Plant Nanobionics: Volume 1, Advances in the Understanding of Nanomaterials Research and Applications [1st ed.] 978-3-030-12495-3;978-3-030-12496-0

Table of contents :
Front Matter ....Pages i-xiii
Recent Advancements and New Perspectives of Nanomaterials (Ezgi Emul, Mehmet Dogan Asik, Ramazan Akcan, Kazim Kose, Lokman Uzun, Semran Saglam et al.)....Pages 1-32
Recent Progress in Applied Nanomaterials (R. Mankamna Kumari, Nikita Sharma, Geeta Arya, Surendra Nimesh)....Pages 33-64
An Insight into Plant Nanobionics and Its Applications (Shubha Rani Sharma, Debasish Kar)....Pages 65-82
Plastics, Micro- and Nanomaterials, and Virus-Soil Microbe-Plant Interactions in the Environment (Gero Benckiser)....Pages 83-101
Characterization Methods for Chitosan-Based Nanomaterials (Ram Chandra Choudhary, Sarita Kumari, R. V. Kumaraswamy, Ajay Pal, Ramesh Raliya, Pratim Biswas et al.)....Pages 103-116
Impact of Nanomaterials in Plant Systems (Rishabh Anand Omar, Shagufta Afreen, Neetu Talreja, Divya Chauhan, Mohammad Ashfaq)....Pages 117-140
Nanoagriculture and Energy Advances (R. G. Cásarez-Santiago, J. J. Chanona-Pérez, C. A. Reséndiz-Mora, N. Gϋemes-Vera, A. Manzo-Robledo, M. J. Perea-Flores et al.)....Pages 141-164
Nanopesticides and Nanosensors in Agriculture (Rajender Boddula, Ujwalkumar Trivedi, Ramyakrishna Pothu, Mahendrapal Singh Rajput, Aditya Saran)....Pages 165-181
Nano-agriculture in the Food Industry (Antony Allwyn Sundarraj)....Pages 183-200
Nanotechnology and Plant Extracts as a Future Control Strategy for Meat and Milk Products (Marija Boskovic, Milica Glisic, Jasna Djordjevic, Milan Z. Baltic)....Pages 201-253
Impact of Nanoparticles on Photosynthesizing Organisms and Their Use in Hybrid Structures with Some Components of Photosynthetic Apparatus (Josef Jampílek, Katarína Kráľová)....Pages 255-332
Nanotechnology and Plant Tissue Culture (Sandra Pérez Álvarez, Marco Antonio Magallanes Tapia, María Esther González Vega, Eduardo Fidel Héctor Ardisana, Jesús Alicia Chávez Medina, Gabriela Lizbeth Flores Zamora et al.)....Pages 333-370
Advances in Nanobiotechnology with Special Reference to Plant Systems (Madan L. Verma, Pankaj Kumar, Deepka Sharma, Aruna D. Verma, Asim K. Jana)....Pages 371-387
Back Matter ....Pages 389-397

Citation preview

Nanotechnology in the Life Sciences

Ram Prasad Editor

Plant Nanobionics Volume 1 Advances in the Understanding of Nanomaterials Research and Applications

Nanotechnology in the Life Sciences Series Editor Ram Prasad

School of Environmental Science and Engineering, Sun Yat-sen University, Guangzhou, China Amity Institute of Microbial Technology, Amity University, Noida, Uttar Pradesh, India

Nano and biotechnology are two of the 21st century’s most promising technologies. Nanotechnology is demarcated as the design, development, and application of materials and devices whose least functional make up is on a nanometer scale (1 to 100 nm). Meanwhile, biotechnology deals with metabolic and other physiological developments of biological subjects including microorganisms. These microbial processes have opened up new opportunities to explore novel applications, for example, the biosynthesis of metal nanomaterials, with the implication that these two technologies (i.e., thus nanobiotechnology) can play a vital role in developing and executing many valuable tools in the study of life. Nanotechnology is very diverse, ranging from extensions of conventional device physics to completely new approaches based upon molecular self-assembly, from developing new materials with dimensions on the nanoscale, to investigating whether we can directly control matters on/in the atomic scale level. This idea entails its application to diverse fields of science such as plant biology, organic chemistry, agriculture, the food industry, and more. Nanobiotechnology offers a wide range of uses in medicine, agriculture, and the environment. Many diseases that do not have cures today may be cured by nanotechnology in the future. Use of nanotechnology in medical therapeutics needs adequate evaluation of its risk and safety factors. Scientists who are against the use of nanotechnology also agree that advancement in nanotechnology should continue because this field promises great benefits, but testing should be carried out to ensure its safety in people. It is possible that nanomedicine in the future will play a crucial role in the treatment of human and plant diseases, and also in the enhancement of normal human physiology and plant systems, respectively. If everything proceeds as expected, nanobiotechnology will, one day, become an inevitable part of our everyday life and will help save many lives. More information about this series at http://www.springer.com/series/15921

Ram Prasad Editor

Plant Nanobionics Volume 1, Advances in the Understanding of Nanomaterials Research and Applications

Editor Ram Prasad School of Environmental Science and Engineering Sun Yat-sen University Guangzhou, China Amity Institute of Microbial Technology Amity University Noida, Uttar Pradesh, India

ISSN 2523-8027     ISSN 2523-8035 (electronic) Nanotechnology in the Life Sciences ISBN 978-3-030-12495-3    ISBN 978-3-030-12496-0 (eBook) https://doi.org/10.1007/978-3-030-12496-0 Library of Congress Control Number: 2019936305 © Springer Nature Switzerland AG 2019 This work is subject to copyright. All rights are reserved 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, express 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 Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Preface

The purpose of this book is to describe the application and advances in the understanding of mechanisms involved in response to smart nanoparticles and plants. This work on nanomaterials and nanotechnologies (herbicides, pesticides, sensors, and food industries) covers the interdisciplinary fields such as plant biology and agriculture and nanotechnological improvements to increase crop yields, with special emphasis on environmental sustainable management. This approach has become an attractive focus in plant nanotechnology research toward resource efficient and sustainable development. The book covers the application of tailored nanoparticles targeted at food, medicine, agriculture, and toward new applications that integrate biological system with nanomaterials to produce bio-hybrids and the next generation of bionic architectures. The first chapter by Emul et al. reviews new perspectives of nanomaterials and applications in the near future. Chapter 2 by Kumari et  al. highlights the recent progress of the nanomaterials in the agriculture and food sector and clinical landscape. In Chap. 3, Sharma and Kar describe plant nanobionics and its applications. Plastics, nanomaterials, and microbe-plant interactions in the environment are discussed by Benckiser in Chap. 4. In Chapter 5, Choudhary et al. emphasize characterization techniques such as DLS, FTIR, XRD, XPS, AAS, SEM, and TEM provide reliable, consistent, and accurate results of chitosan-based nanomaterials. In Chap. 6, Omar et al. highlight on the impact (plant growth and toxicity) of nanomaterials in plant systems. In Chap. 7, Cásarez-Santiago describes that nanoagriculture offers new alternatives to increase the efficiency of crops, the quality of water, and the use of agro-wastes for energy production. In Chap. 8, Boddula et  al. highlight on nanopesticides and nanosensors in agriculture system. In Chap. 9, Sundarraj highlights on nanoagriculture in the food industry. Boskovic et al. detail that nanoencapsulation of plant extracts and plant extract-mediated synthesis of nanoparticles and their potential application improve the safety and quality and prolong the shelf life of meat and milk products in Chap. 10. In Chap. 11, Jampílek and Kráľová give an overview of impact of nanoparticles on photosynthesizing organisms and their use in hybrid structures and components of photosynthetic apparatus. The applications of nanoparticles in plant tissue culture are discussed in Chap. 12 by Álvarez et al. v

vi

Preface

Finally, advances in nanomaterials with special reference to plant metabolism are presented by Verma et al. Chap. 13. This book is designed for undergraduate and postgraduate students, researchers, policy makers, and other professionals in plant biology, biotechnology-, and nanotechnology-related disciplines. I honor the leading experts with extensive, in-depth experience and expertise in plant system and nanoscience who took the time and effort to develop these outstanding chapters. Each chapter is written by globally renowned researchers/scientists so the reader is given an up-to-date and detailed account of knowledge of the nanoscience and innumerable applications of plant biology. I wish to thank Eric Stannard, Senior Editor, Springer; Rivka Kantor, Antony Dunlap, Springer Nature USA; Rahul Sharma, Project Coordinator, Springer Nature; and Ramamoorthy Santhamurthy, Project Manager, SPi Global for their generous assistance, constant support, and patience in initializing the volume. Editor gives special thanks to his exquisite wife Dr. Avita for her infinite support and motivations in putting everything together. Dr. Prasad in particular is very thankful to Professor Ajit Varma, Amity University, for the constant encouragement, and also gives special thanks to his esteemed friends and well-wishers and all faculty colleagues of AIMT, Amity University, India, and School of Environmental Science and Engineering, Sun Yat-Sen University, China. Noida, Uttar Pradesh, India

Ram Prasad

Contents

1 Recent Advancements and New Perspectives of Nanomaterials���������    1 Ezgi Emul, Mehmet Dogan Asik, Ramazan Akcan, Kazim Kose, Lokman Uzun, Semran Saglam, Feza Korkusuz, and Necdet Saglam 2 Recent Progress in Applied Nanomaterials ������������������������������������������   33 R. Mankamna Kumari, Nikita Sharma, Geeta Arya, and Surendra Nimesh 3 An Insight into Plant Nanobionics and Its Applications����������������������   65 Shubha Rani Sharma and Debasish Kar 4 Plastics, Micro- and Nanomaterials, and Virus-Soil Microbe-Plant Interactions in the Environment ����������������������������������   83 Gero Benckiser 5 Characterization Methods for Chitosan-­Based Nanomaterials����������  103 Ram Chandra Choudhary, Sarita Kumari, R. V. Kumaraswamy, Ajay Pal, Ramesh Raliya, Pratim Biswas, and Vinod Saharan 6 Impact of Nanomaterials in Plant Systems��������������������������������������������  117 Rishabh Anand Omar, Shagufta Afreen, Neetu Talreja, Divya Chauhan, and Mohammad Ashfaq 7 Nanoagriculture and Energy Advances ������������������������������������������������  141 R. G. Cásarez-Santiago, J. J. Chanona-Pérez, C. A. Reséndiz-Mora, N. Gϋemes-Vera, A. Manzo-Robledo, M. J. Perea-Flores, and M. Q. Marin-Bustamante 8 Nanopesticides and Nanosensors in Agriculture ����������������������������������  165 Rajender Boddula, Ujwalkumar Trivedi, Ramyakrishna Pothu, Mahendrapal Singh Rajput, and Aditya Saran 9 Nano-agriculture in the Food Industry��������������������������������������������������  183 Antony Allwyn Sundarraj vii

viii

Contents

10 Nanotechnology and Plant Extracts as a Future Control Strategy for Meat and Milk Products��������������������������������������  201 Marija Boskovic, Milica Glisic, Jasna Djordjevic, and Milan Z. Baltic 11 Impact of Nanoparticles on Photosynthesizing Organisms and Their Use in Hybrid Structures with Some Components of Photosynthetic Apparatus��������������������������������������������  255 Josef Jampílek and Katarína Kráľová 12 Nanotechnology and Plant Tissue Culture��������������������������������������������  333 Sandra Pérez Álvarez, Marco Antonio Magallanes Tapia, María Esther González Vega, Eduardo Fidel Héctor Ardisana, Jesús Alicia Chávez Medina, Gabriela Lizbeth Flores Zamora, and Daniela Valenzuela Bustamante 13 Advances in Nanobiotechnology with Special Reference to Plant Systems ��������������������������������������������������������������������  371 Madan L. Verma, Pankaj Kumar, Deepka Sharma, Aruna D. Verma, and Asim K. Jana Index������������������������������������������������������������������������������������������������������������������  389

Contributors

Shagufta Afreen  CAS Key Laboratory of Bio-based materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, PR China, Qingdao, China Ramazan Akcan  Hacettepe University, School of Medicine, Ankara, Turkey Sandra Pérez Álvarez  Universidad Autonóma de Chihuahua, Facultad de Ciencias Agrícolas y Forestales, Delicias, Chihuahua, Mexico Eduardo  Fidel  Héctor  Ardisana  Universidad Técnica de Manabí, Facultad de, Ingeniería Agronómica, Portoviejo, Manabí, Ecuador Geeta  Arya  Department of Biotechnology, Central University of Rajasthan, Ajmer, India

School

of

Life

Sciences,

Mohammad  Ashfaq  School of Life Science, BS Abdur Rahaman Institute of Science and Technology, Chennai, India Department of Mechanical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok, Thailand Mehmet  Dogan  Asik  Ankara Yıldırım Beyazıt University, School of Medicine, Ankara, Turkey Milan  Z.  Baltic  Department of Food Hygiene and Technology, Faculty of Veterinary Medicine, University of Belgrade, Belgrade, Serbia Gero  Benckiser  Institute of Applied Microbiology, Justus Liebig University of Giessen, Giessen, Germany Research Center for BioSystems, Land Use, and Nutrition (IFZ), Justus Liebig University of Giessen, Giessen, Germany Pratim Biswas  Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, MO, USA

ix

x

Contributors

Rajender  Boddula  CAS Key Laboratory for Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing, People’s Republic of China Marija  Boskovic  Department of Food Hygiene and Technology, Faculty of Veterinary Medicine, University of Belgrade, Belgrade, Serbia Daniela  Valenzuela  Bustamante  Departamento de Biotecnología Agrícola, Instituto Politécnico Nacional, CIIDIR-IPN, Unidad Sinaloa, Guasave, Sinaloa, México R.  G.  Cásarez-Santiago  Instituto Politécnico Nacional, Escuela Nacional de Ciencias Biológicas, Departamento de Ingeniería Bioquímica. Av. Wilfrido Massieu s/n Instituto Politécnico Nacional, Mexico City, Mexico J. J. Chanona-Pérez  Instituto Politécnico Nacional, Escuela Nacional de Ciencias Biológicas, Departamento de Ingeniería Bioquímica. Av. Wilfrido Massieu s/n Instituto Politécnico Nacional, Mexico City, México Divya Chauhan  Department of Chemistry, Punjab University, Chandigarh, India Ram Chandra Choudhary  Department of Molecular Biology and Biotechnology, Rajasthan College of Agriculture, Maharana Pratap University of Agriculture and Technology, Udaipur, Rajasthan, India Jasna  Djordjevic  Department of Food Hygiene and Technology, Faculty of Veterinary Medicine, University of Belgrade, Belgrade, Serbia Ezgi  Emul  Hacettepe University, Nanotechnology and Nanomedicine Division, Ankara, Turkey Milica Glisic  Department of Food Hygiene and Technology, Faculty of Veterinary Medicine, University of Belgrade, Belgrade, Serbia N. Gϋemes-Vera  Instituto de Ciencias Agropecuarias, Universidad Autónoma del Estado de Hidalgo (CICyTA), Tulancingo, Hidalgo, México Josef  Jampílek  Division of Biologically Active Complexes and Molecular Magnets, Regional Centre of Advanced Technologies and Materials, Palacký University, Olomouc, Czech Republic Institute of Neuroimmunology, Slovak Academy of Sciences, Bratislava, Slovakia Asim  K.  Jana  Department of Biotechnology, National Institute of Technology, Jalandhar, Punjab, India Debasish Kar  Amity Institute of Biotechnology, Amity University of Jharkhand, Ranchi, India Department of Biotechnology, M.  S. Ramaiah University of Applied Sciences, Bangalore, India Feza Korkusuz  Hacettepe University, School of Medicine, Ankara, Turkey

Contributors

xi

Kazim Kose  Hitit University, Alaca Avni Celik Vocational School, Food Processing Department, Çorum, Turkey Katarína Kráľová  Institute of Chemistry, Faculty of Natural Sciences, Comenius University, Bratislava, Slovakia Pankaj Kumar  School of Biotechnology, Dr YS Parmar University of Horticulture and Forestry, Hamirpur, Himachal Pradesh, India R.  V.  Kumaraswamy  Department of Molecular Biology and Biotechnology, Rajasthan College of Agriculture, Maharana Pratap University of Agriculture and Technology, Udaipur, Rajasthan, India R. Mankamna Kumari  Department of Biotechnology, School of Life Sciences, Central University of Rajasthan, Ajmer, India Sarita Kumari  Department of Molecular Biology and Biotechnology, Rajasthan College of Agriculture, Maharana Pratap University of Agriculture and Technology, Udaipur, Rajasthan, India A. Manzo-Robledo  Laboratorio de Electroquímica y Corrosión, Escuela Superior de Ingeniería Química e Industrias Extractivas-Instituto Politécnico Nacional, Mexico City, México M.  Q.  Marin-Bustamante  Instituto Politécnico Nacional, Escuela Nacional de Ciencias Biológicas, Departamento de Ingeniería Bioquímica. Av. Wilfrido Massieu s/n Instituto Politécnico Nacional, Mexico City, México Jesús Alicia Chávez Medina  Instituto Politécnico Nacional, CIIDIR-IPN, Unidad Sinaloa, Departamento de Biotecnología Agrícola, Guasave, Sinaloa, Mexico Surendra Nimesh  Department of Biotechnology, School of Life Sciences, Central University of Rajasthan, Ajmer, India Rishabh  Anand  Omar  Centre for Environmental Science and Engineering, Indian Institute of Technology Kanpur, Kanpur, India Ajay Pal  Department of Biochemistry, College of Basic Sciences and Humanities, Chaudhary Charan Singh Haryana Agricultural University, Hisar, Haryana, India M.  J.  Perea-Flores  Instituto Politécnico Nacional, Centro de Nanociencias y Micro y Nanotecnologías, Mexico City, México Ramyakrishna  Pothu  College of Chemistry and Chemical Engineering, Hunan University, Changsha, People’s Republic of China Mahendrapal  Singh  Rajput  Department of Microbiology, Marwadi University, Rajkot, India Ramesh Raliya  Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St. Louis, MO, USA

xii

Contributors

C.  A.  Reséndiz-Mora  Departamento de Bioquímica, Instituto Politécnico Nacional, Escuela Nacional de Ciencias Biológicas, Mexico City, México Necdet  Saglam  Hacettepe University, Nanotechnology and Nanomedicine Division, Ankara, Turkey Semran Saglam  Gazi University, Department of Physics, Ankara, Turkey Vinod Saharan  Department of Molecular Biology and Biotechnology, Rajasthan College of Agriculture, Maharana Pratap University of Agriculture and Technology, Udaipur, Rajasthan, India Aditya Saran  Department of Microbiology, Marwadi University, Rajkot, India Deepka Sharma  School of Biotechnology, Dr YS Parmar University of Horticulture and Forestry, Hamirpur, Himachal Pradesh, India Nikita  Sharma  Department of Biotechnology, School of Life Sciences, Central University of Rajasthan, Ajmer, India Shubha  Rani  Sharma  Department of Bio-Engineering, Birla Institute of Technology, Mesra, Ranchi, India Antony Allwyn Sundarraj  Department of Food Technology, Sri Shakthi Institute of Technology and Sciences, Coimbatore, TamilNadu, India Neetu  Talreja  Department Seongnam, South Korea

of

Bio-nanotechnology,

Gachon

University,

Marco  Antonio  Magallanes  Tapia  Instituto Politécnico Nacional, CIIDIR-IPN, Unidad Sinaloa, Departamento de Biotecnología Agrícola, Guasave, Sinaloa, Mexico Ujjawal Trivedi  Department of Microbiology, Marwadi University, Rajkot, India Lokman  Uzun  Hacettepe University, Department of Chemistry, Biochemistry Division, Ankara, Turkey María Esther González Vega  Instituto Nacional de Ciencias Agrícolas (INCA), San José de las Lajas, Mayabeque, Cuba Aruna  D.  Verma  School of Biosciences, Himachal Pradesh University, Shimla, Himachal Pradesh, India Madan  L.  Verma  Centre for Chemistry and Biotechnology, Deakin University, Melbourne, Victoria, Australia School of Biotechnology, Dr YS Parmar University of Horticulture and Forestry, Hamirpur, Himachal Pradesh, India Gabriela  Lizbeth  Flores  Zamora  Instituto Politécnico Nacional, CIIDIR-IPN, Unidad Sinaloa, Departamento de Biotecnología Agrícola, Guasave, Sinaloa, Mexico

About the Author

Ram  Prasad, Ph.D.  is associated with Amity Institute of Microbial Technology, Amity University, Uttar Pradesh, India, since 2005. His research interest includes applied microbiology, plant-microbe interactions, sustainable agriculture, and nanobiotechnology. Dr. Prasad has more than one hundred fifty publications to his credit, including research papers, review articles, and book chapters, and five patents, issued or pending, and has edited or authored several books. Dr. Prasad has 12 years of teaching experience, and he has been awarded the Young Scientist Award (2007) and Prof. J.S. Datta Munshi Gold Medal (2009) by the International Society for Ecological Communications; FSAB Fellowship (2010) by the Society for Applied Biotechnology; the American Cancer Society UICC International Fellowship for Beginning Investigators, USA (2014); Outstanding Scientist Award (2015) in the field of microbiology by the Venus International Foundation; BRICPL Science Investigator Award (ICAABT-2017); and Research Excellence Award (2018). He has been serving as editorial board member in Frontiers in Microbiology, Frontiers in Nutrition, and Academia Journal of Biotechnology including series editor of Nanotechnology in the Life Sciences, Springer Nature, USA.  Previously, Dr. Prasad served as visiting assistant professor at the Whiting School of Engineering, Department of Mechanical Engineering, Johns Hopkins University, USA, and presently working as research associate professor at the School of Environmental Sciences and Engineering, Sun Yat-sen University, Guangzhou, China. xiii

Chapter 1

Recent Advancements and New Perspectives of Nanomaterials Ezgi Emul, Mehmet Dogan Asik, Ramazan Akcan, Kazim Kose, Lokman Uzun, Semran Saglam, Feza Korkusuz, and Necdet Saglam

Contents 1.1  N  anoparticles 1.2  N  anoparticles: Advantages/Disadvantages and Applications 1.3  C  arbon-Based Nanoparticles 1.3.1  Developments in Synthesis Procedures 1.3.2  Characterization 1.3.3  Applications 1.4  Quantum Dots 1.4.1  Carbon-Based Quantum Dots 1.4.2  Developments in Synthesis Procedures 1.4.3  Characterization 1.4.4  Applications 1.5  Metal-/Alloy-Based Quantum Dots 1.5.1  Developments in Synthesis Procedures 1.5.2  Characterization 1.5.3  Applications

   2    3    3    5    8    9  10  10  11  13  13  15  15  16  17

E. Emul · N. Saglam (*) Hacettepe University, Nanotechnology and Nanomedicine Division, Ankara, Turkey e-mail: [email protected] M. D. Asik Ankara Yıldırım Beyazıt University, School of Medicine, Ankara, Turkey R. Akcan · F. Korkusuz Hacettepe University, School of Medicine, Ankara, Turkey K. Kose Hitit University, Alaca Avni Celik Vocational School, Food Processing Department, Çorum, Turkey L. Uzun Hacettepe University, Department of Chemistry, Biochemistry Division, Ankara, Turkey S. Saglam Gazi University, Department of Physics, Ankara, Turkey © Springer Nature Switzerland AG 2019 R. Prasad (ed.), Plant Nanobionics, Nanotechnology in the Life Sciences, https://doi.org/10.1007/978-3-030-12496-0_1

1

2 1.6  F  orensics as an Application Field of Nanotechnological Advancements 1.6.1  Postmortem Interval (PMI) Estimation 1.6.2  Forensic Toxicological Analysis 1.6.3  Forensic Genetics 1.6.4  Crime Scene and Related Investigations 1.7  Conclusion References

E. Emul et al.  17  17  18  19  20  22  22

1.1  Nanoparticles The concept of nanotechnology, introduced for the first time by Richard Feynman in 1959, has reached the dimensions that human beings cannot imagine in the last decade. In addition to the advantages of nanoparticles that have had an impact on the areas of use due to their extrinsic properties (Fig. 1.1), they can however cause severe toxic effects on the organ and tissues biologically due to their very small particle sizes up to 1–2 nm levels. In tissues, nanoparticles can be therefore determined as a “two-sided blade” where one size cures and the other one may injure. The synthesis, characterization, and application of nanoparticles, which have a rapidly increasing use in fields such as textiles, cosmetics, medicine, electronics, computers, food, agriculture, energy, basic sciences, and automotive, are an attractive area of research (Prasad et al. 2014, 2016a, 2017a, b).

Fig. 1.1  Samples of organic and inorganic nanoparticles. (Reprinted with permission from Richards et al. 2017 Published by The Royal Society of Chemistry)

1  Recent Advancements and New Perspectives of Nanomaterials

3

1.2  Nanoparticles: Advantages/Disadvantages and Applications The use of nanoparticle in the fields of dyes, fabrics, civil engineering, diamond coatings, killing cancerous cells without damaging the body, and sensors is perceived as a new technology revolution. Nanoparticles, which are increasingly used in many areas, are making life easier. Although it may seem impossible to estimate the end point of the nanotechnology, the use of nanoparticles may come to the forefront of treating infectious diseases, traveling at speeds close to the speed of light, or even everyday use of computers capable of processing in a shorter time. The interest in nanomaterials has increased when the importance of physical dimension of nanoparticles is understood in today’s technology (Khan et al. 2017). Nanoparticles can be carbon-based (Khan et al. 2017), metallic (Pandey and Prajapati 2018), polymeric (Lam et  al. 2018; Erol et  al. 2017; Prasad et  al. 2017a, b), and magnetic (McNamara and Tofail 2017; Kose and Denizli 2013) in general. Carbon-based nanoparticles can be examined under two headings, mainly carbon nanotubes and graphene. Also, graphene oxide, fullerene, and nano-diamond derivatives play a crucial role in biomedical engineering (Cha et al. 2013). Another structure based on carbon is quantum dots with an analogical structure with graphene (Zeng et al. 2018). The quantum dots, which are much smaller than the graphene, have an excellent solvation property. Although they have a low level of cytotoxicity (Zhu et  al. 2011), they are a potential risk to the living body because they have nanolevel size (Manshian et al. 2017). Graphene quantum dots, which have been used lately in fields such as biochemistry and medicine (Yao et al. 2018), and environmental applications (Lin et al. 2018) can be synthesized in different ways (Kun et al. 2016; Liu et al. 2011; Dengyu et al. 2010; Buzaglo et al. 2016; Yan et al. 2011; Ho et al. 2014). Metal nanoparticles are more commonly known by their names such as alumina, cadmium, gold, silver, silica, iron, and platinum (Pandey and Prajapati 2018). Biosensor (Ma et al. 2018; Faraz et al. 2018), drug delivery (Zhou et al. 2018), bioimaging (Sankar et al. 2017; Prasad et al. 2016a, b), photothermal therapy (Wang et al. 2018b), electronics (Delgado et al. 2017), photonics (Budaszewski et al. 2017), and textile (Salat et  al. 2018) are the main uses. Nanoparticles with an excepted upper limit of 100 nm (Laurent et al. 2008) can be synthesized in sizes ranging from graphene quantum dots with dimensions below 20 nm (Mitchell et al. 2014) to cubic boron nitride (c-BN) nanoparticles with a size of 3 nm (Huang et al. 2018b).

1.3  Carbon-Based Nanoparticles Carbon nanoparticles are synthesized in two ways, top-down and bottom-up. In top-­ down methods (Fig. 1.2), external energy or mechanical force is applied to the bulk material to reduce the size of the material to nanolevel. Mechanical grinding (ball

4

E. Emul et al.

Fig. 1.2  Common (a) top-down and (b) bottom-up synthesis routes of nanoparticles. (Adapted with permission from Khan et al. 2017)

milling) and etching are the main methods (Zhang et al. 2018a). In addition, chemical vapor deposition (CVD) (Yazici et al. 2018), physical vapor deposition (PVD) (Azpeitia et al. 2017), and other decomposition techniques are used (Thambiraj and Ravi Shankaran 2016). The energy consumed while applying top-­down methods increases the cost of this method inevitably. In a bottom-up approach, atomic or molecular-sized structures are grown by chemical reactions, and particle formation is achieved. They are relatively cheaper than top-down methods. Sol-gel (Hintze et  al. 2016; Lim et  al. 2015), green synthesis (Swamy and Prasad 2012; Prasad 2014; Chamoli et al. 2018), spinning (Khan et al. 2017), and biochemical methods are main examples (Iravani 2011). Some of the synthesis and characterization methods for carbon-based nanoparticles are summarized in Table 1.1.

1  Recent Advancements and New Perspectives of Nanomaterials

5

Table 1.1  Some examples of synthesis procedure of carbon-based nanoparticles and other related information Nanoparticle SiC-graphene core-shell nanoparticles CNT aerogel

Synthesis method Mechanical milling FC-CVD

Carbon-encapsulated PVD metal nanoparticles Graphene quantum Chemical dots treatment

Characterization SEM, TEM, FT-IR, XPS, XRD

Application Materials science

Reference Zhang et al. (2018a)

SEM, RAMAN, FT-IR, SEM, TEM, UV-vis adsorption spectrum FE-SEM, TEM, HR- TEM, FT-IR, XRD

CNT reactor

Hoecker et al. (2017) Dai and Moon (2018) Gu et al. (2018)

SPR Optoelectronic applications

1.3.1  Developments in Synthesis Procedures In the milling method, which is one of the well-known and oldest (Benjamin 1970) of the top-down methods, the main purpose is to obtain nanoscale materials by reducing the particle size. In this method, ceramic or metal balls placed in a cabinet simply compress and break down the material placed in the cabinet. Materials with the size below 20 nm in size can be obtained if these balls are moved back and forth successive to rounding of cabinet. Different variables can be mentioned here; the most important of which is milling time (Yadav et al. 2012). The milling time is also a very important variable in determining the particle size. As time elapses, particle size decreases. In addition, temperature, charge ratio, brittleness of materials, size of billing ball, and materials made of balls are important parameters (Bello et al. 2015). In addition, GNS produced is highly irregular due to the strong impact forces between grinding balls if milling process, which can be dry or wet, is dry (Ouyang et al. 2014). In another type of ball milling, a liquid as a process control material for grinding of powders is added to get a wet environment (i.e., wet ball milling). The greatest advantage of this process is that it can operate as a lubricant between the liquid phase and impact/shear balls and convert the impact force into shear (cutting) force, i.e., the impact forces are reduced, and the shear (cutting) forces become dominant (El-Eskandarany 2015; Kumar et al. 2016). Grinding based on shearing force is very useful in peeling of graphene sheets and prevents intensive degradation of GNS (Kumar et al. 2016). Produced GNSs also have a better distribution in the “good solution” designed to prevent GNS re-agglomeration and clustering of nanoparticles (Yi and Shen 2015). Although it seems like a cheap method, it is a limiting aspect of this method that long working times and high-energy ball milling are required for the synthesis of nanoparticles. In addition, pollution that may come from the balls, lack of control on particle morphology, formation of agglomerations, and residual strain in the crystallized phase can be said as other drawbacks of the method (Nowak and Jurczyk 2017). Yousef and colleagues have reported in their

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study that they have achieved high-efficiency graphene nanosheet using simple, inexpensive, and economical multi-roll milling technique (Yousef et  al. 2018). During the application of this method, they have used nonconformal surfaces to solve the problems that are frequently encountered and originate from the spherical surface. DMF was used as the organic solvent. Zhang et al. used ethanol-water mixture as wetting billing media at varying rates to prevent destructive exfoliation of graphene nanosheets in their study of the wet ball milling method and applied grinding for 50 h (Zhang et al. 2018a, b). A graphical flake below 20 nm was obtained in situ. Finally, it has been observed that wet milling is very effective in decreasing the particle size and consequently increasing the surface area in the study performed by Kumar et al. on dry milling and wet milling (Kumar et al. 2018a). In addition, their fluidity and solubility are quite good compared to those obtained with the dry milling technique. The chemical vapor deposition (CVD) method may in fact be regarded as a surface coating method. The chemical structure of the surface is changed. Perhaps the biggest advantage is that it can be applied to all surfaces, and coating can be applied to very low dimensions (Creighton and Ho 2001). It is used intensively, especially in the production of semiconductors. The biggest disadvantage is that it is a very complex process. Using this method, very pure, dense, and fine-grained coatings are performed quickly in a regular or complex shape. With this method, especially optical coatings can be made, and silicon nanobars can be produced. In general, organic CVD can be defined as the introduction of vaporized monomers into the reaction chamber where the reaction takes place and the introduction of these monomers into the chemical reaction to form thin films on the substrate to be coated using different energy inputs (plasma, heat, light, etc.) (Yenice 2015). Studies in which alcohol was used as a precursor have been reported. It has been shown in these studies that the formation of long carbon nanotubes is promoted by alcohol. Unlike alcohol, the use of organic solvents such as acetone may not be feasible in high-temperature cases. It may be said as the reason for this problem at elevated temperatures that these organic solvents dissociate into their atoms and interfere with the CVD reactions through these atoms (Cortés-López et  al. 2018). Cortez-Lopez investigated the effect of acetone used as other organic solvent on the synthesis procedure and reported that the mixture of ethanol affected the synthesis procedure positively: acetone (1:3). Unlike the conventional CVD method, there is considerable time gain in the LCVD method in which the laser is used to heat the substrate. The material will quickly reach the desired temperature, which will be a time-efficient method (Tu et  al. 2018). The coating purity obtained in the CVD method is very high. However, the major drawback of the method that the precursors, such as (NiCO4), explosive (B2H6), corrosive (SiCI4), used can be toxic. In addition, the precursors must be volatile, so this is not a valid feature for many elements in the periodic table resulting in the restriction of application field. In addition, some metal-organic precursors may be expensive. The resulting by-products (CO, H2, HF) may present a health hazard. CVD processes at very high temperatures also severely limit the properties of the coating materials and the integrity of the coatings made (Creighton and Ho 2001). Tu et al. obtained high-quality graphene with large surface area in

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their work using laser CVD. In a study where a uniform heating field was applied, the growth time, laser power, and growth mechanism were controlled so that the layers and quality of graphene were obtained at the desired level (Tu et al. 2018). Cortes-Lopez et al., who used acetone as a carbon precursor, obtained the highest yield especially when the ratio of acetone/ethanol was 3:1 (Cortés-López et  al. 2018). The carbon nanotube radius is also high. Yazici et al. used Ar, N2, H2, and CH4 as the carrier gas, conducting the CVD process at a temperature of 1000 °C. They used ethanol and water to remove the impurities existing in precursor (Yazici et al. 2018). Physical vapor deposition (PVD) is a relatively simple and safe method. This technique is based on the principle that atoms are separated from the surface by evaporation or splashing of the material stored under vacuum and deposited atomically or ionically on the surface to be coated (Aytac and Malayoğlu 2018). It is operated at lower temperatures than in CVD.  Preparation of the material to be coated in the PVD method, transport of the vapor phase, and deposition onto the surface can be controlled independently of each other (Öztürk 2003). Evaporation can be examined under sputtering and ion plating (Ürgen 1997; Johnson 1989). The difference is the way of evaporation, using negative potential or plasma (Aytaç and Malayoğlu 2018). Also, the chemical composition, film thickness, and transition sharpness are maintained at the atomic level in this method. Although it is expensive compared to CVD, it is a very effective. There is also no precursor limitation as in CVD. Another advantage of the method is that the used chemicals and the resulting by-products are not toxic (Keleşoğlu 2011). However, the most important disadvantage is that the thicknesses of the regions where the electric field density is different, such as holes and corners on the base, are different. It is also the limiting side of the technique that transport gases such as chlorine are trapped between atoms due to high pressure and low temperature, which is causing contamination. The yield will be quite good if all the parameters are applied in a sensitive way (Keleşoğlu 2011). Oldfield et  al. have managed to deposit the multilayer graphene film on copper/­ silica surface using PVD (Oldfield et al. 2017). The method used was performed at a relatively high temperature in the filtered cathodic vacuum arc at 750 °C. Azpeitia et al. (2017) have opened the C60 fullerene molecule under ultrahigh vacuum at a lower temperature than in CVD by PVD method and have obtained large area uniform single layer graphene. Narula et al. have examined the factors that influence low-temperature graphene growth on copper (Narula et  al. 2017). In the PVD method they applied, it was possible to obtain films with different stresses of annealing time and temperature. Finally, the chemical oxidation method which takes place in room conditions by use of toluene as a solvent can be mentioned (Thambiraj and Ravi Shankaran 2016). In this method, chemical oxidation is followed by an exfoliation method. The material obtained is carbon quantum dots. The material obtained in high purity has fluorescence feature and has a high quantum yield. The material obtained at radii up to 4 nm is competent at the capacity to be used in applications such as biosensor, bioimaging, and drug delivery. Plant-based materials are used as a carbon source. The dried material is placed in an oven at 60 °C to have carbon formation. The resulting carbon is stirred in toluene for 24 h. Quantum dots are obtained after diluting with

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ethanol, which is passed through dispersion and centrifuge process. Although the organic chemical used in the method is a relatively harmful chemical, the method is simple and inexpensive.

1.3.2  Characterization We can characterize the nanoparticles regarding morphological, structural, particle size and surface, and optical properties (Khan et al. 2017). The morphology of the nanoparticles is very important because it is directly related to the field of use of the nanoparticle. Well-defined morphology means that many structural and physical properties of the nanoparticle are well-known. The most commonly used techniques for characterizing morphology are polarized optical microscopy (POM) which provides superficial information and scanning electron microscopy (SEM) where more detailed features can be seen and transmission electron microscopy (TEM). Other techniques are atomic force microscopy (AFM) (Merle et al. 1999), field emission scanning electron microscopy (FE-SEM) (Merle et al. 1999), focused ion beam scanning electron microscopy (FIB-SEM) (Kim et al. 2014), high-resolution optical microscopy (HROM) (Khenfouch et al. 2012), and scanning transmission electron microscopy (Pan et al. 2014). Almost all techniques mentioned are based on the principle of scanning electron microscopy. Electrons coming from electron gun go to the surface of the synthesized material to provide images. SEM and SEM-based methods can be used if the dispersion properties are to be examined. The situation in the TEM is somewhat different. The TEM is a device that operates on the basis of electron transmission, and therefore larger magnification ratios can be achieved. The TEM also provides information on materials with two or more layers. In AFM, the surface of the material is morphologically scanned with the help of molecular structures connected to the tip of the AFM needle, and the surface mapping of the material is obtained. It gives information about the topology of the material. More detailed information about surface and depth can be obtained by taking AFM images of materials (Khan et al. 2017). For structural characterization, X-ray diffraction (XRD), energy-dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS), infrared (IR), Raman, BET, and zeta analysis are used. XRD provides detailed information about the crystallinity and phase of the synthesized nanoparticle and superficial information about the size. When the number of nanoparticles is less than 100 atoms, the accuracy of the obtained data is reduced. EDX gives information about the composition of the material obtained and can be used as a part of FE-SEM and TEM.  As the amount of substance in the nanoparticle will change the specific X-ray intensity, the composition can be determined, because the X-Ray band of each substance is different. In the XPS method, the material is irritated by X-rays to measure the kinetic energy, and the number of electrons escaping from the material is determined. It gives infor-

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mation about empirical formula, the elemental composition, and an electronic and chemical state in the parts per thousand levels. In the IR method, the generated infrared spectra are sent to the material. Information about the bonds formed can be obtained by the particular calculations through the infrared light absorbed by the material, which provides a great deal of information about the structural characterization. In the Raman spectra, the data about the characteristics of the bonds are obtained in more detail. This gives a kind of fingerprint of the analyzed structure. The BET method is a method to obtain information about the surface area of the materials through gas molecules adsorbed on the surface of the material under certain conditions. The gases used are inert gases, such as nitrogen, since they must not interfere with the material being analyzed. Finally, zeta potential and dimensional analyses are methods used to determine if there is an inter- and intramolecular interaction between the atoms and molecules of the synthesized material and, if so, the degree of this interaction and the size of the materials. The polydispersity index value obtained after analysis gives information about the equi-dimensional feature of the synthesized material.

1.3.3  Applications Nanoparticles, whether simple or complex, are used in physics, biology, and biomedical pharmaceutical applications due to their unusual chemical, physical, and unique properties (Loureiro et al. 2016; Martis et al. 2012; Nikalje 2015). Reddy et al. (2018) examined the interaction between graphene oxide and biomaterials and found that neural cell differentiation was better performed on allotropic carbon-­ based biomaterials. In a study by Zhong et  al. (2018), spindle-shaped graphene oxide (GO) structures were modified with ZnO nanoparticles, and antibacterial composite materials against Gram-positive (B. subtilis and E. faecalis) and Gram-­ negative (E. coli and S. typhimurium) were obtained (Zhong et  al. 2018). In this study, GO increased the antibacterial activity by increasing the ZnO dispersion. Zn2+ ions, however, also supported the creation of ROS by GO on the composite surface. ROS is an important effect on the antimicrobial effect. Xu et al. have developed cobalt nanowires that have the potential for use in the catalytic industry (Xu et al. 2018). They performed this process under the external magnetic field and used reduced graphene oxide to modify the cobalt nanowire. They achieved a very high coercively value depending on the graphene modification. Mahmoudi et al. (2018) synthesized graphene and derivatives for use in solar cell applications, and the performance of the graphene-based solar cell they obtained was significantly enhanced by features such as functionalization, doping, and oxidation provided by the graphene (Mahmoudi et al. 2018; Chen et al. 2018) which have developed graphene hybrid/composite materials with extraordinary features that can be used in high-­ efficiency vacuum field emission devices. There are also many applications in areas such as lithium-ion anode (Yang et  al. 2017), super capacitor (Lee et  al. 2012; Khalid and Honorato 2018), various sensor applications (Nag et al. 2018) such as

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lysozyme sensor (Wang et al. 2017a), biomedical field (Rifai et al. 2018), electrocatalysis (Ensafi et al. 2018; Rajesh et al. 2018), drug delivery (Wang et al. 2018a, b; Hussien et al. 2018), photocatalysis (Yusuf et al. 2018), and separation (Song et al. 2018).

1.4  Quantum Dots 1.4.1  Carbon-Based Quantum Dots Quantum dots, which are themselves carbon-based nanoparticles, are zero-­ dimensional systems that are quantum-mechanically entrapped in space. Their dimensions can be reduced to several nanometers. Like natural atoms, they have intermittent electron counts that can be changed on demand, and they can be termed as artificial atoms with energy levels stable and intermittent spectra. It can be said as the reason for the increased interest in recent years is that the quantum dots have different and new physical effects considering their unusual small dimensions as compared to their counterparts (Kervan et al. 2003). Because of all these features, they are used in the fields such as energy (Kim et al. 2013; Xie et al. 2017), environmental care (Wang et al. 2015; Dong et al. 2012a, b; Zhang et al. 2017a; Zeng et al. 2016), and electronic (Kim et al. 2018; Cui et al. 2017). These extraordinary materials can be synthesized by bottom-up methods (Das et al. 2018) such as hydrothermal, solvothermal, chemical, plasma, and microwave treatment, as well as top-down methods (Zeng et al. 2018) such as hydrothermal/solvothermal, electrochemical, microwave, assisted cutting, and ultrasonic shearing (Table 1.2).

Table 1.2  Examples of synthesis procedure of carbon-based quantum dots and other related information Nanoparticle Carbon quantum dots Carbon quantum dots Graphene quantum dots

Synthesis method One-step hydrothermal treatment Chemical treatment Green chemical method

Microwave-­ Lysine-based carbon quantum assisted dots

Characterization FT-IR, XRD, TEM, HR-TEM, SAED

Application Detection of silver ions

TEM, XRD, AFM, FTIR, XPS XRD, SEM, TEM, AFM, UV-vis adsorption spectrum TEM, HR-TEM, FT-IR, AFM, XRD, NMR (H and C), XPS, FT-Raman

Photovoltaic applications Optical devices, dye-sensitized solar cells Bioimaging

Reference Arumugam and Kim (2018) Lim et al. (2018) Teymourinia et al. (2018) Choi et al. (2017)

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1.4.2  Developments in Synthesis Procedures An organic precursor glucose (Yang et al. 2015), sucrose (Tang et al. 2017), chitosan (Liang et al. 2016), citric acid (Dong et al. 2012a, b, c), orange juice (Sahu et al. 2012), etc. to be selected as a carbon source in this synthesis method are dissolved in deionized water (Shen et al. 2018). It is then filtered successive to treatment at high temperatures in the autoclave and oven. Carbon quantum dots can be obtained after dialyzing about 4–5 days against deionized water. Although this method seems to be feasible for getting good quality crystal structures, it does have the disadvantage considering not being able to follow the crystal growth and expensive autoclave requirement (O’Donoghue 1983). Guo et al. (2018) obtained high-purity carbon quantum dots using a microwave irradiation-assisted hydrothermal method in a short time of 5 min. Shen et al. (2018) used citric acid and glucose as precursors in their work and obtained quantum dots with the size of 2–6 nm. In the study conducted by Sahu et al. (2012), orange juice was mixed with ethanol to get 0.4 g of C-dots. They follow the hydrothermal treatment route at 120  °C for 2.5  h (Sahu et  al. 2012). This study is critical in using biomass to obtain carbon dots, despite the low yield. It is very common to use organic solvent extraction and solvothermal carbonization tandem in the synthesis of carbon quantum dots (Bhunia et al. 2013; Xu et al. 2013). The process is performed with the heating of carbon-yielding compounds in organic solvents with a high boiling point, and then it is extracted (Namdari et al. 2017). Because an organic solvent, which may be potentially harmful, is used in high temperature, solvothermal method is riskier than hydrothermal method. Moreover, the excess amount of solvent used should be treated carefully at the end of the process (Lin et al. 2018). Tian et al. have reduced substantially the cost of the graphene quantum dots production using hydrogen peroxide (Tian et al. 2016). Li et al. have used the coal as a precursor to synthesize nitrogen-doped carbon dots via solvothermal process, and they achieved relatively high quantum yield (Li et al. 2017). Zan et al. followed the solvothermal process using 4-aminosalicylic acid and phosphoric acid as reactants and obtained nitrogen co-doped carbon quantum dots (Zan et  al. 2018). In this study, they synthesized the biocompatible PNCQDs with desired low toxicity. Moreover, the water-soluble material is photostable. This material can be used for the biologic and environmental differentiation of NO2− because nitrite has the great quenching effect. In chemical treatment, namely, thermolysis, organic precursors are carbonized, and then controlled oxidation is applied to cut obtained material into small sheets (Ray et  al. 2009; Tian et  al. 2009). The main disadvantage of this method is the harsh conditions (Namdari et  al. 2017). CQDs were obtained from carbohydrate such as glucose, sucrose, etc. by dissolving in distilled water by the addition of water successive to concentrated H2SO4 (Peng and Travas-Sejdic 2009). After stirring and the centrifugation, black carbonaceous powder was obtained. The neutralization process was performed after refluxing the solution containing carbon powder and nitric acid (Das et  al. 2018). Carbon dots 1.5–2.5  nm in size were obtained,

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which are water soluble via high-temperature heat treatment. CQDs are handy for the application in bioimaging because of biocompatibility and effective photoluminescence performance (Liu et al. 2009). CQD may be obtained by the neutralization of 11-aminoundecanoic acid (H2N(CH2)10COOH) aqueous solution using a strong acid such as NaOH (Zhao et al. 2011). After filtration process, aqueous citric acid is added to the precipitation obtained. An application of a well-organized purification will provide pure CQDs. CQD was synthesized using plasma-induced pyrolysis in a study, in which yolk of an was used as precursor (Wang et  al. 2012). Intense plasma beam was used to irradiate the yolk to obtain a black product containing CQD. After an extraction process, CQD of 2.15 nm in size was obtained. CQD was synthesized from d-fructose in another study of environment-friendly method. After treating the d-glucose with sodium hydroxide (Huang et al. 2015), the solution was divided into two to make a comparison about the yield, one of which was heated under the temperature of 60 °C and the other gone microplasma treatment method. The fluorescence intensity of the CQD obtained by latter method was better as compared to that obtained in the former method. The same comparison is valid considering the sizes of GQD obtained both of the methods as 2.4 nm and 3.5 nm, lower one of which was obtained by a plasma method. Production of carbon-based material via green methods is a desired process by the researchers. Notably, the process should be completed in the shortest time (Tabaraki and Sadeghinejad 2018) with high accuracy. Being time- and cost-­ effective is the primary critical points of a method. Moreover, the surface morphology of particles can be controlled at the desired level because energy is supplied with high uniformity (Rangel-Mendez et al. 2018). Therefore, fast reduction process for graphite oxide/GO is feasible with low energy requirement and thus low amount of heat as an output of the process (Voiry et  al. 2016; Matsumoto et  al. 2015). The required features mentioned above were met by microwave-assisted reduction (Kumar et al. 2018a, b). Because the interaction between carbon-based nanomaterials and radiation released by microwave is quite intense, synthesis assisted by microwave was promising in carbon nanomaterial production (Fig. 1.3) (Kumar et al. 2018b).

Fig. 1.3  An example of GO hybrid synthesis using microwave method. (Reprinted (adapted) with permission from Shown et al. 2014. Copyright (2014) American Chemical Society)

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There are several studies on microwave-assisted procedure and modification method in the literature to synthesize carbon-based nanomaterials (Schwenke et al. 2015; Sridhar et al. 2010; Wei et al. 2009; Hu et al. 2012). It is possible to get CQD synthesis under radiation in a time less than 1  min from the precursor such as sucrose in the reaction medium containing diethylene glycol (DEG) (Jaiswal et al. 2012). These DEG-stabilized CQDs (DEGCQDs) particles disperse very well in water. Effective incorporation into C6 glioma cells was achieved. They can be used in bioimaging because of low cytotoxicity (Namdari et al. 2017).

1.4.3  Characterization Characterization of quantum dots, being a nanoparticle, can also be done by methods used to characterize nanoparticles. Apart from these, the scanning tunneling electron microscope may be used to see the surface more clearly and in the case of mapping (Drbohlavova et al. 2009). Moreover, UV absorption, diffuse reflectance UV (Rangel-Mendez et  al. 2018), and photoluminescence may be used to inves­ tigate the optical properties of quantum dots such as white light-emitting, etc. (Vanessa et al. 2018).

1.4.4  Applications Carbon nanoparticles (CNPs) are used in the construction of biomedical (bio­ labeling, bioimaging, biosensors, etc.), sensors, lasers, photocatalysis, and ­photocatalytic devices with optical properties such as wavelength-dependent photoluminescence (PL) behavior, high fluorescence quantum yield, and up-­conversion fluorescence emission. It is used as a fluorescence agent in applications (Choi et al. 2014; Li et al. 2012a, b; Roy et al. 2015). Also, due to their biocompatibility and low cytotoxicity, CNPs have begun to be used as alternatives to biotechnological, biomedical, and environmental applications, instead of dyes, heavy metal-based quantum dots, and other carbon-based nanostructures (Alaş and Genç 2016; Yao et al. 2018). There are several types of research in the literature on the use of QDs in biomedical applications such as labeling cells (Peng et al. 2012; Pan et al. 2012; Wu et al. 2013; Kumar et al. 2014; Dong et al. 2012a; Shang et al. 2014). Moreover, the use of photoluminescence carbon dots in vitro and in vivo for targeted drug delivery is also reported (Hola et al. 2014). In the drug delivery system (Fig. 1.4) developed by Javanbakht and Namazi, doxorubicin was delivered via carboxymethyl cellulose/graphene quantum dot nanocomposite hydrogel films (Javanbakht and Namazi 2018). H-bonding is the primary interaction between GQDs and CMC. The performance of the nanocomposite system was proved some test. They concluded the feasibility of the use of this nanocomposite material in drug delivery systems. Dong et al. have synthesized arginine-glycine-aspartic acid (RGD)-conjugated graphene quantum dots (GQDs) and used to deliver doxorubicin (DOX) to related tissue for

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Fig. 1.4  Nanoparticles for a drug delivery system (Reprinted with permission from McNamara and Tofail 2017)

targeted imaging without the use of dyes (Dong et al. 2018). The nano-sized carrier was achieved to enter the cell and the release of the drug. In another application, mitochondrial H2O2 was detected via enhanced and multifunctional CQD-based fluorescence resonance energy transfer (FRET) probe. Energy transfer was achieved from the CQDs, as a donor. There is covalent attachment between boron-protected fluorescein, to be used to recognize H2O2, and CQDs (Du et al. 2014). Cai et al. achieved the construction of electrochemical sensor of polyaniline functionalized graphene quantum dots/glassy carbon electrode (Cai et  al. 2018). Polyaniline was doped through –COOH groups on the GQDs, resulting in good dispersion and conductivity. The calycosin can be determined via modification of glassy carbon electrode (GCE by PAGD (PAGD/GCE)). Sahub et al. have detected organophosphate pesticide using graphene quantum dot-based biosensor exploiting the photoluminescence behavior (Sahub et al. 2018). Shin et al. reported the doping of graphene quantum dots (GQDs)-mixed silver nanowires (Ag NWs) GRTCEs on polyethylene terephthalate substrates for highly flexible organic solar cells (OSCs) (Shin et al. 2018). The performance of FOSCs was achieved by modification with the use of GQDs-mixed Ag NWs/GRTCEs. The Ag NWs/GR/PET substrates are highly flexible to contain the GQDs. Zhang et al. used the hydrothermal method to obtain ZnS quantum dots (QDs) with sub-10-nm-­ scale on graphene nanosheets. The composite materials they have synthesized have a specific capacity of 491 mAh/g at 100 mA/g at the end of the 100 cycles. Rate capability of material is 317 mAh/g at 1A/g as anode (Zhang et al. 2018a, b). Kim and Kim (2018) have developed poly(N,N′-bis-4-butylphenyl-N,N′-bisphenyl) benzidine: octadecylamine-graphene quantum dots (Kim and Kim 2018). The ODA-­ GQDs provide the enhancement in the efficiency of the OLEDs through injecting holes (Shan et al. 2017).

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1.5  Metal-/Alloy-Based Quantum Dots Quantum dots may be metal/alloy based as well as being carbon-based (Lin et al. 2018). The size and the composition of quantum dots (QDs) can be modified by alloying or dope process (Mansur et al. 2017) resulting in changing optical properties (Yu et al. 2014; Bailey and Nie 2003; Zhong et al. 2003; Wang et al. 2013). It is possible to obtain cation or anion alloyed quantum dots having different energy gaps, where the energy gap increases with the increase in the constituent having wider energy gap (Adegoke et al. 2015; Regulacio and Han 2010). According to some studies, electronic transitions observed on CQDs are σ→σ*, σ→π*, π→π*, n→π*, and n→σ*, identifying their physicochemical and optical properties (Park et al. 2016; Yuan et al. 2016). There are studies in the literature reporting the facile synthesis of heteroatom-doped CQDs using raw easily accessible raw materials (Li et al. 2012a, b; Wang et al. 2016; Xu et al. 2016; Yao et al. 2015). The charge density of metal ions is combined with the electronic mobility of graphene structure resulting in the modification and enhancement of the physicochemical feature of CQDs (Lin et al. 2018), catalytic property, etc. Moreover, the chemical modification may be possible to chelate the functional groups on the CQDs via bonding elements around metal ions. Studies are demonstrating the possible quenching of fluorescence released by CQDs through interaction between surface functional groups on carbon quantum dots and metal ions (Gao et al. 2016; Sun et al. 2013).

1.5.1  Developments in Synthesis Procedures Liu et al. synthesized the FePt/MgO NPs using high-temperature organic method (Liu et al. 2018). In doing so, they have used 1,2-hexadecanediol as reducing agent and perform the co-reduction of iron acetylacetonate [Fe(AcAc)3] and platinum acetylacetonate [Pt(AcAc)2]. Afterward, the MgO shell on FePt NP surface was grown. In this study, magnesium (II) acetylacetonate [Mg(AcAc)2] using FePt cores was decomposed thermally. In another work by Ramasamy et al., they used the sol-­ gel method for the synthesis of Ca-doped CeO2 quantum dots (Ramasamy et  al. 2018). Sol-gel technique is a very useful method for obtaining both inorganic and organic-inorganic hybrid polymers. The main advantage of this technique is that the entire process is carried out on very moderate conditions. On the contrary to solid-state processes, the sol-gel process provides control at the molecular level in the reaction pathway during the conversion of the precursor species to the final product. Thus, the sol-gel process allows the synthesis of well-­ defined nanoparticles in uniform crystal morphology with very high purity and homogeneity. Being a complex process is a disadvantage for sol-gel synthesis. The reason for this is the dual role of water, one of which is the role in ligand formation and the second the reacting tendency of metal oxide precursors with water. The other reason is that there are a variety of reaction parameters such as temperature,

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pH, stirring method, oxidation rate, hydrolysis, condensation rate, etc. that to be controlled carefully to ensure good reproducibility (Toygun et al. 2013). Also, since organometallic precursors containing different metals can be mixed, homogeneity and controlled addition are easily accessible. With the appropriate chemical modification of the precursor material, the hydrolysis and condensation rate can be controlled. The colloid particle and pore size and the final product porosity and pore surface chemistry can be controlled (Banaz 2009). Precursor materials are often expensive and moisture-sensitive and prevent the transformation of special-purpose applications such as optical coatings to large-scale production sites. The process is also time-consuming and requires careful aging and drying process (Basile and Ghasemzadeh 2017).

1.5.2  Characterization Characterization of metal-/alloy-based quantum dots, being a nanoparticle, can also be done by methods used to characterize nanoparticles. Some of the synthesis and characterization methods for metal-/alloy-based quantum dots are summarized in Table 1.3.

Table 1.3  Some examples of synthesis procedure of metal/alloy quantum dots and other related information Synthesis Nanoparticle method MgO-coated FePt High-­ NPs temperature organic method CuGaS2 quantum Sol-gel synthesis dots embedded borosilicate glass

Magnesium and nitrogen co-doped carbon quantum dots Cobalt(II)-doped carbon dots (CCDs) Gd-doped green-emitting CDs

Hydrothermal method

Solvothermal method Microwave method

Characterization XRD, TEM, XPS, FT-IR, VSM, UV-vis absorption spectra DTA, TGA, DSC, XRD, XPS, TEM, STEM, HR-TEM, SAED, UV-vis absorption spectra HR-TEM, TEM, XPS, FT-IR, UV- vis absorption spectra, NMR (H and C) TEM, FT-IR, XPS, FRET, UV-Vis absorption spectra HR-TEM, XRD, XPS, FT-IR, UV-Vis absorption spectra, confocal laser scanning microscopy

Application Electrochemical applications

Reference Liu et al. (2018)

Photoelectric devices

Zhong et al. (2014)

Detection of metal Liu et al. ions (2016)

Detection of metal Zhang ions et al. (2017b) Gong et al. Medical imaging (2014) (as bimodal nanoprobe)

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1.5.3  Applications Because the chemical composition and size of metal-/alloy-based quantum dots can be adjusted, they can be used in the fields such as high-density memory, optoelectronics, quantum dot lasers, biomedical fluorophores, biolabeling and biosensing, and solar cells. Surana et al. (2018) synthesized CdSe QDs with multiple sizes, and they achieved the trapping photons in the visible spectrum (Surana et  al. 2018). Huang et  al. (2018a, b) using CuInS2/ZnS-based quantum dot synthesized light-­ emitting diodes. They have achieved the efficiency with a rate of 11%, from 5.6 to 6.2 cd/A (Huang et al. 2018a, b).

1.6  F  orensics as an Application Field of Nanotechnological Advancements As a multidisciplinary area, modern forensic sciences have been playing a key role in criminal investigation for over a century. A plenty of scientific methods are utilized to find out crime-related evidences and match them with victims or criminals. On the contrary to conventional methods, use of nanomaterial and nanotechnology takes place among novel applications among forensic sciences. Criminal investigation is now experiencing a new era with the use of nanosensors, lab on a chip application, and nanomaterials facilitating crime-related analyses. Novel methods developed for forensics technologies are based on utilization of a number of spectroscopic techniques; scanning and transmission electron microscopies, light scattering, recently developed imaging technologies, atomic force microscopy, spectroscopies coupled with microscopes (Lloyd-Hughes et al. 2015). Use of novel techniques makes the analyses of evidences of nanoscale possible, and identification and collection of materials recovered from a crime scene become easier and more actual by use of nanomaterial. Recent literature shows paths of successive use of nanotechnology and nanomaterials in forensic pathology, forensic toxicology, forensic genetics, crime scene-related examinations, trace analyses, and material and residue detection that are used in the service of law (Redasani et al. 2016). In this chapter recent advancements regarding use of nanomaterial and nanotechnology in forensic science applications will be presented.

1.6.1  Postmortem Interval (PMI) Estimation Postmortem interval (PMI) estimation describes the duration between the actual time of death and time of discover of the deceased. It takes place among the most important questions throughout history of mankind. Although postmortem interval is one of the most studied topics in forensic science, a valid and highly predictive method that widely used in PMI has not been developed yet.

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A wide spectrum of studies has been published in the literature from different scientific subdivisions including forensic medicine, molecular biology (Adserias-­ Garriga et al. 2017), biochemistry (Mao et al. 2013), biophysics, botany and palynology (Lancia et  al. 2013), entomology (Arnaldos et  al. 2005), anthropology (Cattaneo 2007), and many others. As an emerging methodology, nanoscience and nanotechnology have been rising in all of these scientific branches as well as their applications regarding postmortem interval studies. Biomolecule degradation after death has been under investigation for many years in means of postmortem interval estimation. Specific biomolecule degradation patterns including DNA, RNA, and specific protein and enzymatic markers have been investigated to determine postmortem interval (Li et al. 2014; Strasser et al. 2007). Atomic force microscopy is one of the useful tools to investigate biomolecule ­degradation patterns and degradation-related consequences like elasticity of membranes (Kozlova et al. 2013; Wu et al. 2009; Girasole et al. 2007; Pittner et al. 2016). Determining integrity of protein markers and full-scale proteomics are studied and considered as useful methods to determine postmortem interval (Kwak et al. 2017; Cheng et  al. 2006). Although there are more sophisticated and well-established nanotechnological methods in diagnostic medicine, especially in oncological diagnostics which may be used in proteomic analysis in relation with postmortem interval and have a great potential in forensic sciences, there are very few studies in the literature (Cheng et al. 2006; Wang et al. 2017b; Creagh and Cameron 2017). Surface-enhanced Raman spectroscopy is another tool, which is studied in relation with postmortem interval estimation from skeletal remains via determining bone tissue chemo-metrics.

1.6.2  Forensic Toxicological Analysis The most common and effective use of nanomaterials and nanotechnology seems to be forensic toxicology in terms of detection of a wide spectrum of toxic agents and analyses of various alternative biological samples. Recent advances are promising in terms of detection of illicit drugs and medications at nanoscale in a number of biological samples such as body fluids, hair, and postmortem soft tissue samples (Shyma et al. 2015). Level of detection and quantization of certain toxic agents were decreased, and instrumental detection ability has been enhanced by use of nanoparticles of gold, silver, and titanium in certain steps of analyses (Prasad et al. 2016a, b). Recently, XPS, HPLC, and Tof-MS techniques that developed by nanotechnological implementations utilized for delicate detection of several medical formulations and illicit drugs. Another benefit of this scientific improvement is decreased time of whole analytical process and increased sensitivity and specificity (Butler 2005). Some other researches have showed development of nanosensor, lab on a chip, and similar technologies to actualize fast cost-effective field tests which is easy to use and effectively show toxicological screening immediately. The literature review also reveals successively applied nanosensors’ applications for forensic toxicological analyses on actual biological samples (Bienvenue et al. 2010).

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1.6.3  Forensic Genetics Forensic genetics is a discipline which mainly deals with identification to establish critical information about species of biological samples gathered from crime scenes (i), kind of biological samples (ii), assessment of paternity (iii), and an individual’s personal identity whose biological sample is related with a crime or a crime scene (iv). As the most important part of forensic genetics, current identification methodologies are based on genetic polymorphisms. Through the decades, forensic scientists have used blood type polymorphisms, variable number tandem repeats, and short tandem repeats (STRs) to assess identities. STR loci are useful due to its relatively less time-consuming benchwork and its results easy to store as a database. INTERPOL and FBI still use DNA fingerprint database gathered as 13 different STR loci which are also known as combined DNA index system (CODIS). These STR loci currently determine with real-time quantitative polymerase chain reaction (RT-PCR) by commercial STR kits. In assessment of kind of biological samples, ELISA methods and more recently miRNA-based methods are leading (Kayser 2015). Forensic DNA analysis consists of sample preparation, which is basically DNA extraction, PCR phase, and post-PCR phase that is about gathering DNA fingerprints of biological samples. Reducing analysis time is one of the crucial issues in forensic DNA analysis. In sample preparation, there are several commercial products, which can reduce DNA extraction time with magnetic nanoparticles. Also, many commercial devices use microfluidic nano-systems to reduce analysis time by reducing post-PCR phase time (Chaitanya et al. 2018). Another issue in the field is to determine criminal suspects’ phenotypes from their genetic materials. In the last decade, forensic scientists had great improvement in this topic, and there are different methods which have successful results in estimation of skin color and eye color, and there are commercial RT-PCR kits to assess eye color from biological samples (Prasad et al. 2016a, b). However, it is an argument that these kits are cost-effective or not, especially in developing countries. Besides, ethical considerations about phenotyping an individual based on a suspect still a questionable issue. Many nanotechnologic studies have an effect directly or indirectly on forensic technologies. Microfluidic systems and electrophoretic systems have been studied and as a result have some commercial products in post-PCR phase of STR-based identification. Efficacy of PCR may be enhanced by nanoparticles in forensic DNA analysis. Silica-based magnetic nanoparticles and copper nanoparticles have been utilized in order to enhance the PCR quality and efficacy for obtaining DNA from body fluids and skeletal remains. In this course of analyses, DNA isolation was achieved via PCR amplification with novel adsorbents as magnetite nanoparticles with carboxylic compounds (Satvekar et  al. 2014; Romeika and Yan 2013). Au nanoparticles were also showed to significantly improve PCR efficiency. There are great expectations from single nucleotide polymorphism (SNP)-based identification systems as they are claimed to be more powerful from STR-based systems and have information about ancestry and phenotype. Time dependency and bad

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results with DNA mixtures are two main problems of current SNP-based method studies which may be overcome with successful results of nanoprobe and microarray studies with DNA (Muro and Lednev 2017). The literature suggests that trace evidences of biological samples may be distinguished from others or positively confirmed with atomic force microscopy (AFM) or surface-enhanced Raman spectroscopy (SERS) (Meng et al. 2018; Jones et al. 2012). Also, it is important not to harm the evidence in determining kind of sample to have a chance of getting DNA fingerprints from the evidence. SERS may be used in the field due to its accomplishment in evidence protection. Also these methods require far less sample than current methods. Another superiority of these methods is estimating the deposition time of blood in crime scene at the same time with identification of kind and species.

1.6.4  Crime Scene and Related Investigations 1.6.4.1  Fingerprint Detection Detection of fingerprints is a crucial part of every case of crime scene investigation. Through the decades, fingerprint detection and preserving has been upgraded from diffuse simple conventional powdering to nanotechnological methods, which are also called nano-fingerprinting. Since fingerprints are deposits of sweat, epithelial cell fragments and environmental traces, they may be used to assess identity from both morphologic features of fingerprint and DNA analysis of fingerprint and to gather trace evidences including explosives and drugs. Fingerprints may be found in three different states which two of them, plastic or patent, have less difficulties in obtaining and analysis, but latent fingerprints have been studied with many methods by forensic scientists since they had to be processed before visualizing on porous or semi-porous surfaces. Different nanoparticles have been studied to visualize more prominently and to obtain the fingerprints in detail (Yung-fou 2011). These nanoparticles can enhance contrast of the fingerprint on the surface by binding specific amino acids or lipids in the fingerprint. Scanning electron microscopy is used to reveal latent fingermarks on low-­density polyethylene. Eccrine deposits around sweat pores were shown to interact with cyanoacrylate that cause polymerization. A study utilizing vacuum metal deposition revealed that deposition of zinc was interacted with the polymerized cyanoacrylate, and its fibrils decorated with zinc nanoparticles. Therefore, vacuum metal deposition process was enhanced that result in increased fingerprint display (Solomon et al. 2018). DNA analysis from fingerprints is another topic of the related studies. As fingerprints have very little amounts of DNA, nanoparticle-assisted DNA extraction methods are useful to gather an amount of DNA enough for profiling process (Jones 2011).

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Nanotechnologic developments have improved expectations about information that gathered from fingerprint examination. Forensic scientists suggested that fingerprints may be useful in estimating age, gender, and emotional state from analysis of its content since its chemical content is primarily being effected with these factors. 1.6.4.2  Bloodstain Examination Analyses of biological and samples recovered from crime scene are vital to solve crimes by evaluating characteristics of sample and identification of individuals involved in crime. As conventional applications a number of detection and identification procedures for bloodstains have been utilized. Color change of stains based on interaction with phenolphthalein and tetramethylbenzidine helps to detect bloodstains. Nevertheless, analyses for other characteristics of bloodstains opened the path for novel nanotechnological methods. At this point atomic force microscope rises as an alternative tool that showed promising results in terms of bloodstain characteristics, which are highly useful for crime scene reconstruction. 1.6.4.3  Residue Analysis 1.6.4.3.1  Explosive Detection The use of technology for terrorist activities makes fight against terrorism more difficult. Today, new kinds of explosives have been developed, and methods of use and trafficking have been changed globally. In this respect, nanomaterials and related technology potentially play an active role for improving nanosensors that specifically detect traces and residues of explosives. The literature reveals a plenty examples of nanosensors with marked ability of detection and a number of chemical molecules and biological compounds used as weapons including explosives. Electronic noses are used to find explosives, while nano(electro)mechanical s­ ystems have been used for detection of commonly used explosion materials and plastic explosives. 1.6.4.3.2  Gunshot Residue Analysis Gunshot residue analysis is highly important in investigation of firearm-related crimes and deaths. Following discharge of a firearm, a part of microscopic particles of gunshot residues may be settled on hands, clothes, or possessions of shooter. Today high-resolution scanning electron microscope is used for gunshot residue analysis to locate them, and X-ray spectrometry identifies their elemental composition. Researchers performed studies in order to find out information regarding

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elemental and crystallographic signatures of gunshot residues. Metallic nanoparticles and crystalline Pb and Sb nanoparticles were observed by electron microscopy.

1.7  Conclusion As nanotechnology develops, nanoparticles will inevitably take up more of our lives. It is clear from the information given above how vital the choices made in the synthesis and application of nanoparticles are, considering the adverse effects on living health on the contrary to the life-facilitating and solution-oriented applications. It is inevitable for these innocent substances to enter into our lives, but these effects have to be minimized, or green nanotechnology should rise as much as possible. Incredibly small sizes will undoubtedly cause these nanoparticles to penetrate into our cells, but at the very least, a mechanism that cleans them is essential. Textiles that work in extreme conditions, longer life of batteries, lighter but durable materials for space technology, surface coatings that prevent contamination and infection, and sanitation of water using nanotechnology are not far away from our lives. There is more research that will convert to application in the near future.

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Chapter 2

Recent Progress in Applied Nanomaterials R. Mankamna Kumari, Nikita Sharma, Geeta Arya, and Surendra Nimesh

Contents 2.1  I ntroduction 2.2  N  anotechnology in Agriculture Sector 2.2.1  Effect of Nanoparticles on Germination of Seed 2.2.2  Nanofertilizer and Nanopesticides 2.2.3  Role of Nanosensors in Agriculture 2.3  Role of Nanoparticles in Food Sector 2.3.1  Food Processing and Packaging 2.3.2  Other Advantages of Nanomaterials in Food Industry 2.4  Application of Nanomaterials in Manufacture and Electronics 2.5  Applications in Environment 2.6  Nanotechnology in Medicine 2.6.1  Organic Nanoparticles 2.6.2  Liposomes 2.6.3  Inorganic Nanoparticles 2.7  Conclusion References

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2.1  Introduction Nanotechnology, a new frontier in this century, has evolved as a promising field involving interdisciplinary research. This mainly deals with nanometre-size particles ranging from size 1 to 100 nm displaying varied properties from that of bulk materials that include physical strength, chemical reactivity, electrical conductance, magnetism and optical effects. Nanotechnology is a multidisciplinary field involving integration of biotechnology, nanotechnology, material science and system engineering of sensors, molecular motors and other nanobiomaterials.

R. M. Kumari · N. Sharma · G. Arya · S. Nimesh (*) Department of Biotechnology, School of Life Sciences, Central University of Rajasthan, Ajmer, India © Springer Nature Switzerland AG 2019 R. Prasad (ed.), Plant Nanobionics, Nanotechnology in the Life Sciences, https://doi.org/10.1007/978-3-030-12496-0_2

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Generally, nanoparticles are synthesized using two approaches: “top-down” and “bottom-up” approach. Initially, the most commonly employed approach is “topdown” method, referring to the attrition of the larger particles or materials to nanoscale range through different various methods of communition. However, recently “bottom-up” approach has been increasingly utilized for nanoparticle synthesis. Nanoparticles are made of three main layers: (a) the surface layer, which is capable of functionalization with several small molecules, polymers or ligands and metal ions; (b) the shell layer, a chemically different material from the core; and (c) the core, which basically refers to the nanoparticle itself. Thus, their flexible properties have sparked attention of scientists for development of various compatible products in many industrial sectors such as medicines, plastics, electronics, agriculture, food and energy. The nanomaterials synthesized are used as fillers in plastics, as coatings on surfaces, as UV-protectants in cosmetics, etc. Similarly, efforts are being made all around the world on developing new applications of nanotechnology that probably might revolutionize much of our living in future. In addition, green nanotechnology has also gained attraction to overcome the disadvantages arised by chemical synthesis (Arya et al. 2016, 2018; Kumari et al. 2016). The current chapter mainly deals with the major types of nanoparticles used in various applications such as biological, environmental, health and science.

2.2  Nanotechnology in Agriculture Sector The booming increase in the population around the world has raised concern to feed many mouths. And among all the countries, developing nations depend more on agriculture making 60% of the population depend on agriculture sector for their livelihood (Brock et al. 2011). This further calls for the need of sustainable agriculture to meet the growing needs (Prasad et al. 2017a). Nanotechnology, a novel scientific approach, has already made its way in therapeutics and industrial field. Its incorporation in the agriculture field is made owing to its ability with novel tools for management of diseases and disease detection and enhancing plants’ ability to absorb nutrients or pesticides (Tarafdar et al. 2013). Thus, nanotechnology research and development holds great potential in agriculture sector by aiding in expansion of genetically modified crops, animal production inputs and improvement in farming techniques (Prasad et al. 2012, 2014) (Fig. 2.1).

2  Recent Progress in Applied Nanomaterials

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Fig. 2.1  Represents role of nanotechnology in agriculture sector

2.2.1  Effect of Nanoparticles on Germination of Seed Silver nanoparticles (AgNPs) are the most widely used particles in most of the fields including natural ecosystems. In one of the studies, AgNPs synthesized by different methods were used for determination of its effect on the germination of seeds. Two AgNPs  – 20-nm polyvinylpyrrolidone-coated silver nanoparticles (PVP-AgNPs) and 6-nm gum arabic-coated silver nanoparticles (GA-AgNPs) – were used on testing germination of common wetland plants. It was found that GA-AgNPs reduced the growth of maximum number of plants upon direct exposure. However, the effect was less pronounced in soil exposure experiment. Whereas, PVP-AgNPs and AgNO3 solution did not show any significant effect except one species. Thus, effects were seen to differ from one taxa to another (Yin et  al. 2012). In another study using AgNPs on Bacopa monnieri plant showed enhanced peroxidase and catalase activity depicting stressed condition of plant. However, no toxicity effects were observed (Krishnaraj et al. 2012). Also, silica, palladium, gold and copper nanoparticles are known to influence germination of plants such as lettuce (Shah and Belozerova 2009). Recently, scientists have been probing for fluorescent nanomaterials with

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better photostability and biocompatibility in order to develop novel imaging techniques in plants. In this respect, CdSe quantum dots and highly biocompatible FITC-labelled silica nanoparticles were employed to study its effects on rice seedlings. FITC-labelled silica nanoparticles did not affect the growth of the plant. However, quantum dots arrested the germination (Shah and Belozerova 2009). Oxides of silicon, such as nanosilicon dioxide (nSiO2: size 12 nm), also enhanced the seed germination of tomato (Siddiqui and Al-Whaibi 2014). The findings showed considerable potential of silica nanoparticles to be used as both fertilizers and biolabels. Other nanoparticles, such as TiO2, displayed delay in germination of Zea mays L. and Vicia narbonensis L. upon short-term exposure (24 h). Also, root growth was affected when treated with higher concentration of nanoparticles. Similar results were noticed in another study, where growth of wheat seedling was affected at higher concentrations. At a concentration of 2 and 10  ppm, the shoot length was higher. Thus, at a suitable concentration, the nanosized TiO2 can promote germination in relative to bulk concentration (Castiglione et al. 2011; Feizi et al. 2012). The potential toxicity of zero-valent iron nanoparticles (nZVI) and three types of nanosilver differing in their particle size were employed for determination of seed germination in ryegrass, barley and flax exposed at 0–5000 mg L−1 nZVI or 0–100 mg L−1 Ag. The inhibitory effects were more pronounced in aqueous suspensions at 250 mg L−1 for nZVI and 10 mg L−1 for Ag. It was observed that a complete inhibition of germination was attained at a concentration of 1000–2000 mg L−1 for nZVI, whereas no complete inhibition for Ag. In the presence of soil, the inhibitory effects were observed at 750 and 1500 mg L−1 in sandy soil for flax and ryegrass, respectively. Whereas, in case of barely, 13% of germination occurred even at a higher concentration of 1500 mg L−1. However, the growth was not much affected when grown in clay soil. The results, thus, indicated that the nZVI can be used at lower concentrations for plant growth. However, the use of Ag did not show any size-dependent effect and did not completely impede the seed germination, which indicated less suitability of seed germination tests for the study of environmental impact of Ag (El-Temsah and Joner 2012). Consequently, it becomes necessary to study phytotoxicity of different nanoparticles. Five types of nanoparticles (multiwalled carbon nanotube, aluminium, alumina, zinc and zinc oxide) were taken to test its effect on seed germination and root growth of six higher plant species (radish, rape, ryegrass, lettuce, corn and cucumber). Among these particles, only nanoscale Zinc (nano-Zn) and nanoscale Zinc oxide (nano-ZnO) showed toxicity on ryegrass and corn, respectively. However, the root growth varied greatly depending on the type of nanoparticles and plants. A concentration of 2000 mg/L nano-Zn or nano-ZnO inhibited the root elongation of the plant species. The IC50 of nano-Zn and nano-ZnO was found to be nearly 50 mg/L for radish and 20 mg/L for rape and ryegrass. It was also seen that the inhibition process occurred at seed incubation process and not during seed soaking stage. The results depict its significance in terms of its use and disposal of the engineered nanoparticles. However, further studies highlighting size distribution of nanoparticles on phytotoxicity and its possible uptake, translocation and physical and chemical properties around rhizosphere are required in order to generate more application-oriented ideas in agriculture sector (Lin and Xing 2007).

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2  Recent Progress in Applied Nanomaterials Table 2.1  Recent development of nanoparticles in crop protection Nano-formation Cellulose/silica nanocomposites Lignin/diuron Copper (Cu) nanoparticles Iron oxide (FeO) nanoparticles Ag core – DHPAC shell nanocluster TiO2 with Zn and Ag Chitosan nanoparticle Copper nanoparticles Silver nanoparticles Ag/graphene oxide composite

Crop disease and target pathogen Leaf senescence (rust and moulds) Spot of tomato (Xanthomonas perforans) Fungal disease (Fusarium sp.) Fungal disease (R. solani, B. cinerea and F. oxysporum) Fungal disease (Phytophthora spp.) Spot of tomato (Xanthomonas perforans) Fungal disease (Alternaria alternata, R. solani) Disease in tomato (Phytophthora infestans) Bacterial blight (Xanthomonas campestris) Bacterial spot disease (Xanthomonas perforans)

References Mattos and Magalhaes (2016) Yearla and Padmasree (2016) Bramharwade et al. (2016) Chhipa and Kaushik (2015) Ho et al. (2015) Paret et al. (2013) Saharan et al. (2013) Giannouri et al. (2013) Rajesh et al. (2013) Oscoy et al. (2013)

2.2.2  Nanofertilizer and Nanopesticides Increase in the use of pesticides and fertilizers had caused environmental pollution, emergence of pests and pathogens and loss of biodiversity. By virtue of nanomaterials and its unique properties, the problems related to agriculture could be alleviated. In general, nanotechnology provides a great hope for sustainable agricultural practice by converting conventional farming practice into precision farming (Prasad et al. 2014, 2017a). Precision farming mainly deals with the improvement of crop yield by monitoring all the environmental variables for implementing a specific action according to the situation (Chhipa 2017). Nanofertilizers are broadly divided into three categories: (a) macronanofertilizer, (b) micronanofertilizer and (c) nanoparticulate fertilizer. Few other studies are summarized as given in Table 2.1. 2.2.2.1  Macro- and Micronutrient Nanofertilizers Macronutrients are the nutrients required in large amount in farming practices for plant growth, which comprises of nitrogen (N), phosphorous (P), potassium (K), magnesium (Mg), sulphur (S) and calcium (Ca). The use of nanoparticles benefits farmers by reducing the amount of macronutrients used in relative to conventional fertilizers, owing to their higher surface to volume ratio. Urea-coated zeolite chips and urea-modified hydroxyapatite nanoparticles have been successfully

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developed that displays slow and controlled release of N for longer duration (Millán et al. 2008). Similarly Liu and Lal (2014) synthesized Ca and P hydroxyapatite nanoparticles, which displayed a significant increase in the Glycine max seed yield by 20–33% in relative to conventional phosphorous (Liu and Lal 2014). Also Ca nanoparticles were also synthesized, which showed 15% increase in biomass of Arachis hypogea (Liu et al. 2005). Further, Delfani et al. (2014) synthesized Mg NP and found 7% increment in the seed weight of Vigna unguiculata (Delfani et al. 2014). Micronutrients are trace elements that are required in minute quantity (25 mm in size) into meso- (5–25 mm), micro- (0.1–5 mm), and nanoplastics (