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Bio-Based Nanomaterials Synthesis Protocols, Mechanisms and Applications EDITED BY

Ajay Kumar Mishra Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa

Chaudhery Mustansar Hussain Department of Chemistry and Environmental Science, New Jersey Institute of Technology, Newark, NJ, United States

Table of Contents Cover image Title page Copyright List of contributors Chapter 1. Cellulose-based nanomaterials for textile applications Abstract 1.1 Introduction 1.2 Biomaterials and its sources 1.3 Chitosan, cellulose, banana, and jute fiber derivatives and their advantages 1.4 Nanochitosan, nanocellulose, and natural fibers 1.5 Applications of biobased nanomaterials 1.6 Conclusion and future perspectives References

Chapter 2. Strategies for sustainable synthesis processes of nanocarbons from biomass Abstract 2.1 Introduction 2.2 Biomass and carbon nanostructures 2.3 Synthesis processes of biomass-based nanocarbon materials 2.4 Summary and outlook Acknowledgment References Chapter 3. Production of biopolymer-based nanoparticles Abstract 3.1 Introduction 3.2 Briefs of biopolymers 3.3 Synthesis of biopolymer-based nanoparticles 3.4 Summary and future aspects References Chapter 4. Bio-based nanomaterials for properties and applications Abstract 4.1 Introduction

4.2 Preparation and applications of bio-based nanomaterials 4.3 Future prospects and conclusion Acknowledgments References Chapter 5. Enhanced dye recovery from textile effluents by means of biobased nanomaterials/polymer loose nanofiltration membranes Abstract 5.1 Introduction 5.2 Materials and methods 5.3 Results and discussion 5.4 Conclusions Acknowledgments Data availability References Chapter 6. Biodegradation and water absorption studies of natural gum rosin-based hydrogel Abstract 6.1 Biodegradation of hydrogels 6.2 Methods of biodegradation 6.3 Water-absorption studies

6.4 Results and discussion 6.5 Water absorption properties of hydrogel in soil samples 6.6 Impact of biodegradation of synthesized samples on soil 6.7 Conclusion References Chapter 7. Nanobiochar—a green catalyst for wastewater remediation Abstract 7.1 Introduction 7.2 Modification of surface properties of biochar 7.3 Properties intricate in reactive species and radical generation 7.4 Biochar-based catalysts for wastewater treatment 7.5 Conclusions References Chapter 8. Polyhydroxyalkanoates based systems: the future of drug delivery and tissue engineering devices Abstract 8.1 Introduction 8.2 Biosyntesis, main features, chemical modifications, degradation, and general applications of polyhydroxyalkanoates

8.3 Polyhydroxyalkanoates for drug delivery systems design 8.4 Polyhydroxyalkanoates as tissue engineering materials 8.5 Perspectives and challenges 8.6 Conclusion Acknowledgments References Chapter 9. Advanced applications of biomass for energy storage Abstract 9.1 Introduction 9.2 Materials used for energy storage devices 9.3 Energy storage mechanism in carbon-based materials 9.4 Biomass-derived carbon for energy storage applications 9.5 Summary and outlook References Chapter 10. Sericin-based nanomaterials and their applications in drug delivery Abstract 10.1 Introduction 10.2 Properties of sericin

10.3 Sericin-based biomaterials and their biomedical applications 10.4 Therapeutic potential of sericin-based nanomaterials in drug delivery 10.5 Clinical application of sericin-based biomaterials 10.6 Future perspectives and conclusions Author contributions Conflicts of interest Acknowledgments References Chapter 11. Bone tissue restoration by nanoscale features of biomaterials Abstract 11.1 Introduction 11.2 Formation of a blood clot on a biomaterial during bone healing 11.3 Osteogenic differentiation of stem cells induced by biomaterials: mechanism and pathways 11.4 Neovascularization during bone healing 11.5 Bone apposition stimulation induced by surface properties of biomaterials

11.6 New trends in biomaterials development: bioinspired stratified scaffolds 11.7 Outlooks and perspectives Acknowledgments References Chapter 12. Toxicological effect of biopolymers and their applications Abstract 12.1 Introduction 12.2 Classification of biopolymers 12.3 Properties of biopolymers 12.4 Relative properties 12.5 Synthesizing properties 12.6 Component properties 12.7 Synthesis of biopolymers 12.8 Starch 12.9 Cellulose 12.10 Chitin and Chitosan 12.11 Gelatin 12.12 Polylactic acid

12.13 Poly(vinyl alcohol) 12.14 Polyurethanes 12.15 Poly(hydroxyalkanoates) 12.16 Poly(ε-caprolactone) 12.17 Toxicological effect of biopolymers 12.18 Applications of biopolymers 12.19 Synthesis of nanomaterials 12.20 Synthesis of nanocarriers 12.21 Biomedical field 12.22 Adsorbents for environmental remediation 12.23 Agricultural domain 12.24 Food industry 12.25 Conclusion References Index

Copyright Elsevier Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom 50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States Copyright © 2022 Elsevier Inc. All rights reserved.

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Notices Knowledge and best practice in this field are constantly changing.

As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

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British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-323-85148-0 For Information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals Publisher: Matthew Deans Acquisitions Editor: Sabrina Webber Editorial Project Manager: Mariana Kuhl Production Project Manager: Poulouse Joseph Cover Designer: Christian Bilbow Typeset by MPS Limited, Chennai, India

List of contributors Heidi Abrahamse, Laser Research Centre, University of Johannesburg, Johannesburg, South Africa Stefania Akromah, Department of Materials Engineering, College of Engineering, Kwame Nkrumah, University of Science and Technology, Kumasi, Ghana Bapun Barik, Department of Chemistry, National Institute of Technology, Rourkela, India Uday Bhan, Department of Petroleum Engineering and Earth Sciences, University of Petroleum and Energy Studies, Bidholi, Dehradun, India Pablo R. Bonelli, University of Buenos Aires, Faculty of Exact and Natural Sciences, Department of Industries, Institute of Food Technology and Chemical Processes, National Council for Scientific and Technical Research, University City, Buenos Aires, Argentina Naveen Bunekar, Department of Chemistry, Chung Yuan Christian University, Taoyuan City, Taiwan Ana L. Cukierman University of Buenos Aires, Faculty of Exact and Natural Sciences, Department of Industries, Institute of Food Technology and Chemical Processes, National Council for Scientific and Technical Research, University City, Buenos Aires, Argentina University of Buenos Aires, Faculty of Pharmacy and Biochemistry, Department of Pharmaceutical Technology, Buenos Aires, Argentina Priyabrat Dash

Department of Chemistry, National Institute of Technology, Rourkela, India Center for Nanomaterials, National Institute of Technology, Rourkela, India Sathish Sundar Dhilip Kumar, Laser Research Centre, University of Johannesburg, Johannesburg, South Africa Derrick S. Dlamini State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Membrane Science and Technology, Tianjin, P.R. China School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin, P.R. China Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa Noelia L. D’Elía, INQUISUR - CONICET, Department of Chemistry, Universidad Nacional del Sur, B8000CPB, Bahía Blanca, Argentina Geetanjali, Department of Chemistry, Kirori Mal College, University of Delhi, Delhi, India Lalit Goswami, Center for the Environment, Indian Institute of Technology Guwahati, Guwahati, India Shivani Goswami, Department of Biotechnology, Brahmanand College, Chhatrapati Shahu Ji Maharaj University, Kanpur, India A. Noel Gravina, INQUISUR - CONICET, Department of Chemistry, Universidad Nacional del Sur, B8000CPB, Bahía Blanca, Argentina Nidhi Rani Gupta, Department of Chemistry, Multani Mal Modi College, Patiala, India Ram K. Gupta, Department of Chemistry, Kansas Polymer Research Center, Pittsburg State University, Pittsburg, KS United States

Rajeev Jindal, Department of Chemistry, Dr. B R Ambedkar National Institute of Technology, Jalandhar, India Balbir Singh Kaith, Department of Chemistry, Dr. B R Ambedkar National Institute of Technology, Jalandhar, India Gagandeep Kaur, Department of Chemistry, Sri Guru Teg Bahadur Khalsa College, Sri Anandpur Sahib, India Vaneet Kumar, Department of Applied Sciences, C.T. Institute of Engineering, Management and Technology, Jalandhar, India Vinit Kumar, Department of Electrical and Electronic Engineering, Visvesvaraya Technology University, Belgaum, India Anamika Kushwaha, Department of Biotechnology, Motilal Nehru National Institute of Technology Allahabad, Prayagraj, India Jianxin Li State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Membrane Science and Technology, Tianjin, P.R. China School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin, P.R. China Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa Benedini Luciano INQUISUR-UNS, National University of the South, Buenos Aires, Argentina Department of Biology, Biochemistry and Pharmacy, National University of the South, Buenos Aires, Argentina Banalata Maji, Department of Chemistry, National Institute of Technology, Rourkela, India Bhekie B. Mamba State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Membrane Science and Technology, Tianjin, P.R. China

School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin, P.R. China Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa Christine Matindi State Key Laboratory of Separation Membranes and Membrane Processes/National Center for International Joint Research on Membrane Science and Technology, Tianjin, P.R. China School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin, P.R. China Kwadwo Mensah-Darkwa, Department of Materials Engineering, College of Engineering, Kwame Nkrumah, University of Science and Technology, Kumasi, Ghana Paula V. Messina, INQUISUR - CONICET, Department of Chemistry, Universidad Nacional del Sur, B8000CPB, Bahía Blanca, Argentina Ajay Kumar Mishra, Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa Shivani Mishra, Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa Bezawada Sridhar Reddy, Department of Chemistry, Indian Institute of Petroleum and Energy, Visakhapatnam, India Debasish Sarkar Department of Ceramic Engineering, National Institute of Technology, Rourkela, India Center for Nanomaterials, National Institute of Technology, Rourkela, India Javier Sartuqui, INQUISUR - CONICET, Department of Chemistry, Universidad Nacional del Sur, B8000CPB, Bahía Blanca, Argentina Saruchi, Department of Biotechnology, C.T. Institute of Engineering, Management and Technology, Jalandhar, India

Rachna Sharma, Department of Chemistry, Dr. B R Ambedkar National Institute of Technology, Jalandhar, India Justice M. Thwala, Department of Chemistry, Faculty of Science and Engineering, University of Eswatini, Kwaluseni, Kingdom of Eswatini Kumud Malika Tripathi, Department of Chemistry, Indian Institute of Petroleum and Energy, Visakhapatnam, India Tsung Yen Tsai, Master Program in Nanotechnology & Center for Nanotechnology, Chung Yuan Christian University, Taoyuan City, Taiwan Gcina D. Vilakati, Department of Chemistry, Faculty of Science and Engineering, University of Eswatini, Kwaluseni, Kingdom of Eswatini

CHAPTER 1

Cellulose-based nanomaterials for textile applications Bapun Barik1, Banalata Maji1, Debasish Sarkar2,3, Ajay Kumar Mishra4 and Priyabrat Dash1,3, 1Department of Chemistry, National Institute of Technology, Rourkela, India, 2Department of Ceramic Engineering, National Institute of Technology, Rourkela, India, 3Center for Nanomaterials, National Institute of Technology, Rourkela, India, 4Academy of Nanotechnology and Waste Water Innovations, Johannesburg, South Africa

Abstract Nowadays, researchers are highly focused on the manufacturing of more sustainable and enviro-friendly materials to solve the challenges brought due to the rapid globalization and climate change. For example, the use of plastic waste or nonbiodegradable materials in daily life has to be replaced with more convenient and ecofriendly materials. So, recently, the scientific communities have proposed the use of biobased nanomaterials, which are synthesized from the natural renewable sources as potential alternatives. The biobased nanomaterials possess unique properties such as enhanced functionality, uniform porosity, tunable surface properties, and environmental suitability. It has been found that nanostructures derived from natureproduced biomaterials such as chitosan, cellulose, banana fiber, and jute fiber have shown great promise due to their unique physicochemical properties. These biobased nanomaterials have significantly improved their performances in various interdisciplinary and engineering applications like textile, agricultural, food packaging, biomedical, electronics, and environment. Keeping an eye on these developments, this particular chapter overviews the advantages of chitosan, cellulose, banana fiber, and jute fiber in the synthesis of biobased nanomaterials along with the recent progresses in the field of textile industry applications. The chapter also provides a brief explanation about biobased nanomaterials in future perspective.

Keywords Nanomaterials; cellulose; chitosan; banana fibers; jute fibers; textile application

1.1 Introduction Development of quality textile thread toward manufacturing high value-added clothes and fabrics has been a prominent research field for several years (Mishra et al., 2018; Stokke et al., 2013). Textile industry plays a significant role in the economic development

of a country by enhancing gross production in domestic level (Khaliji et al., 2013). Textile industries demand several fabric materials, which include woolen, cotton, and synthetic fibers (Haraguchi et al., 2017). Conversely, these textile industries generate huge amount of wastewater, which causes environmental pollution aggressively. The textile processes like dyeing, bleaching, printing etc. generate high volume of toxic waste with heavy nitrogen content, acidity, suspended solids, heavy metals, dyes etc. Generally, these textile contaminants can cause severe health impact in human, animals, and plants by degrading water qualities in aquatic ecosystem (Ütebay et al., 2019). Consequently, materials with least byproduct generation have always in demand in textile industries. So, to meet the heavy demand of consumers for low-weight and energy-efficient as well as sustainable materials, large scale industries have extensively focused on developing novel materials derived from the natural renewable resources (Yousef et al., 2020). Materials satisfying environmental safety and reusability with enhanced activity have also resulted in an enhanced interest. Noticeably, the requirement to explore alternatives materials of nonrenewable resources is majorly focused on producing advanced products from various bioderived materials such as cellulose, chitosan, nature-derived polymeric fibers etc.

(Väisänen et al., 2017). Cellulose and chitosan are immensely popular for the synthesis of modified nanostructures with enhanced potential applications. Chitosan is a deacetylated form of chitin, which is a biodegradable, biocompatible, nontoxic, and renewable amine functionalized polysaccharide (Kumar, 2000). It’s unique structural integration, multidimensional properties, and extensive hetero atom functionalization have made it a preferable candidate as a surface-based active material. On a similar note, cellulose is another biopolymer abundantly available in nature and also used as a novel and sustainable polymeric material for several domestic and industrial applications (Roy et al., 2009). Fig. 1.1 shows the various potential applications of bio-based nanomaterials. It possesses sustainable structural, mechanical, and optical properties. Moreover, improved functionality, high strength, and biocompatibility further benefit both chitosan and cellulose-based materials in practical applications. But limitations like low adsorption capacity and hydrophilic nature restrict them from large scale and individual application.

Schematic illustration of applications of biobased nanomaterials.

FIGURE 1.1

In this direction, derivatives of cellulose and chitosan families, nanocellulose and nanochitosan (NCH) were synthesized via controlled acid hydrolysis (Siró and Plackett, 2010; Yu et al., 2020). They have emerged as most preferable biobased nanomaterials due to their tunable size, uniform morphology, higher dispersibility, superior surface chemistry, and improved physicochemical properties. The high surface-to-volume ratio and thermal stability make both Nanochitosan (NCS) and NCH nanomaterial appropriate candidate for large-scale applications (Mishra et al., 2018b). The research communities have extensively studied about natural fibers for their wide range applications and future potentials of these biobased nanomaterials and their derivatives. Natural fibers are biobased nanomaterials derived directly from the agricultural sources. For example, natural fibers are derived from jute, banana, hemp, bamboo, wood etc. These natural fibers provide numerous advantages such as low density, biodegradability and costeffectiveness. Additionally, they have low toxicity, higher tensile strength, improved elasticity, better performance and enhanced energy consumption capacity (Ramamoorthy et al., 2015).

Recently, several NCS and NCH-based nanofibers are designed for textile applications.

In this chapter, we will provide a detailed overview of the recent progress in the field of biobased nanomaterials for textile application with a noble viewpoint of restoration of aquatic ecosystem.

1.2 Biomaterials and its sources The production of biobased nanomaterials has increased rapidly as a more efficient, renewable, and environment friendly sustainable material. With due credit to the nanoscience, nanostructures of the raw bioderived materials are also fabricated and utilized. Cellulose and chitosan are two very abundant biopolymers readily available in nature. Cellulose can be isolated from various natural sources such as woods, aquatic

animals, biomass, agricultural crop and fruit waste, fungi, and algae (Rajinipriya et al., 2018). The composition and stability of cellulose are highly dependent on their source. In general, cellulose is known as a natural polysaccharide first derived from wood in 1838 by treatment with HNO3. Naturally, it contains microfibrils of diameter ranging from 3 to 35 nm owing to its source. Its structure is comprised of linear polymeric chains with monomers called β-1, 4-D-glucose. The average degree of polymerization for cellulose is up to 20,000 whereas for wood, it is approx.10,000 units. With increasing demand of ecofriendly materials, cellulose derived from agricultural crops and fruits are more preferred (Sinquefield et al., 2020). This is because generation of raw cellulose becomes easier, environmental friendly with low cost. Agricultural sources of cellulose are a tremendous resource as they are ecofriendly, inexpensive, easily available, reusable, and have tunable mechanical properties. Moreover, this agricultural sourced cellulose can produce abundant amount of natural fibers. Agriculture waste fibers can be obtained from cotton stalk, pineapple leaf, banana leaf, rice straw, jute, hemp, crop husk, garlic straw, vegetable peel, fruit skin, etc. (Esa et al., 2014). So, agricultural cellulose has multitude applications in various industrial sectors such as textiles, paper, composite fabrication, architecture, furniture, and medicine.

Similarly, chitosan is another bioderived natural biopolymer, which is derived from chitin. Skeleton of shrimp wastes and fungus biomass are generally the most preferred source of chitosan (Kumar et al., 2004). Deacetylation of chitin in alkaline medium produces the biopolyaminosaccaride chitosan. Chitin is a major biopolymer found in crab, shrimp, lobster, jelly fish, coral, some yeasts, and in the cell walls of fungi. In recent years, research on chitosan has enhanced due to its biocompatibility, biodegradability, and environmental safety (Bano et al., 2017). It has highly influential antimicrobial activity, film formation capacity, chelating, and surface adsorption characteristics. Chitosan is composed of poly-(1,4)-2-amino-2-deoxyD-glucopyranose with extensive amino and hydroxyl functionalization as active sites(Islam et al., 2017). Chitosan utilization in various applications is dependent on its viscosity and molecular weight. In a report, Shimojoh and his coworkers reported that high molecular weight chitosan has better activity as food additive compared to that with low molecular weight chitosan (Seyfarth et al., 2008).

Additionally, the polycationic nature of chitosan makes it more suitable as flocculating agent as well as chelating agent for heavy metals. The crustaceous industry wastes are the prime source of chitosan and can be obtained with minimum expenditure. Other sources like Filamentous fungi can provide both chitosan and chitin at large scale which can be synthesized under controlled environment (Ghormade et al., 2017). All the sources of chitosan can be compared but all properties of chitosan depend on the degree of acetylation, homogeneity of molecular weight, viscosity and amount of charge distribution. Optimization of the basic structure of chitosan can explore the opportunity of finding new class of chitosan derivatives with a broad range improved properties and applications. Among them, designing of nanostructures with bioderived chitosan for potential applications in several large scale industries is the most advanced form of it.

Chitosan has been proved as a nontoxic for consumption either as food or drug sectors (Ghormade et al., 2017). So, researchers are more interested in the production of nanochitosan. Moreover, their antimicrobial property further increases its demand in the fabrication of high-quality nanofibers and composites for diversified applications.

1.3 Chitosan, cellulose, banana, and jute fiber derivatives and their advantages To tackle the manmade climatic disasters, biopolymer materials are best alternative materials for greener world. Extracted from living organisms, the polymeric biomolecules have significant environmental suitability. Among all biopolymers, cellulose and chitosan along with their derivatives have the most interesting multipurpose characteristics, which gained significant interest among the researchers in present time (Olivera et al., 2016).

Cellulose is the most abundant organic polymer on Earth. Cellulose is an organic compound with formula (C6H10O5)n. It is a polysaccharide consisting of a linear chain of hundred to many thousands of β (1→4) linked D-glucose units As an important structural component of primary cell wall of green plants, cellulose has gained its reputation (Cichosz and Masek, 2019). Like cellulose, chitosan is the second most abundant organic polymer found on Earth. Chitosan is a copolymer of 2-glucosamine and N-acetyl-2glucosamine. It is obtained by deacetylation of chitin in hot alkali (Kurita, 1998). Till date, these have been proved as a successful material as biological adhesive, biofilm, Antioxidant, Food packaging, Antibacterial, coating, biosensors, surface conditioner, bioadsorbent and catalyst. But the rising interest in cellulose and chitosan nanofibers in the textile industry is undeniable which may be due to its superior sustainability and lowcost mechanical properties. Natural fibers are obtained from various sources but agricultural sources are best as they are made up of 60%–70% pure cellulose, 10%–20% hemicellulose, 5%–15% lignin and around 2% of waxes and pectin (Muthukumar et al., 2020). Banana fiber is a natural fruit fiber extracted from the superimposed leaves of banana plant which has very limited use except as a cattle feed. It is from Musa family (Pothan et al., 2003). Canary Islands of Europe are the major producer of banana. The very precious banana fibers are generally isolated from the pseudo-stems of banana plant after ripening of the fruit. So, one of the prime benefits of these fibers in compared with naturally obtained fibers is their agricultural source is always eco-friendly. Banana fibers possess least toxicity to humans, instruments and the environment, which can be realistic alternatives of other less favored synthetic fibers. Several studies have also been done for the fabrication of banana fibers, some of them with long fibers and others are woven fibers (Venkateshwaran and Elayaperumal, 2010). These studies show that specific mechanical properties of banana fiber composites are similar to those reinforced with glass fiber, although mechanical properties under humid conditions show an important decrease for the natural fiber composites because of their water vapor absorption. Another cellulose based fiber source is jute whose composite materials are gaining attention for due to their easy availability and cheap production cost (Alves et al., 2010). Jute takes only 2–3 months to grow with a height of 12–15 ft in the retting process, the inner and outer stem get separated. The outer part is kept separately to form fiber. These jute fibers are further processed to manufacture high quality lifestyle products (Mishra and Biswas, 2013).

However, these bioderived fibers have high mechanical strength, excellent thermal stability, renewability etc.

1.4 Nanochitosan, nanocellulose, and natural fibers In late 1950s, first time a colloidal suspension of cellulose was reported by Ranby and his group (Habibi et al., 2010). They obtained it by controlled and precise addition of H2SO4

to fabricate cellulose nanofibers. In another work, Nickeson et al. observed that the cellulose nanofibers are degraded to a maximum limit after which the volume of nanofibers remains constant. When further characterized by Transmission electron microscope they revealed the presence of aggregated needle shaped particles of crystalline nature (Miao et al., 2016). Consequently, commercialization of NCS was achieved by large scale synthesis via hydrochloric acid assisted degradation of cellulose obtained from wooden pulps followed by ultrasonication. Chemical inactivity, ultra stability, and physiological inertness along with tremendous surface binding properties, NCS brought a significant chance for multipurpose applications Since its discovery, several improvements in the mechanical as well as surface properties of nanomaterials with NCS and NCS derivatives have been part of substantial research due to the growing interest in fabrication materials derived from renewable resources. NCSs are also referred as nanocrystals, nanowhiskers, nanoparticles, and nanofibers (Melo et al., 2020). But nanofibers have the most versatile and wide range of applications. Methods for separation of CNs and their morphologies, characterization, modification, self-assembly, and applications will be reviewed. In basic process of isolation of cellulose fibers include acid hydrolysis. Preferentially, more disordered and least-crystalline parts of the raw cellulose are hydrolyzed whereas the higher crystalline parts remain intact due to more resistance to acid attack. The acid treatment removes the microfibrils at the loose defects and fiber like nanocellulose structures are produced. Generally, acid hydrolysis induces minimizes the degree of polymerization which is directly related to the nanofiber size along the longitudinal direction of cellulose chain. This concept of hypothesis was supposed as the disordered or paracrystalline domains of cellulose are generally spread through the microfibers leading to more susceptible acid attack. This process results in the formation of homogeneous crystalline nanofibers after acid hydrolysis. Table 1.1 shows the comparison data of different biobased composites with various synthetic procedure.

Moreover, all these speculations were further confirmed from several characterization tools such as X-ray diffraction (XRD) study, electron microscopy, small angle XRD and neutron diffraction analysis (Sun et al., 2016). In recent time, another biopolymeric abundant polysaccharide chitosan have been introduced and vastly studied. Chitosan can be used in several aspects such as support for foreign nanoparticles, enhancing composite stability and activity and metal binder. But the inherent sole use of chitosan has been restricted due to its lack of efficiency and thermal stability. So, nanoform of chitosan has been developed which can be more effective for desired applications due to their enhanced surface area, nanosized, uniform distribution, biodegradability, and higher functionality distribution (Huang et al., 2009). These properties favor nanochitosan in numerous applications, including sensors, carrier for protein molecules, drug delivery systems, textile, adsorption, degradation, and catalysis. There are several methods adopted by several researchers for fabrication of NCS (Yang et al., 2010). Among them methods like coagulation/precipitation, emulsion droplet coalescence method, crosslinking via covalent bonds, and ionic bonds are more favored. But NCH manufactured by ionotropic-gelation method are more stable, nontoxic, and solvent free. NCH possess all the inherent properties of chitosan along with general characteristics of nanosized fibers such as surface activity effect, grain size effect and quantum size effect (Chen and Hsieh, 2011). Also, it has tremendous physicochemical and bioactive properties. Ionic-gelation process includes the deacetylation of raw chitosan with 2% acetic acid solution followed

by the addition of tripolyphosphate or ammonium heptamolybdate to form a white solution. Again, by multiple ringing with distilled water, excess tripolyphosphate or ammonium heptamolybdate were eliminated and the desired NCH was obtained by vigorous centrifugation at 16,000 rpm followed by drying in CO2 atmosphere (Nguyen et al., 2017). Again, Berthold and his group prepared NCH using Na2SO4 as a precipitation agent. The process includes the addition of Tween 80 with raw chitosan in CH3COOF solution drop wise followed by ultra-sonication. Similarly, in another method Tian et al. improvised the method of precipitation and found chitosan nanoparticles of 600–800-nm.

Ohya et al. cross-linked the amino groups of chitosan with glutaraldehyde and emulsified it with water-in-oil emulsifier which resulted in synthesis of 5-fluorouracil chitosan particles of average particle size 0.8–0.1 mm (Hou et al., 2011). NCH has been very frequently used for controlled release of drug for gene transfer in human and animal organs (Huang et al., 2009). Moreover, it has a wide variety of application in textile industry which can enhance the fabric strength and wash ability of the textile with an additional benefit of antibacterial ability.

Table 1.1 Biobased composites synthesis procedure.

Material

Synthesis process

Reference

Chitosan

Enzymatic deproteinization

Younes et al.

(2012)

Nanofibrillated cellulose

Enzyme hydrolysis

Pääkkö et al.

(2007)

Cellulose nanofibrils

TEMPO-mediated oxidation

Jiang and Hsieh (2013)

Cellulose fibers

High-intensity ultrasonication

Wang and Cheng (2009)

Cellulose nanofibrils

Microfluidization

Lee et al. (2009)

Chitosan/ magnetic maghemite (γ-Fe2O3) Solution casting method nanoparticles

Pratiwi and Putri (2019)

ZnO/Ce-ZnO based nanoflowers/chitosan

Saad et al. (2020)

Microwave-irradiation method

1.5 Applications of biobased nanomaterials The progress of biobased nanomaterials has marked an essential mile stone in modern civilization. After invention and gaining popularity, biobased nanoparticles and nanofibers are considered as the new era materials for our advanced technology-based human society. The rapid and unprecedented progress in material world is greatly dependent on the design of bioderived materials with higher activity and phase stability.

Batteries, machines, computers, vehicles, memory devices, display panels, solar cells, and sensory devices are the fundamental part of our daily life, which are made up of advanced metals, ceramics, or plastics. The advancement of technology has brought revolutionary conversion to the environment and humans. Consequently, this results in serious environment and health hazards due to production of enormous amount of secondary waste. The evolution of technology has suggested that the bioderived materials such as cellulose, chitosan and other natural fibers are the most preferred alternatives for the ceramic, metallic and plastic materials. These biobased materials provide unique combination properties such as surface chemistry, transparency, high elasticity, anisotropy, and low thermal expansion. The biobased materials have been addressed for many multipurpose applications such as fuel conversion, energy storage, catalysis, biomedicine, pharmaceutical, environmental application and industrial applications.

Among them, industrial applications of biobased materials have been studied for long time period and still gaining more attention. Here, we will be discussing particularly the textile applications of most popular nanosized cellulose and chitosan. Owing to the requirement of high quality and antibacterial property of textile fabrics, these bioderived nanoforms of chitosan and cellulose can satisfy the purpose in best way. Moreover, the environment friendliness and nontoxicity to human skin have further proved its suitability for textile industry.

1.5.1 Textile applications of nanochitosan Chitosan is a polycationic natural polysaccharide, which possesses many beneficial properties like antifungal, antibacterial, antiacid, nontoxic and total biodegradable and superb film forming capacity. The nanoform of chitosan is comprised of all these inherent properties along with nanosized effect and quantum size effect. In this prospective, nanochitosan has been used for several applications such as cosmetics, food, biomedical, paper, wastewater treatment, agriculture, and industries. Also, these unique characteristics are very advantageous for textile applications. Fig. 1.2 Shows the potential usage of biobased nanomaterials for textile applications. In textile industries nanochitosan can be used as fibers and in the process of dyeing as well as finishing. Recently, nanochitosan have demonstrated versatile application in textiles to enhance the functional coatings which means durability, softness of fabrics, UV protection, breathability, fire and water resistance, antimicrobial, antifungal, self-cleaning properties of fabrics, yarn and fiber. Chitosan has a large impact on production of textile with antimicrobial, hemostatic, moisture controlling, nonallergic, deodorizing, and antithrombogenic properties toward wound dressing bandages, fabrics with scents, active drug carrier, and sutures. The surface quality and morphology of the fiber was analyzed with scanning electron microscope. During the dyeing process in textile industries, numerous toxic coloring agents like direct, anionic, reactive, and azoic dyes are utilized. The conventional dyeing process produce large amount of wastewater which can degrade the aquatic life as well as environment by contaminating with toxic chemicals and macromolecules. In this direction, Iqhrammullah et al. reported the Pb (II) adsorption properties of NCH combined polyurethane-polypropylene glycol from textile effluents (Iqhrammullah et al., 2020). The kinetic and batch adsorption studies revealed that the ternary blend was found to be thermally stable and crystalline in nature which is highly efficient to remove metal ions from textile wastewater. Hadavifar and his coworkers prepared nanochitosan from