carboxyl group of functionalized SWCNTs and the phenolic hydroxyl group of curcumin, and hydrophobic van der Waals forces. Reprinted with permission from Drug Delivery, Copyright 2014, Taylor & Francis [43]. b Overview of the mechanisms through which SWCNT-Cur demonstrates superior inhibition of tumor development compared to curcumin alone. SWCNT-Cur enhances the delivery of curcumin into tumor cells, elevates the blood concentration of curcumin, and inhibits tumor growth through the photothermal effect induced by SWCNT. The combined effects of these factors synergistically enhance the antitumor activity of SWCNT-Cur, adapted from [45]

cells. The viability of these cells decreased considerably with increasing doses (10– 50 μg mL−1 ) and longer incubation periods (24–72 h). For instance, at a lower dose of 10 μg mL−1 , the viability of normal Vero cells was 91%, while cancer cells exhibited a viability of 76%. Even at 50 μg mL−1 , normal cells remained viable, whereas the viability of cancer cells such as MDA-MB-231, HeLa, SiHa, and HepG2 decreased to 12%, 15%, 13%, and 20%, respectively. In summary, the novel approach for synthesizing biohybrid nanomaterials shows great potential, particularly in the field of biomedical applications. For treatment of multiple drug resistance (MDR) in cancer cells, Kumar et al. developed nanoconstructs based on MWCNTs coencapsulated with N-desmethyl tamoxifen (N-TAM) and quercetin, a moderate P-gp efflux inhibitor [48]. The theoretical basis revolves around a comprehensive

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approach targeting MDR mechanisms through three key strategies: drug modification, effective permeation using MWCNTs, and inhibition of P-gp. Tetraethylene glycol, a biodegradable linker, was used to convert tamoxifen into N-TAM and then conjugate it to carboxylated MWCNTs (TEG). The conjugate was adsorbed with quercetin to yield the desired result, which is N-TAM-TEG-MWCNT-QT. Spectroscopic analysis confirmed the successful conjugation of N-TAM and the physical adsorption of quercetin. In vitro release studies demonstrated that the combination of N-TAM-TEG-MWCNT exhibited a controlled release profile of N-TAM, with a more modest release compared to the purified drug under optimal conditions. However, in the acidic pH environment characteristic of cancer cells, a significant increase in drug release was observed. The developed nanometric formulation was discovered to be hemocompatible. Drug-resistant MDA-MB-231 cells exhibited lower IC50 values and improved cellular absorption, followed by an increase in drug availability in the systemic circulation of mice compared to non-resistant cells. The intelligent nanosystem demonstrated precise control over drug release, improved drug effectiveness, biocompatibility, and favorable pharmacokinetics. These are critical and desired characteristics for effectively addressing the increasing challenge of MDR in cancer treatment.

7.3.7 Dendrimers Dendrimers are polymeric nanostructures with multiple branches that terminate in functional groups and are covalently bonded to a central core (with concentric layers known as generation). Dendrimers transport drugs and ligands, which are either conjugated to the surface or confined within the structure. The presence of functional groups on the outer surface of the dendrimer enables the convenient attachment of ligands, thereby enhancing the drug delivery capability to the target site [49]. Drugs are released from dendrimers either as a result of environmental changes like temperature and pH, or by the enzymatic breakdown of the covalent connection between the dendrimer and the drug [50]. As release mechanisms, common chemical or physical reactions include dendrimer swelling and chemical attrition. Covalent conjugates exhibit greater regulated release behaviors in this regard [51]. By forming covalent bonds with biomolecules and being induced by polyethylene glycol, dendrimers can effectively prolong the duration of entrapment [52]. There are not many studies that directly compare the efficacy of dendrimers to other delivery systems, such as nanoliposomes or nanoemulsions, but it is theorized that dendrimers have modifiable branches that allow them to selectively absorb a wide range of compounds. Figure 7.6 depicts the numerous dendrimer-based drug delivery methods. Madaan et al. determine whether polyamidoamine (PAMAM) dendrimers might be used to administer quercetin orally [53]. The aqueous solubility of quercetin was evaluated at concentrations of 0.1, 0.5, 1, 2, and 4 μM in dendrimers of generations G0, G1, G2, and G3. Subsequently, the PAMAM dendrimers successfully incorporated the quercetin and underwent evaluation regarding their stability, size,

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Fig. 7.6 A Illustration depicting the hierarchical structure of dendrimers, including their generations, branching units, and terminal groups. Figure showing two types of drug delivery systems utilizing dendrimers: a active targeting and b passive targeting. Reprinted with permission from Advances in Colloid and Interface Science, Copyright 2020, Elsevier [54]

size distribution, and formulation characteristics as nanocarriers. The in vitro release behavior of quercetin from the quercetin-PAMAM complexes was investigated in PBS (pH 7.4) at 37 °C. Furthermore, the effectiveness of the quercetin-loaded PAMAM dendrimer was assessed using a carrageenan-induced paw edema model to evaluate its acute anti-inflammatory activity. The production of PAMAM dendrimers and their corresponding concentrations both appeared to have the ability to improve quercetin’s solubility. All of the quercetin-PAMAM compounds have limited polydispersity indices and are within the nanometer range (100 nm). Preliminary evidence from a pharmacodynamic study demonstrated the potential of quercetin-PAMAM complexes. In addition, an in vitro analysis revealed a two-phase release profile of quercetin, involving an initial rapid release phase followed by a sustained release phase. According to the study’s findings, the dendrimer-based drug delivery system for quercetin offers a great deal of promise to address the drug delivery problems associated to it. Dendrimers contain two significant phenolic chemicals, resveratrol and curcumin. With G4-PAMAM, which has acetyl terminal groups, and G5 PAMAM, which has amine terminal groups, these two bioactive substances have been successfully

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coupled. The findings showed that resveratrol and curcumin had increased solubilities that were 40 times and 200 times larger than those of their pure forms, respectively [55, 56]. The other class of phytochemicals that dendrimers stabilize is phenolic acids. Gallic acid is one of these substances that is typically nanoencapsulated by dendritic structures [57]. However, due to its exceptional metabolism and quick elimination, its oral bioavailability is constrained. Dendrimer entrapment of this bioactive has yielded promising results. By conjugating gallic acid with G4-PAMAM dendrimer, its release could be extended for up to 12 h. Additionally, in vivo tests showed that conjugating gallic acid with a dendrimer increased its ability to protect the liver [58]. Gallic acid has additionally been employed to stabilize the anthocyanin color in a G4 dendrimer scaffold made of triethylene glycol and gallic acid that includes 162 terminal anionic sulfate groups [59]. The stabilization of anthocyanin hues can be attributed, in part, to the hydrophobic interactions between gallic acid and anthocyanins. PAMAM dendrimers were used in a study by Gupta and colleagues to passively administer berberine (BBR, a nitrogenous cyclic natural alkaloid) [60]. BBR is a nucleic acid dye that inhibits cell proliferation in a variety of cancer cell lines, including breast, lung, and colon cancer cell lines, and induces cancer cell apoptosis (via mitochondria-dependent pathways, such as decreased bcl-2 amount and increased cytoplasmic cytochrome C) [61]. The zeta potential of the formulated BBR formulations, both encapsulated (BPE) and conjugated (BPC), closely resembled that of the PAMAM G4 dendrimer. The entrapment efficiency of BPE was determined to be 29.1%, while the percentage of conjugation in BPC was found to be 37.49%, indicating a high drug payload in the conjugated form. In vitro release studies conducted in different media (water and PBS 7.4) demonstrated a sustained release pattern of BBR. In PBS, the drug is released after 24 h at a rate of around 80% and 98%, respectively, compared to about 72% and 98% in PBS. As the best-fitting release kinetic model, the formulation showed Higuchi and first-order release. The PAMAM-BBR (BPC) demonstrated considerably stronger anticancer activity against MCF-7 and MDA-MB-468 breast cancer cells in the MTT experiment. Even after 24 h, the BPC and BPE’s time-dependent ex vivo hemolytic toxicity was greatly reduced (5%), indicating that the formulations can be considered to be relatively safe and biocompatible. Similar to this, the formulations’ safety and biocompatibility were determined using an auto-analyzer to analyze the in vivo hematological parameters, and the effects were found to be minimal but not significant (p > 0.05). The albino rat model revealed a striking improvement in the in vivo pharmacokinetic characteristics. In comparison to 6.7 h for BBR alone, the t1/2 obtained for BPC was 14.33 h. Result showed that the conjugated formulation exhibited greater efficacy compared to the encapsulated formulation among the developed formulations. Therefore, it is certain that conjugation is the superior method for delivering natural bioactives via dendrimers. In this study, polyethylene glycol (PEG)-modified 3-diaminobutyric polypropylenimine dendrimers were employed as a redox-responsive codelivery system for complexed DNA (as a targeted therapeutic agent) and camptothecin (a hydrophobic anticancer agent) (Fig. 7.7) [62]. By using this treatment approach, it is possible to

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Fig. 7.7 Schematic of dendrimersomes containing camptothecin for gene delivery and redoxresponsive drug delivery to cancer cells. Reprinted with permission from Nanoscale, Copyright 2019, Royal Society of Chemistry [62]

effectively reduce both the severe side effects of therapeutic drugs and the ability of cancer cells to develop drug resistance. In the methodology section, a spontaneous self-assembly approach was employed to fabricate PEG-modified dendrimers loaded with therapeutic drugs (sized between 150 and 200 nm) for the inhibition of prostate cancer cells. By utilizing 50 mM glutathione, which mimics the intracellular tumor tissue environment, efficient condensation of DNA on the surface of spherical dendrimers was achieved with an efficiency exceeding 85%. Moreover, the sustained release of therapeutic drugs demonstrated an efficiency of approximately 70%. According to an evaluation of the impact of dendrimer formation on biocompatibility, it has been widely reported that the size of dendrimers is correlated with their cytotoxicity [63, 64]. Additionally, significant cytotoxicity and hemolytic toxicity were noted. Therefore, neutralizing their surface cationic charges and greatly reducing their toxicity can be accomplished through surface engineering using biomolecules like folic acid (FA). In a study by Kesharwani et al. [65], the targeting capacity of Melphalan (MP: as a phytochemical agent) loaded folic acid-functionalized PPI dendrimers of different generations (PPI3, PPI4, and PPI5) has been investigated. The high-generation dendrimers were found to possess a spacious internal cavity, leading to notable loading efficiencies of 17.82%, 25.42%, and 28.462% for the MP-FA-PPI3, MP-FA-PPI4, and MP-FA-PPI5 nanocomplexes, respectively. This data demonstrates a generational correlation between drug intake values. Additionally, dendrimers’ hydrophobic properties make it easier to include hydrophobic melphalan into them and boost their solubility. Due to the physical attachment of extra melphalan molecules to folic acid, FA-PPI dendrimers achieved a higher loading capacity than pure PPI nanoparticles [139]. In contrast, highgeneration dendrimers offer more opportunity for folic acid conjugation since there are more surface functional groups available, which subsequently improves targeted delivery and loading efficiency. Furthermore, folic acid-conjugated nanocomplexes

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with sustained and controlled melphalan release behavior were suggested by in vitro release profiles. Because surface amine groups were protonated in acidic conditions, they exhibited a quicker release pattern. Contrarily, hemolysis caused by pure melphalan was 13.18%; however, hemolysis caused by FA-PPI3, FA-PPI4, and FAPPI5 was 3.04, 3.58, 5.86, 2.82, 3.06, and 5.22%, respectively, due to melphalan’s successful targeting toward tumor cells. The cytotoxicity investigations on MCF-7 and CASKI tumor cell lines demonstrated a significant inhibition of cell growth (over fourfold) by the MP-FA-PPI4 and MP-FA-PPI5 nanocomplexes, surpassing their non-folic acid-functionalized counterparts. In vitro studies utilizing MTT and flow cytometry assays revealed that the folic acid-functionalized nanocomplexes induced early apoptosis and triggered apoptotic mechanisms, leading to the eradication of cancer cells [65, 66]. In reality, they promote the production of intracellular reactive oxygen species (ROS), which leads to the release of pro-inflammatory markers and cell death. According to in vivo studies, the tumor volumes of mice treated with MP-FA-PPI3, MP-FA-PPI4, and MP-FA-PPI5 nanocomplexes were 259.9, 215.6, and 196.4 mm3 , respectively. According to a pharmacokinetic analysis of these formulations, folic acid-conjugated nanocomplexes had plasma drug concentrations that were nearly four times longer than those of non-conjugated formulations. Dendrimers perform better in biodistribution due, in large part, to their nanosize and inner hydrophobicity.

7.3.8 Quantum Dots Cadmium sulfide (CdS), zinc sulfide (ZnS), cadmium tellurium (CdTe), and other elements from groups II and VI of the periodic table are used to develop quantum dots (QDs), which are inorganic nanorange semiconductors. Their exterior shell is often comprised of one semiconductor, while their inner core is made of another. There is a cap made of any material specifically chosen for the target that covers both layers. Their small size, unique optical properties, including photoluminescence and absorbance, and quantum characteristics make them highly suitable for applications in cancer therapy, specifically in imaging (optical sensing) and drug delivery techniques. QDs cause immunogenicity, which can be reduced by the PEG coating. PEGylation enhances the QDs’ half-life and also promotes their uptake in cancer cells [67, 68]. In numerous cancer models, the dietary phytochemical allyl isothiocyanate (AITC), which is present in some cruciferous vegetables, shows promising anticancer properties [69]. Previous studies conducted on human hepatoma HepG2 cells and AITC demonstrated a dual-phase impact on cell viability, DNA damage, and migration. In a 3D coculture system consisting of HUVEC and pericytes, the effects of AITC on angiogenesis were examined, revealing a dual-phase response. At high concentrations, AITC inhibited tube formation, while at low doses, it promoted angiogenesis. By utilizing siRNA-mediated Nrf2 silencing and glutathione inhibition, the stimulating effects of AITC on cell migration and DNA damage were

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abolished. Liu et al. conducted a pioneering investigation into the biological activity of newly developed AITC-conjugated silicon quantum dots (AITC-SiQDs) [70]. At high concentrations, AITC-SiQDs displayed anticancer characteristics similar to AITC while avoiding the stimulating impact seen at low concentrations. Furthermore, the fluorescence of SiQDs demonstrated that AITC-SiQDs generated a prolonged and reduced Nrf2 translocation into the nucleus, which coincided with their levels of cellular uptake. The generation of ROS may contribute to AITC-SiQDs’ anticancer action. These findings emphasize the potential of nanotechnology in improving the therapeutic efficacy of dietary isothiocyanates for cancer treatment, as well as new insights into AITC’s biphasic effects. Wang et al. demonstrated that quercetin and fluorescent SiQDs can be coencapsulated in poly(ethylene glycol)-block-polylactide (PEG-PLA) nanoparticles, allowing for simultaneous in vitro imaging and increased quercetin biocompatibility [71]. A novel idea for tracking the distribution of anticancer medications can be found in fluorescent imaging with SiQDs. The nanoparticles are created using the double emulsion method, and their cytotoxicity in vitro is then extensively characterized and evaluated. Fluorescence imaging with a confocal microscope showed that HepG2 cells treated with PEG-PLA nanoparticles filled with both quercetin and SiQDs had red fluorescence staining. The encapsulation of quercetin within PEG-PLA nanoparticles demonstrated enhanced efficacy in inhibiting the proliferation of human hepatoma HepG2 cells compared to the pure form of the drug. Moreover, quercetin encapsulated in nanoparticles showed a significant reduction in DNA damage induced by hydrogen peroxide exposure in HepG2 cells. These findings suggest that quercetin nanoparticles have the bioactivity to decrease drug dosage frequency while increasing patient adherence. Polymeric nanoparticles and semiconductor quantum dots can be used to increase biocompatibility, water solubility, and delivery monitoring. Future drug delivery may be affected by these nanoparticulate technologies. According to reports, quercetin is a potent free radical scavenger and has been demonstrated to reduce the risk of oxidative stress-related chronic diseases such as diabetes, arthritis, and inflammation [72]. In this research, Jeyadevi et al. investigated the potential antiarthritic effects of quercetin in Wistar rats with adjuvantinduced arthritis, utilizing thio glycolic acid-capped cadmium telluride quantum dots (TGA-CdTe QDs) as a nanocarrier [73]. The scavenging potential of the QDsquercetin complex against free radicals was assessed using various assays, including ABTS, DPPH, nitric oxide (NO), and superoxide anion scavenging assays. To evaluate its therapeutic effect, rats with induced arthritis were orally administered the QDs-quercetin complex at concentrations of 0.2 and 0.4 mg/kg per day for a duration of three weeks after 15 days of adjuvant induction. The reference medication used by the authors was diclofenac sodium (DF). The results showed that when the QDs-quercetin combination was administered, inflammation was significantly reduced, and cartilage regeneration was improved. Treatment with the QDs-quercetin complex significantly decreased the expression of lipid peroxidation in paw tissue and increased the activities of antioxidant enzymes such as catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPx), and reduced glutathione (GSH).

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Experimental animals’ red blood cells (RBC), white blood cells (WBC), rheumatoid factor (RF), and erythrocyte sedimentation rate (ESR) were also measured. The complete regeneration of cartilage in arthritis-induced rodents treated with the QDsquercetin (QDs-QE) complex was confirmed by histology of hind limb tissue from experimental groups. Figure 7.8a depicts a putative mechanism for the antiarthritic effects of QDs-quercetin. The antiarthritic activity of the QDs-QE complex may be attributed to its ability to counteract the harmful effects of different free radicals produced during inflammation and its capacity to inhibit the synthesis of the COX2 enzyme. Thus, this research suggests that the QDs serve as nanocarriers for the medications used to treat numerous degenerative disorders. Ghanbari et al. successfully synthesized graphene quantum dots conjugated with tryptophan (Trp-GQDs) and conducted a comprehensive investigation on the loading capacity and release kinetics of curcumin, an hydrophobic anticancer drug, as well as its cytotoxicity on human breast cancer cells (Fig. 7.8b) [74]. Tryptophan was conjugated onto GQDs via amide bonds, whereas non-covalent interactions have been utilized for the attachment of curcumin to GQDs and Trp-GQDs. The initial concentration of curcumin was raised, and the drug loading capacity was raised by 23% when GQDs were conjugated with tryptophan. This might be attributed to the increased overall concentration of aromatic structures due to the conjugation of tryptophan aromatic agents to GQDs. This further leads to enhanced π–π stacking interactions with curcumin and thus finally increases the drug loading capacity. The results further showed the pH-sensitive release of the drug at pH 5.5 and pH 7.4. The drug release from the nanoassembly was pH-sensitive, persistent, and 100% more rapid in acidic media than in neutral conditions. This is due to the protonation of curcumin’s OH group under a pH value of 5.5, which weakens the H-bonding contact between curcumin and the nanocarrier. Similarly, the pseudo-second-order model provided an outstanding fit to the experimental release data. MCF-7 cells demonstrated minimal cytotoxicity when exposed to GQD and Trp-GQD nanocarriers in the MTT cytotoxicity experiment, with cell survival exceeding 92% at a dose of 50 μg/ ml. However, both Cur-loaded nanocarriers, particularly Cur/Trp-GQDs, exhibited strong cytotoxic effects. In conclusion, the synthesized Trp-GQDs nanocarrier has improved drug loading capacity, traceability, biocompatibility, and pH responsiveness. Furthermore, it has anticancer effects when coupled with curcumin. The Cur/ Trp-GQDs nanoassembly has a lot of promise for cancer therapy. The Trp-GQDs nanocarrier shows potential for a variety of drug delivery applications due to its high drug loading capacity, biocompatibility, pH-sensitive nature, and traceability. To obtain a synergistic effect, graphene-based compounds complexed with pharmaceuticals have been developed for use in cancer therapy. Curcumin was used to produce graphene oxide (GO) and graphene quantum dots (GQDs) at three distinct weight-to-volume ratios (1:1, 1:3, and 1:5). GO and GQDs were successfully complexed with curcumin using a variety of spectroscopic and microscopy techniques, as demonstrated. The stability of the complex was confirmed by UV– vis spectroscopy, which showed less than 10% aggregation for GQDs-Cur and less than 20% aggregation for GO-Cur within a 48-h period. The loading efficiencies of curcumin in GO-Cur and GQDs-Cur, as determined by UV–vis analysis, were found

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Fig. 7.8 a Schematic of the putative antiarthritic mechanism of the QDs-QE complex against CFAinduced arthritis. Reprinted with permission from Colloids and Surfaces B: Biointerfaces, Copyright 2013, Elsevier [73] b The diagram illustrates tryptophan-functionalized quantum dots (Trp-QDs) that exhibit enhanced curcumin loading capacity and pH-responsive release behavior. Reprinted with permission from Journal of Drug Delivery Science and Technology, Copyright 2021, Elsevier [74]

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to be 80.1% and 83.1%, respectively. To assess their potential as anticancer agents, the complexes GO-Cur and GQDs-Cur were evaluated using the MTT assay against human breast cancer cell lines MCF-7 and MDA-MB-468. After 48 h of incubation with the cell lines, it was determined that the cell viability of GQDs and GO was greater than 75%, whereas the cell viability of 100 g/mL curcumin was only 40%. After 48 h of treatment, the complexes in the ratios of 1:1, 1:3, and 1:5 at 100 μg/mL concentration induced cell death at 60, 80, and 95%, respectively. The optical images of cancerous cells treated with GO, GQDs, Cur, GO-Cur, and GQDs-Cur at three different time points (0, 24, and 48 h) supported the findings of the MTT assay in terms of the percentage of cell death observed. The fluorescent images demonstrate that the curcumin was successfully delivered inside the cancer cell. The discussion centers on the potential mechanism by which the complexes GO-Cur and GQDs-Cur can kill malignant cells. It is intriguing to note that trans-resveratrol protected by a carbon-based nanomaterial exhibited greater antioxidant capacity than the free form. The antioxidant activity of GQDs paired with that of resveratrol had a synergistic impact, which meant that the combined activity was greater than the activities of the nanomaterial and the chemical taken separately. In addition, a novel use of GQDs has been investigated: they have the potential to act as a photoprotective nanomaterial for resveratrol. In this capacity, they would protect the polyphenol from the damaging effects of UV radiation and slow down its rate of isomerization. In order to achieve maximum suppression of the bioactive isomeric transition, Penalver et al. studied several parameters impacting the adsorption efficacy (AE) and loading capacity (LC) of resveratrol into the nanomaterial (Fig. 7.9) [75]. Adsorption of resveratrol to GQDs substantially inhibits the trans-to-cis-resveratrol conversion process under light-induced radiation, thereby conferring photostability on the compound. Various parameters that can affect the loading capacity and adsorption efficiency of resveratrol on GQDs have been investigated. Several methods prove the interaction, thus conforming to the non-toxicity at higher concentrations at which isomerization inhibition occurs. This adsorption also suggests a rise in the polyphenol’s antioxidant activity. This proves that GQDs have the potential to be an efficient trans-resveratrol delivery mechanism for food systems.

7.3.9 Polymeric Nanoparticles Utilizing a variety of polymers, polymeric nanoparticles have been developed. In the synthesis of polymeric nanoparticles, synthetic polymers such as poly(caprolactone) (PCL), poly(ethylene glycol) (PEG), poly(lactide) (PLA), and poly(lactide-coglycolide) (PLGA) as well as natural polymers such as alginate and chitosan, are frequently employed. phytochemicals may be affixed to polymers or encased in polymeric nanoparticles in order to increase their prolonged and regulated release and bioavailability. Polymeric nanoparticles range in size from 10 to 100 nm

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Fig. 7.9 Quantum dots of graphene are an effective nanomaterial to enhance trans-resveratrol photostability in food samples. Reprinted with permission from Food Chemistry, Copyright 2022, Elsevier [75]

and are colloidal in composition [76]. Therapeutic phytochemicals can be covalently attached, adsorb, or be trapped by the special surface chemistry of polymeric nanoparticles to significantly increase delivery. To treat chronic disorders, however, more research is required on the metabolism and safety of polymeric nanoparticles over time [77]. It was discovered through the use of a rodent model that the biodegradable polymeric formulation that contained Syzygium cumini was able to maintain the antioxidant activity of the plant extract [78]. In this study, the authors analyzed and compared the efficiency of an aqueous extract of Syzygium cumini seeds (ASc) and polymeric nanoparticles containing ASc (NPASc) against diabetes complications, as well as the toxicity effect of each treatment in vivo (Fig. 7.10a). Chromatogram analysis revealed that S. cumini’s composition was unaffected, and NPASc demonstrated properties consistent with nanometric systems. The new formulation kept the extract’s antioxidant qualities as well as its substantial protection against oxidized low-density lipoprotein (ox-LDL). In comparison to ASc, NPASc has stronger antifungal action against Candida guilliermondii and Candida haemulonii. Rats and the Artemia salina lethality assay showed no signs of acute harm. These results indicate the potential for S. cumini to be used more widely to treat its chronic consequences. The lack of toxicity of the nanoparticles suggests that NPASc may be a safe candidate for medication delivery systems. When AgNPs were green-synthesized using Vitex negundo L. extracts, the inhibitory effect on human colon cancer cell lines was maintained [79]. The authors used the human colon cancer cell line HCT15 to demonstrate the anticancer efficacy of silver nanoparticles produced from Vitex negundo L. leaf extract. The characterization of silver nanoparticles included techniques such as energy-dispersive spectroscopy (EDS), TEM, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR), following the initial synthesis determination using the UV–visible spectrum. The toxicity assessment involved analyzing alterations in cell morphology, cell viability, nuclear fragmentation, cell cycle distribution, and performing the comet

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Fig. 7.10 a Illustration depicting the formulation of biodegradable polymeric nanoparticles containing syzygium cumini: Investigation of phytochemical profile, antioxidant and antifungal activity, and evaluation of in vivo toxicity. Reprinted with permission from Industrial Crops and Products, Copyright 2016, Elsevier [78]. b Analysis of HCT15-treated cell cycle. Histograms displaying cell population distribution based on DNA content using propidium iodide staining. a Control; b IC50 concentration (20 μg/ml); c Maximum concentration (100 μg/ml). Reprinted with permission from Process Biochemistry, Copyright 2013, Elsevier [79]

assay. MTT assay was utilized to determine the percentage of viable cells. Biosynthesized AgNPs inhibited the proliferation of the human colon cancer cell line HCT15 with an IC50 of 20 g/ml over a 48-h incubation period. Apoptosis was confirmed by conducting nuclear morphological analysis with propidium iodide staining and evaluating DNA fragmentation using single-cell gel electrophoresis, indicating that

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silver nanoparticles have the ability to trigger programmed cell death. Silver nanoparticles inhibited HCT15 cells in the G0/G1 and G2/M phases, resulting in a decrease in the S-phase (Fig. 7.10b). In order to exert their antiproliferative effects, silver nanoparticles may inhibit colon cancer cell proliferation, prevent the G0/G1 phase, reduce DNA synthesis, and induce apoptosis. Mirakabad et al. demonstrated that PLGA-PEG nanoparticles containing curcumin inhibit the proliferation of the MCF-7 human breast cancer cell line significantly more than unbound curcumin [80]. Result shows that the release of curcumin from PLGA-PEG particles is dose- and time-dependent, indicating that the inhibition of cancerous cell lines is also dose- and time-dependent. In order to distinguish between healthy and malignant cells, PLGA-PEG nanoparticles can be modified with cell surface receptors that can be overexpressed in cancer cells. Moreover, curcuminloaded PLGA-PEG may one day be used in a clinical trial for breast cancer patients if in vivo studies support its utility. Before curcumin-loaded PLGA-PEG nanoparticle technology can function as the next generation of drug-delivery systems to treat breast cancer, it must undergo further development. As reported, resveratrol is a natural phenol with potential antitumor properties; however, its poor stability and low water solubility make it ineffective for the treatment of in vivo cancer. For enhanced stability and regulated distribution, Jung et al. devised polythene glycol-polylactic acid (PEG-PLA; M.W. 5000-5000) nanoparticles infused with resveratrol [81]. In vitro and in vivo analyses of its metabolic and antitumor activities have been conducted. CT26 colon cancer cells treated for 72 h with 40 and 20 μM resveratrol nanoparticles exhibited a significant reduction in cell number to 5.6% and colony-forming capacity to 6.2%, compared to control cells. Increased apoptotic cell death has been observed in flow cytometry and western blot analysis, and resveratrol nanoparticles dramatically decreased 18F FDG absorption and reactive oxygen species generation. When compared to free resveratrol, all of these effects are significantly higher or comparable. Resveratrol nanoparticles showed a significant reduction in 18F FDG uptake by Positron emission tomography/computed tomography (PET/CT), by day 4 of their intravenous administration in animals having CT26 tumors. In comparison to the control group receiving empty nanoparticles injections, resveratrol nanoparticles longer treatment resulted in a slow growth of the tumor and an increase in the survival rate. These findings suggest that PEG-PLA NP loading preserves the metabolic and antitumor effects of resveratrol in vitro and in vivo and offers a positive view on the potential of polymeric nanoparticles as a potent vehicle for resveratrol delivery in the treatment of cancer. The nanoparticle formulation of curcumin using Eudragit® RLPO (ERL) exhibited reduced particle sizes (245 ± 2 nm) and improved redispersibility after freezedrying compared to poly(lactic-coglycolic acid) (PLGA) and polycaprolactone (PCL) nanoparticles [82]. The curcumin-loaded Eudragit® RLPO (ERL) nanoparticles demonstrated a lower encapsulation efficiency of curcumin (62%) compared to PLGA and PCL nanoparticles (90% and 99%, respectively). However, the ERL nanoparticles exhibited a fast release of curcumin, with 91% released within one hour. All three types of curcumin-loaded nanoparticles developed in this study showed

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compatibility with intestinal cells. Among them, the ERL nanoparticles show the most potential as a vehicle to enhance the oral bioavailability of curcumin. Udompornmongkol et al. created polymeric nanoparticles as drug carriers for encapsulated curcumin, which has enhanced anticolorectal cancer properties [83]. Using emulsification and solvent diffusion, nanoparticles were fabricated from the natural polysaccharides chitosan and gum arabic. Utilizing FTIR spectroscopy and differential scanning calorimetry, it was possible to successfully synthesize curcumin nanoparticles and prove their existence. The findings indicated that curcumin could be encapsulated inside of carriers that had a positive surface charge of + 48 mV, a particle size of 136 nm, and a high encapsulation effectiveness of 95%. According to the findings of in vitro release experiments, the curcumin nanoparticles displayed resistance to hydrolysis by the enzymes found in the small intestine and gastric acid, which suggests that they have the capacity to remain intact and make it to the colon. Additionally, when compared to free curcumin, the increased cellular absorption of curcumin nanoparticles resulted in higher anticolorectal cancer benefits. Chitosan and gum arabic nanoparticles had superior anticancer efficacy against colon cancer and were excellent at encapsulating curcumin. Oyeyemi et al. evaluated the antiplasmodial activity and safety of nanoparticles containing curcumin and artesunate in a mouse model [84]. By evaporating the solvent from an oil-in-water single emulsion, curcumin and artesunate were incorporated into poly (D,L-lactic-coglycolic acid) (PLGA). Characterization of the generated nanoparticles included determining their size, PDI, zeta potential, and entrapment efficiency. A determination was also made regarding the in vitro release profile of the medicine. It was determined that CAPLGA nanoparticles had antiplasmodial action at doses of 5 and 10 mg/kg when Plasmodium berghei was used as the test organism. On days 5 and 8, assessments of the substance’s efficacy were made, and investigations into the toxicity of the substance to the liver and the blood were carried out. With a drug entrapment effectiveness of 22.3 ± 0.4%, the drug-loaded PLGA nanoformulation had an average particle size of 251.1 nm and a particle size distribution of spherical particles. The PLGA nanoparticles demonstrated sustained drug release over the course of a week. Outperforming the positive control group, the CA-PLGA 5 mg/kg group consistently and significantly inhibited the development of P. berghei, with suppression rates of 79.0% on day 5 and 72.5% on day 8. When compared to the group that served as the negative control, the aspartate aminotransferase (AST) levels in the group that was treated with microCA-PLGA at doses of 5 and 10 mg/kg resulted in a substantial decrease. Although the levels of alanine aminotransferase (ALT) were lower in the group that was treated with microCA-PLGA compared to the group that served as the negative control, the difference did not reach the level of statistical significance. Only the platelet counts were significantly greater in the positive control group, whereas the exposed groups did not show any significant differences from one another in any of the blood parameters that were measured. This research demonstrates a straightforward method that is both efficient and effective for the dual encapsulation of curcumin and artesunate, which leads to increased antiplasmodial action with minimal side effects.

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In cellular and animal models of Huntington’s and Alzheimer’s diseases, quercetin exhibited neuroprotective properties, as reported. However, due to its low solubility in water and cytotoxicity at working concentrations between 20 and 100 μM, its therapeutic applicability is limited. Nanoquercetin inhibits polyglutamine (mutant huntingtin) aggregation in a cell model for Huntington’s disease and possesses antiamyloidogenic activity at lesser quercetin concentrations (one micromolar) (Fig. 7.11) [85]. Nanoquercetin refers to a polyaspartic acid-based polymer micelle that encapsulates quercetin at a concentration of 3–5% by weight. These micelles have a hydrodynamic size of approximately 100 nm. Upon cellular uptake via endocytosis, nanoquercetin gradually releases quercetin molecules over a period exceeding three days. This controlled release mechanism enhances its antiamyloidogenic properties by promoting upregulated autophagy processes. The findings from this study suggest that nanoformulations of antiamyloidogenic compounds may exhibit greater efficacy compared to individual molecules alone. In a separate investigation, Sunoqrot et al. developed polymeric nanoparticles composed of quercetin for oral administration. These nanoparticles were based on the pH-sensitive polymer Eudragit® S100 and aimed to achieve targeted drug release specific to the colon pH environment [86]. Nanoparticles with a mean diameter of 66.8 nm and a surface charge of − 5.2 mV were created via nanoprecipitation. An average of 2.2% by weight of quercetin was encapsulated within nanoparticles with a 41.8% encapsulation efficiency. Intermolecular interactions, most likely involving hydrogen bonding, increased the drug loading of quercetin in Eudragit® S100 nanoparticles. X-ray diffraction examination also revealed the existence of amorphous material within the nanoparticles. In vitro release tests found that drug release was slowed at acidic pH levels, but complete release was observed within 24 h at pH 7.2. When compared to free quercetin (IC50 = 65.1 μM), the cytotoxicity of quercetin-loaded nanoparticles against CT26 murine colon cancer cells was much higher (IC50 = 0.8 μM). These findings show that this nanomedicine could be used to deliver quercetin to the colon in diseases such as colon cancer.

7.4 Antimicrobial Activity of Nanophytochemicals To adhere to the fundamental principles of green chemistry, researchers have focused on developing ecofriendly methods for synthesizing metal nanoparticles. One such approach involves utilizing plant extracts as reducing agents in the nanoparticle synthesis process [87, 88]. For the production of diverse antibacterial metal nanocomposites, these methods have proven to be ecofriendly and cost-effective. Plants contain soluble carbohydrates, phenolic acids, alkaloids, flavonoids, and terpenoids, among other phytochemicals. In the synthesis of antimicrobial nanoparticles, they can therefore function as reducing and stabilizing agents [89]. Nanoparticles mediated by plants are alternate treatments and growth regulators for viral infections. Introducing viruses into a host is highly irresponsible and calls for an accelerated translation process to increase their colony numbers. The biosynthesis of silver nanoparticles

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Fig. 7.11 Schematic of quercetin encapsulated polymer nanoparticle for inhibiting intracellular polyglutamine aggregation. Reprinted with permission from ACS Applied Bio Materials, Copyright 2019, American Chemical Society [85]

can act as effective and versatile antiviral agents, impeding the functioning of virus cells. Candida vaginitis, also known as vulvovaginal candidiasis (VVC), is a common fungal infection that causes irritation, discomfort, and inflammation in the vaginal area. In spite of how common it is, the treatments that are currently available have poor efficacy and a high likelihood of recurrence. In addition, the increasing problem of resistance to azole drugs that are utilized in the currently available treatments underscores the requirement for more effective therapeutic choices. The use of antimicrobial polyphenols as part of a therapy strategy that targets many pathways at once is an example of a novel technique. In this particular setting, Giordani and colleagues developed novel liposomes that are capable of simultaneously delivering two different polyphenols (quercetin and gallic acid). After being released into the vaginal canal, these polyphenols work together in a synergistic manner to remove the infection and improve the symptoms of VVC (Fig. 7.12) [90]. Gallic acid was selected for its purported antifungal properties, while quercetin was chosen for its antipruritic and anti-inflammatory properties. The authors have synthesized approximately 200 nm-sized liposomes containing either quercetin (LP-Q), gallic acid (LPGA), or both polyphenols (LP-Q+GA). Quercetin was effectively entrapped in both LP-Q and LP-Q+GA (85%), but gallic acid was more effectively entrapped in LPQ+GA (30%) than in LP-GA (25%). Liposomes, specifically LP-Q+GA, enhanced the sustained release of polyphenols. The interaction between quercetin and gallic acid enhanced the antioxidant activity of a single polyphenol. Polyphenol-liposomes possessed stronger anti-inflammatory properties than pure polyphenols and were non-cytotoxic. Ultimately, LP-GA and LP-Q+GA inhibited C. albicans development significantly.

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Fig. 7.12 Effect of quercetin and gallic acid loaded liposome in treatment of VVC infection, adapted from [90]

In another approach, Almeida et al. developed micellar formulations of resveratrol and investigated their cytotoxic and antibacterial properties [91]. Different quantities of F127 (5 or 10% w/w) and resveratrol (500 or 5000 μM) were used to prepare the formulations via the cold dispersion method. Its antimicrobial effect has been evaluated on different microorganisms, including E. coli, S. aureus, and C. albicans. Monodisperse formulations (10% w/w F127 and 5000 μM resveratrol) with a high encapsulation rate have been selected for the antimicrobial activity assay. It was evident from the results that MS-10+RES-3 was able to maintain the antibacterial and cytotoxic effects that resveratrol possessed. At each and every concentration that was evaluated, both MS-10+RES-3 and free resveratrol were successful in reducing the total number of viable S. aureus germs. On the other hand, MS-10+RES-3 was significantly more effective than free resveratrol in all of the concentrations that were evaluated. At doses of 62.5 μM and 7.81 μM, respectively, MS-10+RES-3 and free resveratrol were both effective in reducing the number of live E. coli bacteria. Only the highest doses of free resveratrol and MS-10+RES-3 (250 μM) were able to significantly reduce the amount of C. albicans bacteria that were viable. The results of this study, which is the first of its kind to examine the antibacterial activity and cytotoxicity of micelles containing resveratrol on bladder cancer cells, reveal

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that micellar nanostructures may also sustain the biological activity of resveratrol. Table 7.1 shows the various based phytochemical delivery system.

7.5 Summary This chapter examines how the use of nanocarriers can improve both the transport and stability of phytochemicals in food. The chapter starts off with an explanation of the concept, focusing on the role that nanocarriers could play in enhancing therapeutic efficacy and the ability of phytochemicals to target specific areas of the body. The limitations of phytochemicals are also examined, with a particular emphasis placed on the difficulties associated with condition optimization and stability. These constraints lay the groundwork for the investigation of nanomaterials as nanocarriers. This chapter discusses several different types of nanocarriers, including liposomes, niosomes, bilosomes, archaeosomes, solid lipid nanoparticles, carbon nanotubes, dendrimers, quantum dots, and polymeric nanoparticles. When it comes to transporting phytochemicals, many types of nanocarriers are analyzed in terms of their structures, properties, and possible uses. The antibacterial action of nanophytochemicals is also discussed in this chapter. This section sheds light on the ability of nanophytochemicals to combat microbial infections found in food. In this section, we investigate the potential health advantages connected with phytochemicals as well as the antimicrobial effects that phytochemicals have. This summary offers a condensed overview of the primary topics that have been covered throughout the chapter. The significance of nanocarriers in increasing the bioavailability, stability, and antibacterial characteristics of phytochemicals found in food is emphasized throughout this article. In general, the purpose of this chapter is to present a thorough investigation into nanocarriers as a unique method for the delivery of phytochemicals in food. This chapter makes a contribution to the advancement of both the study of and the application of nanotechnology in food science by addressing the limitations of phytochemicals, investigating various nanomaterials as carriers, and exploring the antimicrobial properties of the phytochemicals.

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Table 7.1 Various nanocarrier-based phytochemicals delivery system Nanoformulations

Phytochemical

Observation

Reference

PLGA-casein core/ Epigallocatechin shell nanoparticles gallate (EGCG)

The core/shell nanocarrier [92] demonstrated a sequential release of EGCG and paclitaxel, which had a synergistic effect on paclitaxel-resistant MDA-MB-231 cells. This sensitized the cells to paclitaxel treatment, resulting in cell death. Furthermore, the nanocarrier inhibited the activation of NF-B, downregulated genes associated with angiogenesis, tumor metastasis, and tumor survival. Notably, it also suppressed the production of P-glycoprotein induced by paclitaxel, both at the protein and gene levels

Dendrimers

Drug-dendrimers have global [93] binding constants ranging from 102 to 103 M−1 . Curcumin exhibited greater drug-polymer stability than cisplatin, genistein, and resveratrol. The stability of genisten-PAMAM-G4 was greater than that of curcumin-PAMAM-G4 and resveratrol-PAMAM-G4 (G = 4.75 kcal/mol)

Resveratrol, genistein and curcumin

Silver nanoparticles P. geminiflorum extract (PE)

In vitro, silver nanoparticles and AgNPs-PE at 100 g/ml effectively suppressed Fusarium oxysporum. When sprayed on tomato plants under regulated conditions, the same remedies tested against Fusarium produced nearly one hundred percent plant survival without detectable phytotoxicity

[94]

Zinc oxide nanocomposite

Ethanol extract and Dodonaea viscosa and Juniperus procerus fractions

At 2.5 and 1.25 μg/mL MIC, nanocomposites exhibited remarkable antibacterial efficacy against Staphylococcus aureus

[95]

Chitosan nanoparticles

Catechin and According to the current study, [96] epigallocatechin gallate encapsulating catechins in chitosan nanoparticles improves their intestinal absorption and is a promising strategy for enhancing their bioavailability (continued)

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Table 7.1 (continued) Nanoformulations

Phytochemical

Observation

Selenium nanoparticles

Ferulic acid

Ferulic acid selenium [97] nanoparticles suppressed HepG2 cell growth by triggering cell death via the mitochondrial route; ferulic acid selenium nanoparticles’ anticancer effects may also be due to their interaction with DNA

Reference

Arginine-based poly(ester urea urethane) nanoparticles

Gambogic acid

The FA-Arg-PEUU nanoparticle [98] carriers loaded with gambogic acid (GA) demonstrated significant inhibition of MMP-2 and MMP-9 activity in cancer cells, even at low concentrations of 0.6 g/mL. This suggests that the GA-loaded Arg-PEUU nanoparticles have the potential to effectively suppress cancer cell invasion and metastasis

Gold nanoclusters

Kaempferol

The synthesized kaempferol gold [99] nanoclusters primarily targeted and damaged cancer cell nuclei. This nanocluster was less toxic to normal human cells and more toxic to the A549 lung cancer cell, making it suitable for anticancer drug delivery and bioimaging applications

Gold nanoparticles

Lycopene

The combination of lycopene and gold nanoparticle nanoemulsion shows promise as a viable treatment for colon cancer. The nanoemulsion inhibited the expression of Bcl-2, procaspases-8, -3, pro-MMP-2/ 9and -9, PARP-1, Akt, and NF-B while increasing the expression of Bax and E-cadherin

[100]

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48. Kumar, M., et al., N-desmethyl tamoxifen and quercetin-loaded multiwalled CNTs: A synergistic approach to overcome MDR in cancer cells. Mater Sci Eng C Mater Biol Appl, 2018. 89: p. 274–282. 49. Huang, D. and D. Wu, Biodegradable dendrimers for drug delivery. Materials Science and Engineering: C, 2018. 90: p. 713–727. 50. Tripathy, S. and M.K. Das, Dendrimers and their applications as novel drug delivery carriers. Journal of Applied Pharmaceutical Science, 2013. 3(9): p. 142–149. 51. Kurtoglu, Y.E., et al., Drug release characteristics of PAMAM dendrimer–drug conjugates with different linkers. International journal of pharmaceutics, 2010. 384(1–2): p. 189–194. 52. Zhu, S., et al., Partly PEGylated polyamidoamine dendrimer for tumor-selective targeting of doxorubicin: the effects of PEGylation degree and drug conjugation style. Biomaterials, 2010. 31(6): p. 1360–1371. 53. Madaan, K., V. Lather, and D. Pandita, Evaluation of polyamidoamine dendrimers as potential carriers for quercetin, a versatile flavonoid. Drug Delivery, 2016. 23(1): p. 254–262. 54. Yousefi, M., A. Narmani, and S.M. Jafari, Dendrimers as efficient nanocarriers for the protection and delivery of bioactive phytochemicals. Advances in Colloid and Interface Science, 2020. 278: p. 102125. 55. Wang, L., et al., Encapsulation of curcumin within poly (amidoamine) dendrimers for delivery to cancer cells. Journal of Materials Science: Materials in Medicine, 2013. 24: p. 2137–2144. 56. Chauhan, A.S., Dendrimer nanotechnology for enhanced formulation and controlled delivery of resveratrol. Annals of the New York Academy of Sciences, 2015. 1348(1): p. 134–140. 57. Wang, Q., et al., Effect of the structure of gallic acid and its derivatives on their interaction with plant ferritin. Food chemistry, 2016. 213: p. 260–267. 58. Abdou, E.M. and M.M. Masoud, Gallic acid–PAMAM and gallic acid–phospholipid conjugates, physicochemical characterization and in vivo evaluation. Pharmaceutical development and technology, 2018. 23(1): p. 55–66. 59. Cruz, L., et al., Impact of a water-soluble gallic acid-based dendrimer on the color-stabilizing mechanisms of anthocyanins. Chemistry–A European Journal, 2019. 25(50): p. 11696–11706. 60. Gupta, L., et al., Dendrimer encapsulated and conjugated delivery of berberine: A novel approach mitigating toxicity and improving in vivo pharmacokinetics. International journal of pharmaceutics, 2017. 528(1–2): p. 88–99. 61. Chen, W., et al., Bioavailability study of berberine and the enhancing effects of TPGS on intestinal absorption in rats. Aaps Pharmscitech, 2011. 12: p. 705–711. 62. Laskar, P., et al., Camptothecin-based dendrimersomes for gene delivery and redox-responsive drug delivery to cancer cells. Nanoscale, 2019. 11(42): p. 20058–20071. 63. Narmani, A., et al., Folic acid functionalized nanoparticles as pharmaceutical carriers in drug delivery systems. Drug development research, 2019. 80(4): p. 404–424. 64. Mishra, V., U. Gupta, and N. Jain, Influence of different generations of poly (propylene imine) dendrimers on human erythrocytes. Die Pharmazie-An International Journal of Pharmaceutical Sciences, 2010. 65(12): p. 891–895. 65. Kesharwani, P., R.K. Tekade, and N.K. Jain, Generation dependent safety and efficacy of folic acid conjugated dendrimer based anticancer drug formulations. Pharmaceutical research, 2015. 32: p. 1438–1450. 66. Shao, N., et al., Comparison of generation 3 polyamidoamine dendrimer and generation 4 polypropylenimine dendrimer on drug loading, complex structure, release behavior, and cytotoxicity. International journal of nanomedicine, 2011: p. 3361–3372. 67. Matea, C.T., et al., Quantum dots in imaging, drug delivery and sensor applications. International journal of nanomedicine, 2017. 12: p. 5421. 68. Kumari, A., S.K. Khare, and J. Kundu, Adverse effect of CdTe quantum dots on the cell membrane of Bacillus subtilis: Insight from microscopy. Nano-Structures & Nano-Objects, 2017. 12: p. 19–26. 69. Zhang, Y., Allyl isothiocyanate as a cancer chemopreventive phytochemical. Molecular nutrition & food research, 2010. 54(1): p. 127–135.

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Chapter 8

Regulatory and Safety Concerns Regarding the Use of Active Nanomaterials in Food Industry

Abstract Last but not least, one of the main worries about using nanoparticles in the food business is safety. As a result, this chapter discusses risk assessment as well as safety standards for using nanomaterials in the food and agriculture industries. Innovation in nanotechnology resulted in the emergence of numerous nano-based scientific and industrial fields, as well as goods utilizing nanomaterials. However, the use of nanotechnology in the food industry has brought up ethical and regulatory concerns as well as safety concerns for people and the environment. Nanomaterials differ biologically and physiologically from their usual form, which can have unforeseen and dangerous effects. Even though the food sector has extensively researched the nanoencapsulation technology of bioactive chemicals, the dangerous effects of nanomaterials when consumed orally remain a big worry. Depending on how susceptible a nanocarrier is to being hydrolyzed by different digestive enzymes and gastrointestinal tract circumstances, the environment of the gastrointestinal tract mostly determines the fate of the nanocarrier. However, since unbound nanocarriers are able to pass through intestinal and cellular barriers, the bioaccumulation of foreign substances in human blood, cells, and tissues increases. Due to their toxicity, the organic solvents and emulsifiers utilized in the manufacture of nanocarriers raise the risk factor. Organic solvents can be eliminated by the evaporation process, however unanticipated residual solvents that may remain in the finished product and have an unknown concentration create safety concerns. The safe usage level of hazardous solvents and emulsifiers has been reported by the World Health Organization (WHO), the Food and Drug Administration (FDA), and the European Food Safety Authority (EFSA). There is little evidence now available about the risk of nanotechnology, so further research is needed to estimate the risk. Exploring nanomaterials direct and indirect effects on human health is necessary, as well as their behavior in the gastrointestinal tract, biological fate after digestion, and potential interactions with biological systems. To safeguard the general population from any potential negative effects of nanotechnology, regulatory measures are necessary. Several world organizations regulate issues related to the effect of nanomaterials used in food on consumer health. As there is a lack of regulation and risk management systems for nanotechnology, the safety of nanomaterials in the food industry can be assured by information transparency and new nanotechnology regulations. Moreover, the small size of nanomaterials can enhance their bioaccumulation in © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4_8

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body organs and tissues, i.e., silica nanoparticles are used as anticaking agents but proved to be cytotoxic when exposed to human lungs. Dissolution can be affected by various factors like surface energy, particle surface morphology, aggregation, adsorption, and concentration. A migration study of nanoparticles from food packaging demonstrated the migration of copper and silver from nanocomposites and found that nanofiller percentage in nanocomposites governs the migration more than particle size, contact time, or temperature. Different nanomaterials have different properties, so toxicity can be studied on a case-by-case basis. Moreover, regulatory bodies should develop the standards to ensure the quality of commercial products, health and safety, and environmental regulations.

8.1 Introduction Nanotechnology has piqued the curiosity of many scientists and technologists due to its unique features and possible applications. Nanotechnology has been used in the food sector for a variety of applications, including food processing, packaging, and preservation [1]. Nanotechnology has enabled the development of novel and creative food products with better attributes such as texture, flavor, and shelf life. It has been used in the food industry for a variety of purposes, such as food processing, packaging, and preservation [2]. Some examples are as follows: (i) Food Processing: Nanotechnology has been used to produce novel food processing procedures that can improve nutritional content and food quality. Nanoscale emulsions, for example, have been utilized to increase the solubility and bioavailability of lipophilic vitamins like vitamin E and carotenoids in food products. Furthermore, nanocarriers have been used to encapsulate bioactive compounds like omega-3 fatty acids and probiotics in order to improve their stability and delivery [3, 4]. (ii) Food Packaging: Nanotechnology has also been used to create sophisticated food packaging materials that can increase the shelf life of food products while decreasing the danger of deterioration and contamination. For example, nanocomposites are being utilized to develop packaging sheets that are highly effective at blocking oxygen, moisture, and UV light, preventing food degradation and bacterial growth. Furthermore, nanosensors for detecting and monitoring the quality and safety of packaged food products, such as the presence of oxygen, carbon dioxide, and microbial contaminants, have been developed. (iii) Food Preservation: Nanotechnology has also been employed to produce unique preservation strategies that can keep food products fresh and quality for a longer period of time. Nanoscale silver particles, for example, have been utilized as antibacterial agents in food products like fruits and vegetables to prevent spoilage and contamination. Figure 8.1 depicts nanotechnology applications in all disciplines, including agriculture, food processing safety, packaging, and nutrition science. Furthermore, nanocomposites have been developed to develop active packaging systems that can release antimicrobial agents or antioxidants to extend food product shelf life [5, 6]. Overall, the use of nanotechnology in the food industry has opened up new opportunities for the development of innovative and sustainable solutions

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Fig. 8.1 Applications of nanotechnology that are feasible throughout many industries, from agriculture to food processing, packaging, and nutrition [1]

to improve the safety, quality, and nutritional value of food products [7]. Nanotechnology has enabled the creation of unique and inventive food products with improved texture, flavor, and shelf life. Nanosensors and nanocapsules, for example, can be used to detect and release tastes and nutrients in food. This enables more accurate and controlled delivery of these traits, resulting in a more satisfying sensory experience for customers [8, 9]. Furthermore, nanoparticles can be used to improve the texture and appearance of foods, such as when nanoclay particles are used to improve the mechanical properties of food packaging materials [10]. Nanoparticles can also be utilized as antibacterial agents, extending the shelf life of food and decreasing the need for preservatives [11]. Overall, the application of nanotechnology in the food sector has the potential to transform the way we manufacture, package, and consume food, resulting in safer, healthier, and more sustainable food items. However, the potential safety and regulatory concerns associated with the use of nanomaterials in food, as well as the ethical implications of using such technology, must be considered. The use of nanoparticles in the food sector, on the other hand, has prompted worries about their safety and potential hazards to human health and the environment. Nanomaterials have different biological and physiological properties than ordinary materials, which can result in unforeseen outcomes when consumed. Concerns have been expressed regarding the safety of nanoparticles in the food industry, as well as their potential risks to human health and the environment. Nanoparticles’ distinctive properties can result in unpredictable and unintended effects on living organisms. Nanoparticles’ small size and high surface area can increase their reactivity and ability to permeate biological membranes, which may result in toxicity. Nanoparticles that have been ingested can accumulate in tissues and organs, causing negative effects

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such as inflammation, oxidative stress, and DNA damage. In addition, nanoparticles may have environmental consequences, such as accumulation in soil and water systems and potential effects on non-target organisms. Consequently, it is essential to evaluate the safety and potential dangers associated with the use of nanoparticles in food products. Due to their small size and large surface-to-volume ratio, nanomaterials have distinct biological and physiological properties than conventional materials. These properties can have unanticipated effects when ingested, as they interact with biological systems in novel ways. For instance, nanoparticles may be more toxic than their larger counterparts because they can penetrate cells and tissues more readily and accumulate in specific organs. In addition, nanoparticles may have altered chemical reactivity and physical properties, which may influence their behavior in the body and toxicity potential. Inflammation, oxidative stress, DNA damage, and cellular function disruption are all potential unintended consequences of nanoparticle consumption. It is essential to note, however, that not all nanoparticles are dangerous; the potential hazards depend on the material’s specific properties and how it is used. Before incorporating nanomaterials into food products, it is crucial to conduct exhaustive risk assessments and safety evaluations. The purpose of this chapter is to discuss the safety and regulatory issues surrounding the use of active nanoparticles in the food business. Several safety and regulatory concerns are raised by the use of active nanoparticles in the food industry, including: (i) Risk assessment: The safety of nanoparticles in food products, including the risk assessment of these materials, is one of the main concerns. It is crucial to ascertain the potential risks associated with the use of nanoparticles in food products, along with their toxicology, exposure, and safety. (ii) Environmental impact: Nanoparticles have the potential to have an effect on the environment due to their unique properties, such as their small dimension and large surface area. Therefore, an environmental impact assessment of nanoparticles used in the food industry is required. (iii) Ethical considerations: The use of nanoparticles in food products raises ethical concerns, such as the absence of transparency and information regarding their safety and potential impact on human health and the environment. (iv) Regulatory requirements: Regulatory requirements and guidelines for the use of nanoparticles in the food industry are currently lacking. The regulatory agencies must ensure that nanoparticles used in food products are secure and do not pose a threat to consumers. (v) Consumer perception: The use of nanoparticles in food products can raise consumer concerns, which can have an effect on the acceptability and popularity of these products. To address consumers’ concerns regarding the safety of nanoparticles in food products, there is a need for transparency and open communication with consumers. Overall, the safety and regulatory issues surrounding the use of active nanoparticles in the food industry must be carefully evaluated to ensure that they do not pose a threat to human health and the environment [12]. Now is the time to work on enhancing the safety evaluations of nanoparticles in foods based on the exposure and toxic response mechanisms depicted in Fig. 8.2. Nanoparticles in food are associated with oxidative stress reactions, protein denaturation, and DNA damage. Globally, there is still no standardized safety review

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Fig. 8.2 Illustration of nanoparticles in food-related difficulties and their resolution [1]

methodology for nanoparticles, especially nano-based foods. It is essential to regulate the use of nanoparticles in food by devising risk assessments and safety risk management techniques that comply with twenty-first-century toxicity test goals and objectives [1]. It emphasizes the importance of risk assessment and safety requirements for nanoparticles used in food and agriculture. The following is a summary of the significance of risk assessment and safety requirements for nanoparticles used in food and agriculture [13]. (i) Protection of public health: Nanoparticles have the potential to be harmful to human health, particularly when ingested. To ensure that their use in food and agriculture does not pose a threat to public health, it is essential to assess the hazards associated with their application. (ii) Protection of the environment: The use of nanoparticles in agriculture can also have an effect on the soil and water quality. Consequently, it is essential to evaluate the risks associated with their use and to take the necessary precautions to protect the environment. (iii) Compliance with regulations: Standards and guidelines for the use of nanoparticles in food and agriculture have been established by regulatory bodies. Compliance with these regulations is required to ensure that the use of nanoparticles in these industries does not endanger public health or the environment. (iv) Transparency and trust: Conducting risk assessments and adhering to safety requirements can contribute to the development of trust and transparency among manufacturers, regulatory bodies, and consumers. This can foster the responsible application of nanoparticles in the food and agriculture industries. (v) Innovation and development: Risk assessment and safety requirements can facilitate the development and use of safe and innovative nanotechnology-based products in the food and agriculture industries [14]. This can

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Fig. 8.3 Application of nanotechnology to food safety, packaging, and processing [2]

contribute to the development of new and improved food products, as well as more sustainable and efficient agricultural practices. Figure 8.3 shows the application of nanotechnology to food safety, packaging, and processing. The chapter covers a variety of topics related to nanoparticles in food and agriculture, such as toxicity and risk assessment, public opinion, and regulatory difficulties. The chapter also discusses the present regulatory frameworks for nanomaterials in the food and agricultural industries, including those established by the WHO, FDA, and the EFSA. Finally, the chapter emphasizes the importance of additional research to fill knowledge gaps about the potential risks associated with the use of nanomaterials in the food industry. Overall, this chapter introduces the regulatory and safety considerations associated with the use of active nanoparticles in the food business. It emphasizes the importance of responsible innovation and regulation in order to assure the safety of nanomaterials for human health and the environment.

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8.2 Toxicity and Risk Assessment of Nanomaterials Used in Food Application To ensure the safety of nanomaterials used in food applications, it is essential to evaluate their toxicity and potential risks [15]. Due to their unique physicochemical properties, nanomaterials have the potential to interact with biological systems differently than their larger counterparts, leading to increased toxicity [16]. Prior to their use in food and agricultural products, accurate risk assessments and safety evaluations are essential [17]. For assessing the toxicity of nanomaterials, several methods are available, including in vitro and in vivo assays, physicochemical characterization, and computational modeling. The objective of these techniques is to assess the potential adverse effects of nanomaterials on human health and the environment. Figure 8.4 illustrates the classifications and various types of nanomaterials. In addition, the risk assessment of nanomaterials should consider the possibility of exposure via multiple routes, such as ingestion, inhalation, and skin contact. Before approving the use of nanomaterials in food applications, regulatory agencies must conduct safety and risk assessments to ensure their safety [12]. The evaluations consist of the evaluation of nanomaterials’ toxicity, exposure potential, and risk characterization. In addition, regulatory agencies mandate labeling requirements to inform consumers of nanomaterials’ presence in food products [18]. To ensure the

Fig. 8.4 Depicts the classification of diverse nanomaterials. Reprinted with permission from Journal of Molecular Liquids, Copyright 2023, Elsevier [17]

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safety of these products for human health and the environment, it is vital to assess the toxicity and risk of nanomaterials used in food applications [19]. To ensure the safe and responsible use of nanomaterials in the food and agriculture industries, proper safety evaluations and risk assessments, along with regulatory oversight and labeling requirements, are required [8].

8.2.1 Toxicity of Nanomaterials in Food This section discusses regarding the food nanomaterial toxicity. Nanomaterials’ unique properties make them useful for a variety of applications, including food packaging, processing, and preservation [20]. However, these characteristics also make them potentially toxic when ingested. Nanomaterials can interact with biological systems in unanticipated ways when ingested. For instance, nanoparticles can cross biological barriers that would normally prevent larger particles or molecules from accessing the body due to their diminutive size. This can cause nanoparticle accumulation in various organs and tissues, which can cause injury over time [21]. Due to their chemical properties, nanoparticles can also cause toxicity. When interacting with biological fluids, some nanoparticles may emit toxic substances, such as heavy metals or reactive oxygen species [17]. In addition, nanoparticles are capable of interacting with proteins and other biological molecules, which could potentially disrupt normal biological processes. As food is the primary source of exposure for most people, the toxicity of nanomaterials in food is a significant concern. Consequently, it is essential to evaluate the potential dangers associated with the use of nanomaterials in food products [22]. This involves conducting toxicity experiments to determine the effects of nanomaterial exposure on cells, tissues, and organisms. In addition, risk assessments should be conducted to evaluate the likelihood and severity of any potential adverse effects. These evaluations should consider factors such as dose, duration of exposure, and route of exposure (i.e., ingestion or inhalation).

8.2.2 Risk Assessment of Nanomaterials in Food Risk assessment is the process of identifying potential hazards, evaluating the likelihood and severity of damage, and implementing control or mitigation measures. Risk assessment in the context of nanomaterials in food involves evaluating potential adverse effects on human health and the environment [23]. Current approaches to assessing the risk posed by nanomaterials make use of regulatory frameworks and guidance documents that have been adapted to account for the unique properties of nanomaterials [24]. For instance, EFSA and FDA of the USA have devised specific guidance documents for the safety assessment of nanomaterials in food. These guidance documents include testing methods, exposure assessments, and hazard identification recommendations. Nonetheless, nanomaterials risk assessment is hampered

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by a number of limitations and obstacles. Lack of standardized testing methodologies for nanomaterials is one of the greatest obstacles. Nanomaterials’ distinctive properties necessitate the use of specialized testing methods that are not always available or well-established. Another difficulty is the dearth of information on nanomaterials’ toxicity and exposure. Numerous nanomaterials have not been exhaustively evaluated for their potential adverse effects, and little is known about their exposure levels in the food supply chain. In addition, the toxicity of nanomaterials can be influenced by a variety of factors, including their size, shape, surface area, and chemical composition, which complicates the risk assessment of nanomaterials. It is challenging to anticipate the behavior of nanomaterials in complex biological systems, such as the human body, as well as the potential for interactions with other substances, such as drugs or food ingredients. In conclusion, despite the fact that risk assessment is essential for ensuring the safety of nanomaterials in food, it is necessary to recognize the limitations and difficulties associated with the current approaches. Improving the accuracy and reliability of nanomaterials risk assessment requires continued research and development of testing methodologies, exposure assessment, and hazard identification.

8.2.3 Safety Requirements for Nanomaterials in Food Ensuring the safety of nanomaterials in food is a matter of utmost importance, and several regulatory agencies have implemented guidelines to ensure their safe application. Notably, the European Union (EU) and FDA of the USA are two prominent regulatory bodies that have established specific guidelines concerning nanomaterials in the food industry. To address the use of nanomaterials in food, the EU has introduced a regulation that requires the labeling of all food products containing nanomaterials. This regulation also mandates manufacturers to provide EFSA with safety data on the nanomaterials used in food, allowing for thorough risk assessment. Similarly, the FDA in the USA has developed guidelines pertaining to the utilization of nanomaterials in food products. These guidelines serve as a framework to ensure the safe incorporation of nanomaterials and provide recommendations for manufacturers to follow during the development and assessment of nanotechnologybased food products. By implementing these guidelines, both the EU and the FDA aim to address potential risks associated with nanomaterials in food and safeguard consumer health. These regulatory efforts aim to strike a balance between promoting innovation in the food industry and ensuring the safety of nanomaterials used in food products. The safety considerations related to the application of nanomaterials in food production and packaging are thoroughly examined. The authors specifically address potential risks linked to various nanomaterials, such as titanium dioxide, silver nanoparticles, and quantum dots, that are commonly employed in the food industry. Emphasis is placed on the necessity for comprehensive safety assessments of nanomaterials before their approval for use in food-related applications, taking into

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account factors such as toxicity, bioaccumulation, and potential environmental impacts. The article also highlights the existing regulatory frameworks governing the utilization of nanomaterials in food production and packaging, spanning regions including the USA, Europe, and Asia. It underscores the importance of international collaboration and standardization in effectively regulating the use of nanomaterials in the food industry to ensure consumer safety and environmental protection. Overall, the study provides a comprehensive and insightful overview of the safety concerns associated with nanomaterials in food production and packaging. It underscores the need for ongoing research, evaluation, and adherence to rigorous safety standards in this field. The article serves as a valuable resource for understanding the current state of knowledge and the regulatory landscape concerning nanomaterials in the context of food safety [8]. Nanomaterials are also used in food packaging to improve barrier properties, extend expiration life, and reduce food waste. However, the safety of these substances is crucial, as they can migrate from the packaging into the food, posing health risks. Consequently, numerous safety standards have been established for nanomaterials used in food packaging. The EU has issued regulations requiring food packaging manufacturers to undertake safety assessments on nanomaterials. The FDA in the USA also mandates manufacturers to provide data on the safety of nanomaterials utilized in food packaging. Thus, to assure the safety of consumers, safety requirements for nanomaterials in food are crucial. In order to ensure the secure use of nanomaterials in food products, regulatory bodies have established several guidelines and laws. The safety requirements for nanomaterials used in food packaging and food additives are essential for preventing potential health risks resulting from the migration of these materials from the packaging into the food. Figure 8.5 shows the application of nanotechnology in various sectors of the food industry, including materials, processing, products, and food safety and security.

8.2.4 Case Studies of Toxicity and Risk Assessment of Nanomaterials in Food This section presents case studies highlighting the toxicity and risk assessment of nanomaterials in the context of food applications. These case studies serve to underscore the importance of evaluating the safety of nanomaterials used in the food industry. Arshad et al. [25] conducted a comprehensive review of recent advancements and applications of lab-on-a-chip (LOC) nanomaterial-based devices in sustainable agrifood industries. These LOC devices offer rapid, sensitive, and precise analysis of food samples, making them increasingly popular in recent years. The utilization of nanomaterials in the fabrication of LOC devices is particularly noteworthy due to their unique properties, such as a large surface area and high reactivity. These nanomaterial-based LOC devices have found diverse applications

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Fig. 8.5 Application of nanotechnology in various sectors of the food industry, including materials, processing, products, and food safety and security [2]

in the agrifood industry, including the detection of pathogens, toxins, and pesticides in food samples. The incorporation of nanomaterials into LOC devices enables enhanced performance and improved sensitivity in food analysis. By exploring case studies and advancements in nanomaterial-based LOC devices, the article highlights the importance of evaluating the safety and potential risks associated with nanomaterials used in the food industry. It showcases the growing significance of employing advanced analytical tools to ensure the quality and safety of food products. The authors discuss the various nanomaterials used in LOC devices, including metal nanoparticles, carbon nanotubes, and quantum dots, as well as their benefits and drawbacks. They also provide an overview of the fabrication techniques used to develop these devices, including microfluidics and inkjet printing. In addition, the application of paper-based microfluidics for point-of-care diagnostics has also been discussed. The review emphasizes the potential of nanomaterial-based LOC devices for enhancing food safety and security, reducing food waste, and enhancing agricultural productivity as shown in Fig. 8.6. Nonetheless, the authors stress the need for cautious consideration of the potential health and environmental risks associated with the use of nanomaterials. Overall, the authors propose future research directions, such as the development of multifunctional LOC devices and the integration of artificial intelligence and machine learning algorithms for data analysis.

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Fig. 8.6 Applications of lab-on-a-chip devices based on nanomaterials for sustainable agrifood industries. Reprinted with permission from Trends in Food Science & Technology, Copyright 2023, Elsevier [25]

Titanium Dioxide Nanoparticles in Food Titanium dioxide (TiO2 ) nanoparticles are commonly used as a food additive in confections, baked products, and sauces to improve the appearance and texture of these foods [26]. Concerns exist, however, regarding the possible health dangers associated with the ingestion of TiO2 nanoparticles [27]. Several studies have demonstrated that TiO2 nanoparticles can induce oxidative stress and inflammation in the gut, leading to intestinal injury and impaired gut function [28]. In addition, TiO2 nanoparticles have been found to accumulate in various organs, including the liver, spleen, and kidneys, where they may have deleterious effects [29]. To evaluate the safety of TiO2 nanoparticles in food, scientists have conducted risk assessment studies. These studies have uncovered a number of areas of concern, including the potential for TiO2 nanoparticles to accumulate in the body and the absence of information regarding the effect of long-term exposure to these particles [30]. Regulatory agencies in some countries, such as France, have banned the use of TiO2 nanoparticles in food products, whereas regulatory agencies in others, such as the USA, continue to permit their use but require labeling of products containing these particles [31]. Chen et al. [29] present a summary of the safety of TiO2 nanoparticles used in culinary applications. Due to their potential toxicity, the safety of TiO2 nanoparticles, which are commonly used as food additives, especially as bleaching agents, has been a topic of concern [32]. The paper reviews the literature on the safety of TiO2 nanoparticles, including studies on their potential toxicity, absorption, distribution, metabolism, and excretion in the human body. The authors discovered that although

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TiO2 NPs are generally considered safe for use in food, there is still some uncertainty and variability in the data due to variations in particle size, surface coatings, and exposure levels. The paper also discuss the potential hazards associated with the use of TiO2 nanoparticles in food, such as their potential to induce oxidative stress, inflammation, and DNA damage, as well as their potential to cross the blood–brain barrier and accumulate in organs including the liver, spleen, and lungs. Overall, the authors conclude that while the safety of TiO2 nanoparticles in food is generally supported by the available data, additional research is necessary to fully comprehend their potential risks and develop more accurate risk assessment models. The authors suggest that regulatory agencies continue to monitor the use of TiO2 nanoparticles in food and update safety guidelines as required. Figure 8.7 depicts the in vivo destiny and biological mechanisms of TiO2 nanoparticles. According to the graph, TiO2 NPs have a very poor absorption rate through the gastrointestinal tract and are primarily ejected with feces. Under short-term and high-dose exposure, TiO2 nanoparticles have been observed to be transported and stored in various organs. However, no significant transport or accumulation has been detected under long-term and low-dose exposure. The liver is the primary organ affected by TiO2 nanoparticles, although adverse effects on the gastrointestinal tract, heart, spleen, kidney, and central nervous system have also been reported. The biological effects of TiO2 nanoparticles are attributed to both direct and indirect mechanisms. Through the direct pathway, TiO2 nanoparticles accumulate in organs and tissues, leading to direct injury. This accumulation in various organs is responsible for the observed adverse effects. Additionally, TiO2 nanoparticles can induce biological effects through indirect mechanisms, which may involve complex interactions with cellular components and signaling pathways. Understanding the transport, accumulation, and biological effects of TiO2 nanoparticles is crucial for assessing their potential risks and ensuring safety. Further research is needed to elucidate the mechanisms underlying these effects and develop appropriate risk assessment strategies for the use of TiO2 nanoparticles in various applications. TiO2 nanoparticles can also induce oxidative stress and inflammatory reactions via the indirect pathway, causing systemic damage. Overall, the image illustrates the complicated biological pathways of TiO2 nanoparticles and emphasizes the need for additional research into the health impacts of these nanoparticles. The graph also emphasizes the significance of risk assessment and regulation of TiO2 nanoparticles in culinary applications in order to maintain consumer safety.

Silver Nanoparticles in Food Packaging Silver nanoparticles are frequently employed in food packaging materials like plastic films and coatings due to their antimicrobial properties. These nanoparticles effectively inhibit the growth of bacteria and other microorganisms, thereby extending the shelf life of food products. The use of silver nanoparticles in food packaging aims to minimize the risk of contamination and maintain the quality and safety of the packaged food. By incorporating silver nanoparticles into packaging materials, a

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Fig. 8.7 Fate and biological mechanisms of titanium dioxide nanoparticles in vivo after oral intake. Reprinted with permission from NanoImpact, Copyright 2020, Elsevier [29]

protective barrier is created against microbial growth, reducing the need for chemical preservatives and enhancing food preservation [33, 34]. However, there are concerns about the potential migration of silver nanoparticles from packaging materials into food products [35]. Multiple studies have demonstrated that silver nanoparticles are deleterious to human cells and can induce oxidative stress and DNA damage [36]. In addition, various organs, including the liver, spleen, and kidneys, have been found to accumulate silver nanoparticles. The safety of silver nanoparticles used in food packaging has been evaluated through risk assessment studies. These studies have revealed several areas of concern, such as the potential for nanoparticle migration into food products and the paucity of information regarding the long-term effects of exposure to these particles. Regulatory agencies in some nations, such as the European Union, have imposed restrictions on the migration of nanoparticles of silver from food packaging materials. In addition, a number of businesses have created packaging alternatives that do not contain silver nanoparticles. Irene Zorraqun-Pea

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et al. [37] explored the potential use of silver nanoparticles as an antimicrobial agent against pathogenic microbes in food. The study assessed the effects of silver nanoparticles on the intestinal tract as well as the possible health risks associated with their use. The results indicated that silver nanoparticles have potent antimicrobial activity against foodborne pathogens, but their long-term use may have negative health effects. The study highlighted the need for additional research to establish silver nanoparticles’ safe and effective use in food applications. Figure 8.8 shows the possible factors and mechanisms underlying the antimicrobial activity of silver nanoparticles (AgNPs). The circle in the center of the diagram represents AgNPs, which have antimicrobial properties against a variety of infectious pathogens. The outer circles of the figure depict the factors that influence the antimicrobial activity of AgNPs, including their size, shape, surface charge, concentration, and exposure duration. The figure also suggests some of the potential antimicrobial mechanisms through which AgNPs may exert their activity. These mechanisms include disrupting the bacterial cell membrane, producing reactive oxygen species (ROS) that damage bacterial DNA, and interfering with the metabolic processes of bacteria. In addition, the figure illustrates the potential for AgNPs to induce resistance in bacteria via genetic mutation or horizontal gene transfer. Overall, the figure emphasizes the complexity of the mechanisms underlying the antimicrobial activity of AgNPs and the need for additional research to fully comprehend their potential advantages and limitations in food safety applications.

Zinc Oxide Nanoparticles in Food Additives Zinc oxide (ZnO) nanoparticles are commonly used as a food additive to improve the nutritional value of a variety of products, including breakfast cereals and dietary supplements [38]. However, there are concerns regarding the potential health hazards associated with ZnO nanoparticle ingestion. Multiple studies have demonstrated that ZnO nanoparticles can induce oxidative stress and inflammation in the gastrointestinal tract, which can result in intestinal injury and impaired gastrointestinal function [39]. In addition, ZnO nanoparticles have been found to accumulate in organs such as the liver, spleen, and kidneys, where they may have toxic effects. There have been risk assessment studies conducted to evaluate the safety of ZnO nanoparticles in food. Several areas of concern have been identified by these studies, including the potential accumulation of nanoparticles in the body and the paucity of information on the long-term effects of exposure to these particles [40]. In some nations, such as the European Union, regulatory agencies have placed restrictions on the use of ZnO nanoparticles in food products. In addition, a number of businesses have devised substitute food additives that do not contain ZnO nanoparticles. Youn and Choi [41] investigated the potential toxicity of zinc oxide nanoparticles added to food. The author discusses the dissolution, interaction, and fate of ZnO nanoparticles in the gastrointestinal tract, as well as their potential cytotoxicity and oral toxicity. The study suggests that pH and surface modification affect the dissolution of ZnO NPs in simulated gastric fluid. The interaction between ZnO NPs and food

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Fig. 8.8 Principal influencing factors and proposed mechanisms for the antimicrobial activity of silver nanoparticles [37]

components can influence their fate in the digestive tract. The author also investigates the cytotoxicity and oral toxicity of ZnO nanoparticles using in vitro and in vivo animal models, respectively. The conclusion of the study is that the cytotoxicity and oral toxicity of ZnO NPs depend on a number of factors, including particle size, surface modification, and exposure duration. The author suggests additional research to ascertain the safety of ZnO nanoparticles as a food additive. Figure 8.9 is a schematic representation of the dissolution properties of ZnO nanoparticles, the effects of environmental pH and the digestive systems used, and the interactions between ZnO and the matrices. The graph illustrates that the pH of the environment influences the dissolution of ZnO nanoparticles, with dissolution increasing at lower pH values. In addition, the figure depicts the various digestive systems used to evaluate the dissolution of ZnO nanoparticles, including simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The figure also depicts the interactions between ZnO nanoparticles and matrices, such as food and biological secretions. The interactions may influence the dissolution and release of Zn ions from the nanoparticles, thereby influencing the cytotoxicity and oral toxicity of ZnO nanoparticles. Overall, Fig. 8.9 provides an overview of the factors that can influence the dissolution and fate of ZnO nanoparticles in the gastrointestinal tract and emphasizes the importance of considering these factors when assessing their safety as a food additive.

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Fig. 8.9 Schematic representation of the dissolution properties of ZnO NPs as influenced by environmental pH, digestion systems, and the interactions between ZnO and matrices [41]

8.2.5 Future Directions for Toxicity and Risk Assessment of Nanomaterials in Food This section discusses the potential areas for future research and development in the field of food nanomaterial toxicity and risk assessment. As the current methods for nanomaterials risk assessment have a number of limitations and challenges, it is necessary to develop new approaches that can produce more accurate and trustworthy results [40]. Utilizing high-throughput screening methods, that can rapidly assess the toxicity of a large number of nanoparticles, is one of the promising approaches [42]. Most investigations on the toxicity of nanomaterials in food have concentrated on their immediate effects. However, the long-term effects of these nanoparticles, particularly their cumulative and chronic effects on human health, require investigation [43]. To ensure the safe use of nanomaterials in food, it is essential to inform the public of the potential risks and benefits associated with these nanoparticles. This can help establish trust and confidence in the food industry’s use of nanomaterials. This section concludes by emphasizing the significance of sustained research and development in the field of nanomaterials risk assessment in order to ensure the safe use of nanoparticles in the food industry. Steinhäuser and Sayre [43] discusses the dependability of methods and data used in the regulatory evaluation of nanomaterial hazards. The author emphasizes the difficulties in developing reliable methods for nanomaterial risk assessment, such as the lack of validated methods, the complexity of nanomaterials, and the variety of exposure scenarios. The author contends that existing regulatory frameworks may not be adequate to address the unique properties and potential hazards of nanomaterials. Thus, there is a need for the development of novel risk assessment strategies that are tailored to nanomaterials and account for their complexity. In addition, the importance of data quality and dependability in the risk assessment procedure is discussed. The author emphasizes the need for standardized data collection and analysis methods, as well as the significance of transparency

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and reproducibility in risk assessment. Overall, the paper emphasizes the need for continued research and development of dependable methods for nanomaterial risk assessment, as well as the significance of stringent data quality and regulatory process transparency. Similarly, Oomen et al. [44] provide an overview of the current status of risk assessment frameworks for nanomaterials and outline prospective directions for increasing their efficiency. The authors emphasize the significance of a well-defined and standardized risk assessment procedure for nanomaterials, which is crucial for ensuring the safety of these substances for human health and the environment. Beginning with a discussion of the scope of risk assessment frameworks for nanomaterials and the need for a comprehensive approach that takes into consideration all phases of the material’s life cycle, from production to disposal, the section proceeds to outline the need for a comprehensive approach. The authors also emphasize the significance of incorporating exposure assessments as an integral part of the risk assessment procedure, which should take into account various routes of exposure and the possibility of long-term exposure. The paper also discusses the current regulatory environment for nanomaterials, emphasizing the need for harmonization and standardization among regulatory bodies. The authors note that many existing regulations do not specifically address nanomaterials and suggest a proactive approach is required to assure the long-term safety of these substances. The authors then discuss the applicability of existing risk assessment frameworks for nanomaterials, noting that many of these frameworks were developed for conventional compounds and may not be applicable to nanomaterials due to their unique properties. The chapter provides an overview of some of the obstacles associated with adapting existing frameworks to nanomaterials, such as data availability issues and the need for novel testing methods. The chapter concludes with a discussion of prospective directions for enhancing the efficacy of risk assessment frameworks for nanomaterials. The authors recommend the development of new testing strategies and techniques, as well as the incorporation of new technologies and approaches, such as high-throughput screening and in silico modeling. In order for risk assessment frameworks for nanomaterials to remain effective and up-to-date, they also emphasize the need for increased collaboration and information-sharing among various stakeholders, including regulators, industry, and academia.

8.3 Assessment of Nanomaterials Used in Agriculture Sector This section provides an overview of the evaluation of nanomaterials utilized in agriculture. Also, it discusses the increasing use of nanotechnology in the agriculture industry and the potential benefits it can provide, such as increased crop yields, pest management, and fertilizer efficiency. However, the section also discusses the potential hazards associated with the use of nanomaterials in agriculture, as well

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as the necessity of risk assessment and safety regulations. This section addresses a number of subtopics, including.

8.3.1 Applications of Nanomaterials in Agriculture This section discusses various applications of nanomaterials in agriculture, such as nanofertilizers, nanopesticides, and nanosensors. It also discusses the prospective advantages of using nanomaterials in agriculture, such as increased plant growth, enhanced nutrient absorption, and decreased water consumption. This section concentrates on the environmental risks associated with the use of nanomaterials in agriculture. It discusses the possibility of nanomaterials accumulating in soil and water, which could be detrimental to ecosystems and fauna. The necessity of effective disposal and recycling of nanomaterials to reduce their environmental impact is also addressed. Nanotechnology has demonstrated immense potential for enhancing agricultural practices through the creation of novel materials and methods [45, 46]. Agricultural applications for nanomaterials include nanofertilizers, nanopesticides, and nanosensors, among others. Nanofertilizers are designed to more efficiently deliver nutrients to crops, resulting in enhanced plant growth and yield [47]. These fertilizers are typically composed of nanoparticles of essential nutrients, such as nitrogen, phosphorus, and potassium, which are bound with a barrier to prevent their release until they reach the plant roots. This results in decreased nutrient loss and enhanced plant absorption. Another application of nanotechnology in agriculture is nanopesticides. These pesticides are designed to be more effective and targeted than conventional pesticides, thereby reducing the quantity of chemical required for pest control. Nanopesticides employ nanoparticles that can permeate insect defenses and deliver the active ingredient directly to the target organism. This results in increased effectiveness, decreased environmental impact, and enhanced safety for humans and other non-target organisms. Figure 8.10 is a schematic representation of the potential agricultural applications of nanotechnology. It describes the various applications of nanotechnology, such as nanosensors, nanofertilizers, nanopesticides, and nanoformulations. It is possible to use nanosensors to detect and monitor environmental conditions, soil moisture, and nutrient levels, thereby optimizing crop growth and yield. Nanofertilizers can increase the efficacy of nutrient delivery to plants, resulting in improved crop growth and yield. Nanopesticides have the ability to target specific pests, thereby reducing the quantity of pesticide required and minimizing the impact on non-target organisms. Nanoformulations, such as encapsulation or coating of agrochemicals, can increase their stability, decrease their toxicity, and boost their delivery to target sites. This can result in decreased agrochemical use, enhanced productivity, and reduced environmental impact. The use of nanoscale agrochemicals in agriculture has the potential to transform traditional agro-practices and make them more sustainable and efficient, resulting in greater food security. Also being developed are nanosensors for use in agriculture. These sensors can detect a variety of environmental factors, including temperature, humidity, and

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Fig. 8.10 Schematic representation of agricultural nanotechnology applications. Reprinted with permission from Heliyon, Copyright 2022, Cell Press [48]

nutrient levels, and provide producers with real-time data. This information can be used to optimize crop growth and reduce waste, resulting in more efficient and sustainable agricultural practices. Nanomaterials have the potential to promote plant growth, nutrient absorption, water efficiency, and pest control when used in agriculture. Concerns have been expressed, however, regarding the potential dangers and environmental impact of these materials. Prior to the pervasive adoption of nanomaterials in agriculture, it is crucial to conduct rigorous risk assessments and safety evaluations.

8.3.2 Environmental Concerns Associated with Nanomaterials in Agriculture This section discusses the potential risks of nanomaterial exposure for farmers, agricultural workers, and consumers. It emphasizes the importance of employing protective equipment and minimizing direct contact with nanomaterials in order to safeguard individuals from potential damage. The potential for farmers, agricultural

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workers, and consumers to be exposed to these nanoparticles raises concerns for human health in relation to nanomaterials in agriculture. Exposure to nanoparticles is associated with adverse health effects, including respiratory issues, inflammation, and oxidative stress, according to studies [49]. Farmers and farm workers who handle nanomaterials during the production and administration of nanofertilizers and nanopesticides are more likely to be exposed. Nanoparticles inhaled during spraying or absorbed through the epidermis can cause health issues [50]. In addition, nanoparticles can accumulate in soil and water, increasing the likelihood of exposure via contaminated food or water [51]. The consumption of food products treated with nanopesticides or grown using nanofertilizers may also expose consumers to nanomaterials. The toxicity and potential accumulation of these nanoparticles in the human body are still being studied, and the long-term impacts of exposure are unknown [52]. To reduce the potential health hazards associated with the use of nanomaterials in agriculture, it is crucial to implement the necessary safety precautions. These precautions include wearing protective gear during handling and application, minimizing direct contact with nanoparticles, and adhering to disposal and decontamination guidelines [53]. In addition, regular monitoring and risk assessments are required to assure the safety of agricultural nanomaterials [54].

8.3.3 Risk Assessment and Safety Regulations This section addresses the need for appropriate risk assessment and safety regulations for agricultural nanomaterials. It describes the current regulatory environment for nanomaterials in agriculture and identifies regulatory gaps that must be addressed to assure the safe use of nanomaterials in agriculture. The use of nanomaterials in agriculture is a rapidly expanding field, but their potential impact on human health and the environment raises concerns [50]. To ensure the safe use of nanomaterials in agriculture, proper risk assessment and safety regulations are essential. There are currently no comprehensive regulatory frameworks designed specifically for nanomaterials in agriculture. However, the USA, Canada, and Australia have developed guidelines for the use of nanomaterials in agricultural settings. Evaluation of the potential hazards posed by the use of nanomaterials in agriculture requires a thorough risk assessment. It entails identifying the risks associated with the use of nanomaterials and evaluating the probability and severity of any potential damage. To ensure the safe application of nanomaterials in agriculture, it is crucial to establish safety regulations. These regulations can aid in minimizing potential dangers and ensuring that the necessary safety precautions are followed. Safety regulations for nanomaterials in agriculture may include guidelines for handling and disposal, as well as requirements for personal protective equipment and labeling [55]. In addition to regulatory measures, public awareness and education campaigns may be required to promote safe practices and resolve any concerns related to the agricultural use of nanomaterials. Farmers, farm employees, and consumers must be aware of the potential risks associated with nanomaterials and be properly trained in their safe

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handling and use. To assure the safe use of nanomaterials in agriculture, a comprehensive risk assessment and safety regulations are essential. It is crucial to evaluate the potential risks and benefits of utilizing these materials and to devise measures to mitigate any potential damage [56]. Overall, Sect. 8.3 emphasizes the significance of risk assessment and safety regulations for the use of nanomaterials in agriculture to ensure that their potential benefits are realized while potential risks to the environment and human health are minimized.

8.4 Public Opinion Regarding Use of Nanoparticles in Food and Agriculture Industry This section examines the public’s perspective on the use of nanoparticles in the food and agriculture industries. This section also discusses the significance of comprehending public opinion and perception regarding nanotechnology in the food and agriculture industry, as well as the factors that influence public opinion. To examine the public’s perspective on the use of nanoparticles in the food and agriculture industries, surveys, focus groups, and social media analysis can be utilized. The public’s knowledge, attitudes, and beliefs regarding nanotechnology in the food and agriculture industry can be assessed through surveys [57]. Focus groups can provide a deeper understanding of the causes of public perceptions and concerns. In the food and agriculture industry, social media analysis can also be used to identify common themes and sentiment regarding nanotechnology. It is crucial to employ these techniques in order to comprehend the public’s viewpoint, as they can inform regulatory decisions and industry practices [58]. Understanding public opinion and perception concerning nanotechnology in the food and agriculture industry is crucial for a number of reasons. First, it aids in the identification of potential obstacles to the acceptance and implementation of nanotechnology in these sectors. This information can be used to develop effective communication strategies and outreach programs in response to public concerns and to increase public acceptance. Understanding public perception can also contribute to the development of appropriate regulations and policies for the food and agriculture industry’s use of nanotechnology. It can assist policymakers in the development of regulatory frameworks that resolve public concerns and guarantee the safety of nanotechnology for human health and the environment. Lastly, public perception can influence the market demand for food and agriculture products founded on nanotechnology. A negative perception of nanotechnology can reduce consumer demand and, consequently, commercial interest in the development of products based on nanotechnology. Understanding and addressing public concerns is therefore essential for the successful incorporation of nanotechnology in the food and agriculture industry. The section notes the general public’s limited understanding of nanotechnology and its prospective applications in the food and agriculture industries. As a consequence, there is a lack of knowledge regarding the potential benefits and risks associated with the use of nanoparticles in food and agriculture. Several

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potential benefits are associated with the use of nanoparticles in agriculture and food production: (i) Nanofertilizers have the potential to enhance nutrient assimilation and plant growth, resulting in higher crop yields. It is possible to use nanotechnology to enhance the texture, flavor, and shelf life of culinary products. (ii) Nanopesticides can reduce the quantity of pesticides required for pest control, thereby reducing environmental impact and enhancing sustainability. However, there are hazards associated with the use of nanoparticles in agriculture and food: (i) There is concern regarding the potential toxicity of nanoparticles to humans and animals, as well as the potential accumulation of nanoparticles in the food chain. (ii) Nanoparticles have the potential to have negative effects on ecosystems and the environment. (iii) The regulation of nanoparticles in food and agriculture is intricate, and standardized testing protocols and safety regulations are required to ensure their safe use. This lack of comprehension can lead to mistrust and skepticism of nanotechnology among the general public. The extent that the general public understands nanotechnology and its potential applications in the food and agriculture industries is a significant factor influencing public opinion. Many individuals are unfamiliar with nanotechnology, making it difficult for them to comprehend the benefits and hazards associated with its application in food and agriculture. Due to the lack of information available to them, some people may have misconceptions or concerns about the safety of nanotechnology. This dearth of comprehension and knowledge may result in skepticism and opposition to the use of nanotechnology in these industries. Regarding the safety of nanotechnology, there are a number of misconceptions and concerns, including: (i) Many individuals are concerned about the unknown long-term effects of exposure to nanoparticles, especially in food and agricultural applications. (ii) There is a common belief that nanoparticles are inherently hazardous to human health and the environment. (iii) Some individuals are concerned that there is a lack of regulation surrounding the use of nanoparticles in food and agriculture, and that companies may be utilizing these materials without appropriate safety testing. Some consumers may be concerned that they do not have a choice regarding whether or not they ingest food or agricultural products containing nanoparticles. Concern exists regarding the potential environmental impact of nanoparticles, particularly with regard to their effect on soil health and biodiversity. Some individuals may have ethical concerns about the use of nanotechnology in food and agriculture, particularly in terms of animal welfare and the use of genetic modification. It is crucial to note that, despite the existence of these concerns, research is ongoing, and regulations are in place to ensure the safe use of nanoparticles in these industries. This section also emphasizes some of the factors that influence public opinion regarding nanotechnology, including media coverage, personal values and beliefs, and confidence in regulatory agencies. Several factors can influence public opinion about nanotechnology, including: (i) The media plays a vital role in influencing public opinion and can affect how individuals perceive nanotechnology. Positive or negative media coverage can affect public perceptions of nanotechnology’s safety and potential benefits. (ii) The values and beliefs of individuals can also influence their perspectives on nanotechnology. Some individuals may view nanotechnology as a threat to the natural environment or a potential danger to human health, whereas others may view it as an innovative

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solution to global challenges in food and agriculture. (iii) The public’s confidence in regulatory agencies and their capacity to assure the safety of nanotechnology can also influence their views. If individuals lack confidence in regulatory agencies, they may view nanotechnology with skepticism and safety concerns. (iv) Knowledge and comprehension of nanotechnology can influence people’s opinions. If individuals lack knowledge or have misconceptions about the technology, they may have misconceptions regarding its safety and potential applications. Overall, the public’s perception of nanotechnology is complex and influenced by a number of factors. It is essential for scientists, industry professionals, and regulatory agencies to communicate effectively and transparently with the public in order to address any concerns and establish trust in the safe use of nanotechnology in food and agriculture [59]. The section notes that negative media coverage can affect public perception of nanotechnology and that personal values and beliefs can influence how individuals perceive the potential benefits and risks of using nanoparticles in food and agriculture [60]. Negative media coverage can contribute to a general dearth of understanding and fear of nanotechnology, resulting in negative public perceptions. This fear can be exacerbated by a lack of transparent communication and explicit government and industry regulation. Individuals’ perceptions of the potential benefits and hazards of using nanoparticles in agriculture and food may also be influenced by their personal values and beliefs. Those who value organic and natural products, for instance, may be more skeptical of the use of nanotechnology in agriculture and food, whereas those who value efficiency and innovation may be more supportive of its application. In order to facilitate informed decision-making and responsible use of nanotechnology, it is essential to identify and address these influences. The section elaborates on the significance of public participation in discussions regarding nanotechnology in the food and agriculture industry. The public’s participation can help raise awareness and comprehension of nanotechnology and its potential benefits and hazards. Participation of the public in discussions about nanotechnology in the food and agriculture industry is crucial for a number of reasons. First, it increases awareness and understanding of nanotechnology and its potential benefits and risks. This is significant because the general public’s limited knowledge and comprehension of nanotechnology can lead to misunderstandings and concerns. Second, public participation in the development and regulation of nanotechnology in the food and agriculture industry can promote transparency and accountability. Important because there may be uncertainties and unknown risks associated with the use of nanoparticles, and public involvement can help ensure that these risks are identified and mitigated. Thirdly, public participation can help create trust and confidence in the regulatory agencies and companies responsible for the development and application of nanotechnology in the food and agriculture industry. This is essential for the successful implementation of new technologies, as public trust and confidence are essential. Lastly, public participation can help ensure that the perspectives and concerns of various stakeholders, such as consumers, farmers, and environmental organizations, are considered in the development and regulation of nanotechnology in the food and agriculture industry. This can help to ensure that nanotechnology’s benefits and hazards are distributed fairly and that the technology

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is used in a socially responsible and environmentally sustainable manner. The section also observes that effective communication is essential for fostering public trust and confidence in the food and agriculture industry’s use of nanoparticles. Effective communication is essential for cultivating public trust and confidence in the use of nanoparticles in the food and agriculture industry. The public is more likely to embrace the use of nanoparticles in food and agriculture if they believe they have been adequately informed of the benefits and risks associated with these technologies. Effective communication can help address concerns and misperceptions about the use of nanoparticles and establish trust among stakeholders, such as regulatory agencies, industry, and the general public. Effective communication requires the use of understandable language and the provision of accurate and current information. Additionally, it entails engaging with constituents and listening to their concerns and feedback. By involving the public in discussions about the use of nanoparticles, stakeholders can better comprehend and address the public’s concerns. This can contribute to the development of trust and a sense of shared responsibility for the safe and responsible use of nanoparticles in food and agriculture. In conclusion, effective communication is necessary for building public trust and confidence in the use of nanoparticles in food and agriculture. By providing clear and accurate information, engaging stakeholders, and involving the public in discussions, stakeholders can work to address concerns and develop trust, thereby contributing to the safe and responsible use of nanoparticles in these industries. The section emphasizes the significance of incorporating public opinion and perception into the development of regulations and guidelines for the use of nanoparticles in the food and agriculture industries. It may be possible to foster public trust and confidence in the safe and responsible use of nanoparticles in food and agriculture by contemplating public opinion and engaging the public in discussions about nanotechnology. It is crucial for multiple reasons to incorporate public opinion and perception into the development of regulations and guidelines for the use of nanoparticles in the food and agriculture industries. First, it guarantees that regulatory decisions reflect the public’s values and concerns. This can help create trust and confidence in the regulatory process and the technology’s safety. Second, involving the public in discussions about nanotechnology can increase awareness and comprehension of the potential benefits and dangers. This can lead to increased public acceptance of the technology and more informed decision-making. Incorporating public opinion and perception into regulatory decision-making can assist in identifying potential knowledge deficits or areas of concern that may require additional research and evaluation. This can help ensure that the regulatory process is based on the finest scientific evidence available and that potential risks are identified and addressed. Effective communication with the public is also essential for cultivating public trust and confidence in the food and agriculture industries’ use of nanoparticles. This includes providing clear and transparent information regarding the benefits and risks of the technology and the regulatory process for assuring its safety. Involving the public in two-way communication and actively soliciting feedback and input are also required. Overall, incorporating public perception and opinion into the regulatory process and fostering effective communication with the public are essential for

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ensuring the safe and responsible use of nanoparticles in the food and agriculture industries.

8.5 Regulation Regarding Safety Concerns of Nanomaterials in Food and Agriculture Industry To ensure the safe and responsible use of nanoparticles in the food and agriculture industries, nanomaterial safety regulations are crucial. Global regulatory agencies have devised guidelines and regulations for the use of nanomaterials in agriculture and food [56, 61]. These regulations address numerous aspects of nanomaterial safety, such as testing for toxicity, labeling requirements, and risk assessments. However, there are still voids in current regulations, and additional work is required to ensure that nanomaterials are used safely and responsibly in the food and agriculture sectors. It is crucial that regulatory agencies, industry stakeholders, and the general public collaborate to develop effective regulations and guidelines that safeguard public health and the environment while fostering innovation in the use of nanomaterials in food and agriculture [62]. This section covers the following topics related to nanomaterial safety regulations in the food and agriculture industries.

8.5.1 Overview of Current Regulatory Landscape This section discusses the regulations and guidelines currently governing the use of nanomaterials in the food and agriculture industries. It outlined the duties of regulatory agencies such as the FDA, EPA, and USDA in regulating the use of nanomaterials in food and agriculture. It provides an overview of the current regulatory environment for nanomaterials used in the food and agriculture industries [45, 46]. The FDA, the Environmental Protection Agency (EPA), and the United States Department of Agriculture (USDA) are among the regulatory agencies responsible for regulating nanomaterials in these industries [63]. The section emphasizes that the FDA regulates the use of nanomaterials in food and food packaging, while the EPA regulates the use of nanomaterials in pesticides. The USDA is also responsible for regulating the use of nanomaterials in agriculture, particularly in terms of animal feed safety. The Food and Drug Administration oversees the use of nanomaterials in food and food packaging. Before being permitted on the market, they evaluate the safety of nanomaterials used in food and food packaging products. Additionally, the FDA mandates that nanomaterials used in food and food packaging must be labeled so that consumers can make informed decisions. The Environmental Protection Agency of the USA is responsible for regulating the use of nanomaterials in pesticides. Before sanctioning the use of nanomaterials in pesticides, the risks to human health and the environment are assessed. The USDA

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regulates the use of nanomaterials in agriculture, particularly with regard to the safety of animal feed. To ensure the safety of the food supply, the USDA evaluates the safety of nanomaterials used in animal feed and establishes standards for their use [64]. In addition, the section notes that while there are no specific regulations for nanomaterials in agriculture at the present time, they are subject to the same regulations as conventional agricultural compounds. Currently, there is no specific regulation for the use of nanomaterials in agriculture because the technology is still in its infancy and research on the potential hazards and benefits is ongoing. In addition, regulatory agencies may lack the resources and capacity to establish and enforce specific regulations for each new technology due to resource constraints. Consequently, nanomaterials are governed by the same regulations as conventional agricultural compounds. However, as the potential hazards and benefits of nanomaterials in agriculture become better understood, more specific regulations may be required to ensure their safe and responsible use [47, 65]. However, regulatory agencies are continually discussing and debating the need for specific nanomaterials regulations in agriculture. Due to the potential risks associated with the use of nanomaterials in agriculture, including contamination of the environment and health risks for humans and animals, specific nanomaterials regulations are required. Nanomaterials’ distinctive properties necessitate regulations that address their potential toxicity, stability, and environmental behavior. Nanomaterials in agriculture is a relatively new field, and there is still a great deal of research to be conducted in order to completely comprehend their potential risks and benefits. Consequently, it is necessary to implement specific regulations to guarantee their safe and responsible use in the industry [66]. This section highlights the significance of regulatory agencies in ensuring the safe application of nanomaterials in the food and agriculture industries. It emphasizes the need for continued monitoring and evaluation of the regulatory environment in order to address any potential regulatory gaps and assure the safety of nanomaterials for human health and the environment. To ensure the safe application of nanomaterials in the culinary and agriculture industries, regulatory agencies play a crucial role. It is the responsibility of the FDA, EPA, and USDA to regulate the use of nanomaterials in these industries and ensure their safety for human health and the environment [67]. These agencies are responsible for evaluating the risks associated with the use of nanomaterials and devising guidelines and regulations to mitigate those risks. Effective nanomaterials regulation necessitates continuous monitoring and assessment of the regulatory environment. As new information becomes accessible and new nanomaterial applications emerge, regulatory agencies must adapt and update their regulations and guidelines to address any potential regulatory breaches and ensure the safety of nanomaterials. This ongoing evaluation and modification of the regulatory environment is necessary for ensuring the responsible use of nanomaterials in the food and agriculture industries and protecting human health and the environment.

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8.5.2 Gaps in Current Regulations This section examined the restrictions and omissions in the current regulations governing the use of nanomaterials in the food and agriculture industries. To ensure the safe use of nanomaterials in agriculture, it can emphasize areas where regulations need to be updated or improved (He, Deng et al. 2019). Current regulations regarding the use of nanomaterials in the food and agriculture industries contain a number of restrictions and omissions [68]. Some examples include: (i) Presently, there are no labeling requirements for nanomaterial-containing products, making it difficult for consumers to make informed decisions about their use. (ii) Insufficient data on the toxicity of many nanomaterials makes it difficult to assess their potential dangers to human health and the environment. (iii) The current risk assessment methods for nanomaterials are frequently insufficient, as they may not completely account for the unique properties and behaviors of these materials. (iv) Regulatory gaps exist, notably in regards to the use of nanomaterials in agriculture. To ensure the safe use of nanomaterials in agriculture, it is important to address these areas where regulations need to be updated or improved. This may involve: This could include: (i) Establishing mandatory labeling requirements for nanomaterialcontaining products. (ii) To better understand the hazards associated with the use of nanomaterials, we must conduct more extensive toxicology studies. (iii) Developing risk assessment methodologies that take into account the unique properties and behaviors of nanomaterials. (iv) Developing specific regulations for the use of nanomaterials in plant growth regulators or soil amendments to address regulatory deficiencies in the use of nanomaterials in agriculture. Overall, ensuring the safe use of nanomaterials in agriculture necessitates ongoing monitoring and evaluation of the regulatory environment, as well as a commitment to updating and enhancing regulations as needed to address any potential risks.

8.5.3 International Regulations This section provided an overview of the international regulations that regulate the use of nanomaterials in the food and agriculture industries. As nanotechnology is a global issue, the regulation of nanomaterials in the food and agriculture industries is not limited to a single country or region [69]. Therefore, international regulations governing the safe use of nanomaterials in the food and agriculture industries have been established. The Organization for Economic Cooperation and Development (OECD) is one of the primary international organizations tasked with regulating nanomaterials. Several documents published by the OECD provide guidance on the evaluation of the safety of nanomaterials, including those used in food and agriculture [70]. Additionally, the OECD has established the Working Party on Manufactured Nanomaterials (WPMN) to evaluate and manage the hazards associated with nanomaterials. Additionally, the EU has enacted regulations regarding the use of

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nanomaterials in food and agriculture. The EU has a specific regulation on novel foods that includes provisions for assessing the safety of nanomaterials in food. In addition, the EU has established EFSA to evaluate the safety of foods and animal feeds containing or produced with nanomaterials. Other international organizations that regulate nanomaterials in food and agriculture include the Food and Agriculture Organization of the United Nations (FAO) and the WHO. The Joint FAO/WHO Expert Committee on Food Additives (JECFA) was established by the FAO to evaluate the safety of food additives, including nanoscale additives. The World Health Organization has also established the International Agency for Research on Cancer (IARC), which assesses the carcinogenicity of chemicals, including nanomaterials [71]. Globally, international regulations offer a framework for assuring the safe application of nanomaterials in the food and agriculture industries. However, continued international cooperation and harmonization are required to assure consistency in regulatory approaches and close any potential regulatory gaps. It may include information on regulations in the European Union, Canada, and other nations that have enacted regulations for the use of nanomaterials in agriculture. In EU, nanomaterials are governed by the precautionary principle [72]. The EU defines nanomaterials as materials with at least one dimension between 1 and 100 nm and requires companies to provide safety data and labeling information for all nanomaterial-containing products. In addition, the EU has specific regulations regarding the use of nanomaterials in food, including a list of nanomaterials permitted for use in food, labeling requirements, and risk assessment procedures. Health Canada and the Canadian Food Inspection Agency (CFIA) are responsible for the oversight of nanomaterials in food and agriculture in Canada. The CFIA enforces labeling requirements and monitors the use of nanomaterials in food and animal feed, while Health Canada requires companies to provide safety data for any product containing nanomaterials [73]. Other nations, including Australia, New Zealand, and Japan, have also enacted regulations regarding the agricultural use of nanomaterials. The purpose of these regulations, which vary in scope and requirements, is to ensure the safety of nanomaterials for human health and the environment [56, 74]. Globally, the international regulations regulating the use of nanomaterials in food and agriculture have similar objectives of ensuring safety and promoting transparency; however, regional and national requirements and approaches vary [75].

8.5.4 Safety Assessment Requirements This section discussed the safety assessment requirements for nanomaterials used in the food and agriculture industries. It can include information on the types of safety evaluations required, the methodologies used for safety evaluation, and the criteria for determining the safety of nanomaterials in food and agriculture [76]. The assessment of the safety of nanoparticles used in the food and agriculture industries entails assessing the potential dangers connected with their usage as well as guaranteeing their safety for human health and the environment. The standards for

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assessing nanoparticles used in food and agriculture are determined by the regulatory framework in which they are utilized [77]. Some common safety evaluation needs, however, are as follows: (i) To understand the behavior and possible risks of nanomaterials, their physicochemical parameters such as size, shape, surface area, and chemical composition must be studied. (ii) Toxicity studies are carried out to assess the potential detrimental effects of nanomaterials on human health and the environment. The investigations look at the acute and chronic toxicity of nanomaterials, as well as their genotoxicity and cancer-causing potential. (iii) Exposure evaluation entails assessing the potential exposure pathways and routes of exposure for nanomaterials. It comprises assessing the risk of exposure through ingesting, inhalation, and skin contact. (iv) To establish the potential dangers associated with the use of nanomaterials, risk characterization combines information from physicochemical characterization, toxicity investigations, and exposure assessment. (v) Nanomaterials used in food and agriculture must adhere to all applicable regulations and norms. Regulations often stipulate the requirements for safety evaluation, such as the types of research necessary, methodology employed, and criteria for assessing the safety of nanomaterials. Nanomaterials used in food and feed are regulated in the EU under the Novel Foods Regulation (EU) 2015/2283, which requires a safety assessment before a new food product is placed on the market [78]. The assessment involves an examination of the nanomaterial’s physicochemical qualities, possible toxicity, and exposure risk [79]. The FDA has issued recommendations on the use of nanotechnology in food and feed in the USA, outlining the safety evaluation standards for nanomaterials. Manufacturers must undertake a safety assessment of the nanomaterial, including its physicochemical qualities, toxicity, and probable exposure routes, according to the guidelines. The regulatory environment for nanomaterials used in food and agriculture in Canada is comparable to that in the USA. Nanomaterials are governed by the Canadian Food and Drugs Act and the Pest Control Products Act. The standards mandate a safety study of the nanomaterial, which includes an assessment of its toxicity, potential for exposure, and environmental impact. In summary, assessing the safety of nanomaterials used in the food and agriculture industries entails assessing potential dangers and assuring their safety for human health and the environment. Physicochemical characterization, toxicity studies, exposure assessment, and risk characterization are all common components of the assessment. Regulations governing the use of nanomaterials in food and agriculture vary by location, but in general, a safety assessment is required before the nanomaterial is placed on the market.

8.5.5 Labeling Requirements This section discussed the labeling requirements for food and agricultural products containing nanomaterials. It may include information on the categories of products that require labeling, the information that must be included on labels, and the regulations governing the labeling of agricultural nanomaterials [56]. Labeling rules for

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nanomaterial-containing food and agricultural goods differ by country and regulatory agency. In the USA, the FDA mandates that food products containing nanoparticles be labeled with the word “nano” in the ingredient list, such as “nanotitanium dioxide.” The FDA also suggests that companies voluntarily provide data on the safety of nanomaterials in their products to the agency for assessment, including any relevant characterization data. Nanomaterials used in food and food contact materials in the EU must be allowed and listed in the EU’s Novel Food Catalogue, and their presence must be disclosed on the label. The EU also demands that nanoparticles used in food contact materials be tested for safety before they may be utilized. Products containing nanomaterials must be labeled as such in Canada if the nanomaterial is present in a concentration of at least 0.1% of the total weight of the product. The label must also include the chemical name of the nanomaterial or the name of the nanomaterial’s supplier. In general, agricultural products incorporating nanomaterials have less developed labeling standards than food products. The OECD has developed guidelines for labeling nanomaterials in pesticides, recommending that the label include a statement stating the presence of nanoparticles as well as any relevant safety information. These principles, however, are not legally binding. In summary, the labeling regulations for nanomaterials in food and agriculture differ per country and regulatory body. In general, the presence of nanoparticles must be disclosed on the label, and certain nations may need extra information, such as the chemical name or supplier of the nanomaterial. Labeling standards for agricultural products containing nanomaterials, on the other hand, are less developed than those for food products.

8.5.6 Future Regulatory Directions This section discussed potential future regulatory directions for nanomaterials in the food and agriculture industries. It may include information on novel technologies and approaches to risk assessment, as well as regulatory changes that may have an impact on the use of nanomaterials in agriculture. Nanomaterials regulation in the food and agriculture industries is a developing topic, with various potential future regulatory orientations that could affect their use. Among these instructions are.

Novel Technologies and Approaches to Risk Assessment In the food and agriculture industries, there is a need for more advanced and unique ways to risk assessment of nanomaterials. Nanoinformatics, which employs data science to organize, integrate, and analyze massive amounts of data on nanoparticles, could aid in better understanding the dangers and safety of nanomaterials [80]. Furthermore, in vitro and non-animal testing methods could be used to assess the safety of nanomaterials, potentially reducing the need for animal testing [81].

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Changes in Regulations and Guidelines Regulations and guidelines may need to be revised or amended as our understanding of nanomaterials and their potential effects on human health and the environment evolves. Regulatory agencies, for example, may need to develop particular definitions and rules for the use of nanomaterials in agriculture, such as requirements for safety evaluation, labeling, and reporting.

Increased Collaboration and Harmonization To better understand the safety and risks associated with nanomaterials, there is a need for increased collaboration and harmonization between regulatory agencies and scientific communities. Collaboration among regulatory authorities from various nations may aid in the development of more comprehensive and harmonized regulations that address the safety and dangers of nanomaterials in a uniform and unified manner.

Transparency and Public Participation There is a need for greater transparency and public participation in the regulation of nanomaterials in the food and agriculture industries. This includes incorporating stakeholders such as consumers, farmers, and industry representatives in the creation of legislation and standards, as well as providing the public with clear and intelligible information about the safety and dangers of nanomaterials [82].

Emphasis on Sustainability In the food and agriculture industries, there is an increasing interest in sustainability and the environmental impact of nanomaterials. As a result, future laws may need to include nanoparticles’ sustainability and environmental impact in addition to their safety and dangers. In summary, future regulatory directions for nanomaterials in the food and agriculture industries will most likely include novel technologies and risk assessment approaches, changes in regulations and guidelines, increased collaboration and harmonization, increased transparency and public engagement, and a focus on sustainability. These guidelines will assist in ensuring the safe and responsible use of nanomaterials in food and agriculture while reducing possible dangers to human health and the environment.

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8.6 Summary This chapter examines the use of nanomaterials in the food and agriculture industries, as well as the regulatory framework regulating their application. It highlights the potential benefits and risks of using nanomaterials in these industries, as well as the significance of ensuring their safe and responsible application. The chapter describes the current regulations and guidelines for the use of nanomaterials in food and agriculture, with an emphasis on the duties of regulatory agencies including the FDA, EPA, and USDA. It also discusses the need for continuous monitoring and evaluation of the regulatory environment in order to resolve any potential regulatory gaps and guarantee the safety of nanomaterials. The chapter also focuses on the labeling requirements for food and agricultural products containing nanomaterials, as well as the safety evaluation requirements for nanomaterials used in these industries. It investigates the potential future regulatory orientations for nanomaterials in food and agriculture, including novel technologies and approaches to risk assessment as well as regulatory changes that may affect their use. Overall, the chapter emphasizes the significance of balancing the potential benefits and risks of using nanomaterials in food and agriculture, as well as assuring their safe and responsible use through the implementation of pertinent regulations and guidelines.

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Index

A Abiotic stressors, 90, 93, 166 Agricultural productivity, 85, 166, 177, 178, 182, 279 Agriculture, 1, 3, 34, 83, 90, 94, 96, 97, 124, 149, 150, 157, 158, 166, 182–184, 187, 269–271, 273, 274, 276, 286–301 Agriculture sector, 1, 90, 148, 157, 286, 294 Agrifood industry, 3, 90, 178, 278–280 Agro-defense, 124, 125 Agro-defense biosensors, 124 Agrofood processing, 9 Agro-sector, 3 Alanine aminotransferase, 257 Aluminium oxide, 7, 8, 29, 89 Antiamyloidogenic, 258 Anticaking agent, 89, 111 Anticounterfeiting device, 121, 123, 143–145, 153 Antimicrobial activity, 12, 20, 56, 62, 96, 110, 111, 178, 182, 258, 260, 283, 284 Antimicrobial effects, 4, 21, 55, 110, 260, 261 Archaeosomes, 240, 261 Aspartate aminotransferase, 257

B Bacillus cereus, 71, 137, 184 Bacterial biosensors, 125 Bakery, 70 Beverages, 4, 9, 25, 48, 65–67, 108, 224 Bilosomes, 239, 240, 261 Bioactive food ingredients, 3

Biosensors, 3, 119, 121–126, 128–135, 137–141, 143–147, 149, 151, 152 Biostimulant impact, 98 Breast cancer, 198, 200, 201, 212, 214, 238, 239, 241, 247, 251, 253, 256

C Cancer, 196–200, 217, 221, 236, 238, 243–245, 248–251, 256–258, 263 Cancer cells, 197, 198, 200, 202, 211, 213, 217, 238, 241, 244, 247–249, 253–256, 258, 260, 263 Carbon based nanomaterials, 164 Carbon nanotubes, 4, 12, 28, 121, 122, 124, 137, 138, 142, 145, 149, 216, 227, 242, 243, 261, 279 Carbon quantum dots, 91–93 Cardiovascular disease, 195, 196, 205, 235 Chemical fertilizers, 157 Chemical pesticide, 100 Clostridium spp, 132, 133 Colorimetric sensors, 129, 132, 140, 142, 143, 152, 153 Consumer perception, 272 Conventional food packaging, 3, 11, 44 Copper, 29, 67, 68, 94, 158, 160, 161, 172, 177, 270 Copper oxide nanoparticles, 160, 172, 174 Curcumin, 18, 98, 100, 199–201, 205, 207–211, 214, 217, 223–226, 236, 237, 241–244, 247, 251–253, 256, 257, 262

© The Editor(s) (if applicable) and The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2023 R. Singh and S. Kumar, Nanotechnology Advancement in Agro-Food Industry, https://doi.org/10.1007/978-981-99-5045-4

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308 D Dairy products, 67, 68, 73, 119, 133, 203, 218 Dendrimers, 104, 130, 217, 227, 245–249, 261, 262 Diosgenin, 238, 239 Disease control, 94, 111

E Electrochemical sensors, 124, 139–143 Engineered nanomaterials, 3 Environmental contamination, 33, 169, 178 Environmental impact, 17, 96, 272, 278, 287, 288, 291, 298, 300 Enzyme-Linked Immunosorbent Assay biosensors, 151 Enzyme-Linked Immunosorbent Assay (ELISA), 131 Escherichia coli (E. coli), 8, 12, 16, 26, 57, 62, 64, 110, 124, 125, 127, 128, 130, 136, 152, 212, 260 Ethical considerations, 272 Eugenol, 241

F Fertilisers, 3, 90, 95, 100, 157–162, 164, 165, 169, 170, 172, 187, 286, 287 Field-effect transistor-based sensors, 149 Fish and sea food products, 59, 61 Fish preservation, 28, 59, 61 Flavors, 3, 6, 7, 12, 22, 44, 46, 67, 81, 89, 104, 111, 120, 233, 270, 271, 291 Food, 1–9, 11, 12, 15, 16, 18, 19, 21–34, 43–48, 50–54, 57, 58, 61–63, 65–71, 73, 81, 82, 86, 89, 90, 98, 100, 110, 111, 119–153, 157, 175, 178, 181, 187, 195, 196, 202, 210, 212, 215, 218–220, 224, 227, 233, 235, 236, 254, 261, 269–285, 289–301 Food adulteration, 123, 141–143, 152, 153 Food and beverage flavours, 67 Foodborne illness, 120, 124, 128, 134, 137 Food handling, 44 Food industry, 2–4, 7, 12, 27, 44, 51, 81, 89, 90, 100, 110, 111, 119–121, 123–125, 129, 140, 141, 143, 145, 148, 197, 213, 269–272, 274, 277–279, 285 Food nanotechnology, 2, 6 Food packaging material, 12, 16, 17, 31, 120, 270, 271, 281, 282

Index Food preservation, 3, 18, 20–22, 43–45, 50, 54, 55, 58, 65, 71, 73, 270, 282 Food preservatives, 19 Food safety monitoring, 152 Fullernes, 85 Functional foods, 3, 9, 22, 25, 48, 195, 196, 218, 219, 227 Functionalized nanomaterials, 158 Fungal contamination, 123–125, 138–141, 148, 149, 151–153

G Global agriculture, 90 Global warming, 82 Glutathione, 85, 110, 177, 185, 248–250 Glycyrrhizic acid nanoparticles, 86 Gold, 1, 3, 28, 71, 131, 139, 176 Gold and graphene oxide, 28 Gold nanoclusters, 263 Gold nanoparticles, 106, 121, 132, 134, 198, 263 Gram-negative bacteria, 12, 110, 135 Gram-positive bacteria, 12, 110 Graphene oxide, 21, 28, 50, 55, 131, 144, 147, 251, 253 Graphene oxide nanoribbons, 125

H Herbicides, 3, 90, 157, 178, 180 Hydroxyapatite nanoparticles, 169, 170, 187 Hypoglycemic effects, 234 Hypsochromic effects, 201

I Impedimetric sensors, 140, 149 Inflammation and oxidative stress, 205, 227 Insecticides, 3, 90, 157, 165 Intelligent nanosensors, 120–125, 138–141, 148, 152, 153 Intelligent packaging, 4, 12, 53, 65, 73 Intelligent packaging system, 3

L Labeling requirements, 294, 296–298, 301 Lipid, 2, 5, 23–25, 27, 62, 68, 71, 73, 81, 83, 85, 178, 179, 203, 204, 211–213, 216, 217, 224, 227, 236–241, 250 Liposomes, 201, 210, 217, 227, 236–239, 259–261

Index Listeria, 26, 61, 64, 127, 129, 130 Localized surface plasmon resonance, 142 M Magnetic nanoparticles, 102–104, 106–109, 135 Magneto-responsive bacteria, 102 Microfluidic devices, 125, 126, 148 Microorganism detection, 12, 16, 25, 47, 52, 55, 57, 62, 70, 102, 119, 125–128, 137, 139, 140, 173, 180, 260, 281 Molecular imprinted polymers, 106 Multiwalled carbon nanotubes, 29, 145, 165, 171, 243, 245 Mycotoxin detection, 148 N Nanobiosensors, 82, 129, 133, 145–147, 149–153 Nanocarriers, 3, 6, 7, 43, 95, 157, 170, 178, 227, 233, 235, 236, 240, 241, 246, 250, 251, 261, 262, 269, 270 Nanoclays, 16, 63, 168, 169, 187, 271 Nanocomposites, 2, 3, 12, 15–17, 21, 22, 27, 28, 43, 50, 54–57, 65, 68, 70, 71, 161, 178, 185, 186, 258, 262, 270 Nanoemulsification, 46, 73, 225 Nanoemulsion, 21–23, 26, 47, 48, 62, 67, 203, 210, 213, 218, 224–227, 240, 245, 263 Nanoenabled food, 24 Nanoencapsulation, 7, 23, 43, 46, 47, 73, 81, 89, 158, 197, 214, 234, 269 Nanofabrication technique, 121, 124 Nanofertilizers, 86, 95, 96, 111, 157–162, 164, 166–177, 187, 287, 289, 291 Nanofiltration, 9–11, 30, 34, 48–50, 73, 104, 105, 263 Nanoformulations, 158, 159, 180–182, 195, 198, 203, 205, 207, 225, 257, 258, 287 Nanomaterials, 82, 119, 122 Nanomaterials in food packaging, 11, 31, 33, 45 Nanomaterials in food preservation, 18 Nanonutraceuticals, 196, 198, 202, 227 Nanoparticles, 1–8, 12, 16, 18–21, 23–25, 29, 31–34, 43, 44, 54, 55, 57, 60, 62–65, 67–69, 73, 81–83, 85, 86, 89–98, 100, 102, 106–111, 121, 129, 134, 135, 138, 142, 144, 149,

309 158–161, 164, 165, 168–176, 178–182, 185–187, 195, 197–201, 203, 205, 207–210, 212, 214, 217–223, 225, 226, 234, 241, 242, 250, 254, 256–259, 261–263, 271–274, 276, 279–285, 287, 289–294, 298–300 Nanopesticides, 90, 158, 178, 182, 185–187, 287, 289, 291 Nano-phytochemicals, 258, 261 Nanopolymers, 3, 43 Nanoscience, 2, 31, 81, 157, 218 Nanosensors, 3, 43, 82, 119, 270, 271, 287 Nanostructures, 3, 22, 23, 25, 31, 104, 159, 165, 217, 245, 261 Nanotechnology, 2–4, 7, 11, 22, 24, 25, 31, 33, 43, 44, 48, 52–54, 59, 62, 66, 67, 70, 81–83, 86, 90, 100, 102, 103, 106, 111, 120, 121, 123, 134, 141, 147, 157, 158, 175, 178, 187, 196, 205, 207, 210, 215, 218, 219, 234, 235, 250, 261, 269–271, 273, 274, 277–279, 286–288, 290–293, 298 Nanotitanium oxide, 62 Niosomes, 211, 238, 239, 261 Nonbiodegradable materials, 67 Novel nanomaterials, 145, 146 Nutraceuticals, 3, 67, 195–197, 199, 201, 210–215, 217, 220, 221, 226, 227 Nutrigenomics, 195, 196, 210, 215, 227

P Packaging, 11, 17, 27, 28 Packaging nanomaterials, 52 Pathogens, 3, 21, 25, 62, 63, 82, 94, 96–98, 100, 119, 121, 122, 124, 126, 127, 129–131, 149, 152, 168, 182, 184–186, 198, 279, 283 Pesticides, 3, 31, 50, 149, 157, 177, 178, 180–183, 186, 279, 287, 291, 294, 299 Phytochemicals, 22, 90, 218, 233–240, 247–249, 253, 255, 258, 261–263 Polyamidoamine, 130, 245–247, 262 Polymer fillers, 44 Polymeric micelles, 215, 216, 227 Polymeric nanoparticles, 21, 170, 187, 250, 253–258, 261 Polysaccharides, 26, 55, 219, 223, 227, 239, 257 Potentiometric sensors, 144, 149 Poultry, 63, 73, 128, 218

310 Preserving, 4, 18, 30, 34, 44, 54, 62, 67, 96 Processing agent, 43 Protein removal, 107, 111 Q Quality preservation, 44 Quantum dots, 122, 128, 130, 133–135, 144, 249–252, 254, 261, 277, 279 R Reactive oxygen species, 8, 12, 83, 85, 89, 95, 96, 166, 168, 173, 175, 178, 179, 184, 201, 207, 249, 250, 256, 276, 283 Regulatory requirements, 272 Risk assessment, 1, 31, 34, 269, 272, 273, 275–278, 280–283, 285–290, 294, 296, 297, 299–301 S Selenium, 83 Shigella, 135–137 Silicon nanofertilizer, 166 Silver, 1, 3, 5, 16, 17, 25, 27, 33, 57, 61, 62, 65, 67, 68, 71, 98, 109, 110, 158, 176, 270, 282 Silver nanoparticles, 4, 5, 12, 15–17, 27, 33, 57, 58, 62, 63, 65, 68, 70, 73, 98, 100, 109–112, 173, 176–181, 185, 212, 243, 254–256, 258, 262, 277, 281–284 Single walled carbon nanotubes, 130, 145, 242–244

Index Smart packaging, 2, 43, 44, 66, 73 Smart sensor, 141 Staphylococcus, 131, 212, 262 Stress treatment, 90, 111 Surface plasmon resonance, 139, 144 Systematic Evolution of Ligands by Exponential Enrichment (SELEX), 135, 150, 151

T Therapeutic agents, 202, 235, 247 Titanium dioxide nanoparticles, 5, 55, 91, 95, 96, 175, 280–282 Toxicity, 1, 2, 4, 5, 24, 28, 31, 33, 34, 90, 148, 159, 197, 198, 200, 214, 216, 235, 239, 240, 243, 247, 248, 254, 255, 257, 269–278, 280, 283, 285, 287, 289, 291, 294–296, 298 Toxicity and safety concern, 31 Toxins, 3, 73, 120, 123, 132, 133, 138, 139, 146–148, 153, 279 Transferosome, 217, 227 Tryptophan, 86, 96, 251, 252

V Vibrio parahaemolyticus, 134 Viticulture, 82, 90, 96, 100, 111

Z Zinc oxide nanoparticles, 12, 55, 70, 85–88, 159, 186, 283, 285