Handbook of Chitin and Chitosan

Volume 3: Chitin- and Chitosan-based Polymer Materials for Various Applications

Sabu Thomas, Anitha Pius, Sreerag Gopi, Sabu Thomas, Anitha Pius, Sreerag Gopi

• Publisher: Elsevier
• Year: 2020
• Print ISBN: 9780128179666
• eBook ISBN: 9780128179673
• Topic: Physical Sciences
• Subtopic: Organic Chemistry

The Handbook of Chitin and Chitosan: Chitin and Chitosan Based Polymer Materials for Various Applications, Volume Three, is a must-read for polymer chemists, physicists and engineers interested in the development of ecofriendly micro and nanostructured functional materials based on chitin and their various applications. The book addresses their isolation, preparation and properties and their composites, nanomaterials, manufacturing and characterizations. This is the third of three volumes in a series that contains the latest on the major applications of chitin and chitosan based IPN's, blends, gels, composites and nanocomposites, including environmental remediation, biomedical applications and smart material applications. - Provides a comprehensive overview of Chitin and Chitosan materials, from their synthesis and nanomaterials, to their manufacture and applications - Volume Three focuses on the applications of Chitin and Chitosan - Includes contributions from leading researchers across the globe and from industry, academia, government and private research institutions - Highlights current status and future opportunities

Chapter 1

Polymer blends, IPNs, gels, composites, and nanocomposites from chitin and chitosan; manufacturing, and applications

Sabrina Sultana¹, Md. Shirajur Rahman², Md. Minhajul Islam², Md. Nurus Sakib² and Md. Shahruzzaman², ¹1Department of Arts and Sciences, Ahsanullah University of Science and Technology, Dhaka, Bangladesh, ²2Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering and Technology, University of Dhaka, Dhaka, Bangladesh

Abstract

Chitin and chitosan are the most abundant amino polysaccharides and have immense structural possibilities for chemical modifications to allow them to exhibit outstanding properties, functions, and applications in biomedical, pharmaceutical, chemical, cosmetics, environmental, and agricultural areas. Their versatility and unique characteristics, such as hydrophilicity, film-forming ability, biodegradability, biocompatibility, antibacterial and antifungal activity, and the nontoxicity of chitin and chitosan clearly point to an immense potential for future development. These biopolymers can be easily processed into gels, sponges, membranes, beads, and scaffold forms. This chapter emphasizes recent research on different aspects of chitin- and chitosan-based blends, gels, IPNs, composites, and nanocomposites, including their preparation and applications.

Keywords

Biopolymer; nanocomposites; biomedical; interpenetrating polymer network; polymer blends

Outline

Outline

• 1.1 Introduction 2
• 1.2 Chemical structure and preparation of chitin and chitosan 4
  • 1.2.1 Chemical structure and preparation of chitin 4
  • 1.2.2 Chemical structure and preparation of chitosan 5
• 1.3 Polymer blends from chitin and chitosan 6
  • 1.3.1 Blends with synthetic polymers 7
  • 1.3.2 Blends with natural polymers 8
  • 1.3.3 Applications of chitin and chitosan blends 8
• 1.4 Interpenetrating polymer networks from chitin/chitosan 9
  • 1.4.1 Chitosan-based full-interpenetrating polymer network and semi-interpenetrating polymer network systems 10
  • 1.4.2 Interpenetrating polymer network hydrogels based on chitosan and synthetic ionic matrices 11
  • 1.4.3 Interpenetrating polymer network hydrogels based on chitosan and synthetic nonionic matrices 12
  • 1.4.4 Interpenetrating polymer network cryogels based on chitosan and synthetic matrices 12
  • 1.4.5 Applications of chitin/chitosan-based Interpenetrating polymer networks 13
• 1.5 Chitin- and chitosan-based gels 14
  • 1.5.1 Physically associated gels 14
  • 1.5.2 Polyelectrolyte complexation 17
  • 1.5.3 Covalently cross-linked gels 18
  • 1.5.4 Applications of chitin- and chitosan-based gels 19
• 1.6 Chitin- and chitosan-based composites 22
  • 1.6.1 Composites from synthetic fillers 22
  • 1.6.2 Composites from natural fillers 23
  • 1.6.3 Applications of chitin- and chitosan-based composites 25
• 1.7 Chitin- and chitosan-based nanocomposites 27
  • 1.7.1 Nanocomposites from chitin and chitosan 28
  • 1.7.2 Applications of chitin- and chitosan-based nanocomposites 29
• 1.8 Conclusions and future prospective 32
• References 33

1.1 Introduction

Natural polymers are the most widespread and effective materials, mainly due to their abundance, environmental concerns (renewability and biodegradability), and wide applicability. The demand of natural polymeric materials has been increasing over the last two decades because natural polymers have better biocompatibility and less toxic effects than most synthetic polymers. This has led to the utilization of their useful inherent properties for a wide range of applications in different fields [1,2]. Many studies have been carried out on the manufacturing of advanced polymeric materials, such as blends, gels, composites, and nanocomposites, by mixing natural polymers with other natural or synthetic polymers and fillers.

Among the natural polymers, chitin and chitosan occupy a distinct position due to their abundance, versatility, ease of modification, and unique properties including biodegradability, biocompatibility, nontoxicity, antibacterial and antifungal properties, hydrophilicity [3–5], etc. In addition, the structural units of chitin and chitosan contain a reactive amino group that makes them much easier to be modified by chemical reactions than cellulose. These have made chitin and chitosan very useful and outstanding candidates for a broad range of applications in biomedical, pharmaceutical, chemical, agricultural, cosmetics, and environmental fields. There are many reviews focusing on the properties, modifications, and applications of chitin and chitosan [6,7].

A lot of derivatives of chitin with different functional properties have been synthesized by chemical modifications. Shalumon et al. [8] reported the synthesis of water-soluble carboxymethyl chitin and poly(vinyl alcohol) (PVA) blend by an electrospinning method which was used for tissue engineering applications. Morin and Dufresne [9] reported the preparation of nanocomposites from a colloidal suspension of chitin whiskers and poly(e-caprolactone) as the matrix. In another study, Madhumathi et al. developed novel chitin/nanosilver composite scaffolds that have excellent antibacterial activity against Staphylococcus aureus and Escherichia coli as well as good blood-clotting ability [10]. The results of their study suggested that α-chitin/nanosilver composite scaffolds could be used for wound-healing applications. In addition, SiO₂-chitin/carbon nanotubes (CNTs) bionanocomposites have also been reported by many researchers [11].

Recently, much attention has been paid to chitosan as a potential biopolymer due to its remarkable intrinsic properties [12,13]. Huang et al. reported the synthesis of various metal–chitosan nanocomposites including silver (Ag), gold (Au), platinum (Pt), and palladium (Pd) in aqueous solutions [14]. In another work, Berger and his coworkers prepared chitosan hydrogels by blending chitosan with other water-soluble nonionic polymers such as PVA [15].

Chitin and chitosan inherently have poor mechanical properties that results in difficulties for their use in bone repair and reconstruction. Therefore the mechanical properties of chitin and chitosan can be improved only when the addition of biomaterials like hydroxyapatite (HAp), bioactive glass ceramic (BGC), etc. is possible. Recently, our group reported the preparation of chitosan/nanohydroxyapatite bioceramic scaffold for spongy bone regeneration [16]. BGC are a group of osteoconductive silicate-based materials used for bone repair. Wheeler et al. reported BGC coating on the surface of titanium which was used for osteointegration [17].

Different types of preparation techniques for the manufacture of advanced polymeric materials with chitin and chitosan have been discussed by Paillet and Dufresne. These include casting and evaporating technique, freeze-drying and hot-pressing techniques, polymer grafting, nonaqueous solvent dispersion technique, extrusion, impregnation, and electrospinning. This chapter intends to focus on the basic fundamentals of chitin and chitosan including their structure, preparation, and applications.

1.2 Chemical structure and preparation of chitin and chitosan

Chitin is a naturally occurring polysaccharide found in the shells of living organisms such as crabs, lobsters, tortoise, shrimps, and insects [18] or it can be generated via fungal fermentation processes. And chitosan is a unique biobased polymer that is a derivative of chitin and forms the exoskeleton of arthropods. It is obtained by partial deacetylation of chitin using a chemical method or by enzymatic hydrolysis. In general, chitin with a degree of deacetylation of 70% or above is considered to be chitosan [19].

1.2.1 Chemical structure and preparation of chitin

Chitin is a naturally occurring polymer consisting of 2-acetamido-2-deoxy-D-glucose via a β(1-4) linkage (Fig. 1.1). Three forms of chitin are available, namely α-, β-, and γ-chitin, however, the structure of α-chitin has been investigated more extensively than that of either the β- or γ- form. Very few studies have been carried out on γ-chitin because γ-chitin may be a distorted version of either α- or β-chitin [20].

Figure 1.1 Chemical structure of chitin.

A suspension of chitin crystallite particles was first prepared by Marchessault et al. [21] in 1959. In this method, 2.5 N hydrochloric acid solution was used to treat purified chitin under reflux for 1 h. After the reflux, the excess acid was separated by a decantation process and then distilled water was added to obtain the suspension. It was observed from their method that the acid-hydrolyzed chitin spontaneously dispersed into rod-like particles that could be concentrated to a liquid crystalline phase and self-assembled to a cholesteric liquid crystalline phase above a certain concentration [22]. Though chitins are present within numerous taxonomic groups, on the commercial scale they are usually extracted from marine crustaceans, mainly because a large amount of waste is available as a by-product of food processing.

1.2.2 Chemical structure and preparation of chitosan

As the second most abundant natural biopolymer after cellulose, chitosan consists of β(1-4)-linked D-glucosamine with randomly located N-acetylglucosamine groups depending upon the degree of deacetylation of the polymer (Fig. 1.2). Deacetylation is normally conducted by repetitions of alkaline hydrolysis due to the resistance of such groups owing to the trans arrangement of the C2-C3 substituents in the sugar ring [23]. The conditions during deacetylation must be properly controlled so that the chitin may be deacetylated to chitosan resulting in a better yield.

Figure 1.2 Chemical structu...

Table of contents

• Cover image
• Title page
• Table of Contents
• Copyright
• List of Contributors
• Chapter 1. Polymer blends, IPNs, gels, composites, and nanocomposites from chitin and chitosan; manufacturing, and applications
• Chapter 2. Chemically modified chitin, chitosan, and chitinous polymers as biomaterials
• Chapter 3. Chitin and chitosan composites for wearable electronics and energy storage devices
• Chapter 4. Investigation into the functional properties of cotton, wool, and denim textile materials finished with chitosan and the use of chitosan in textile-reinforced composites and medical textiles
• Chapter 5. Chitin blends, interpenetrating polymer networks, gels, composites, and nanocomposites for adsorption systems: environmental remediation and protein purification
• Chapter 6. Functional properties of chitin and chitosan-based polymer materials
• Chapter 7. Fundamentals of chitosan for biomedical applications
• Chapter 8. Electrospun chitosan materials and their potential use as scaffolds for bone and cartilage tissue engineering
• Chapter 9. Injectable polymeric gels based on chitosan and chitin for biomedical applications
• Chapter 10. Preparation and application of biomimetic and bioinspired membranes based on chitosan
• Chapter 11. Chitin, chitosan, marine to market
• Chapter 12. Chitin- and chitosan-based oleogels: rheological and thermal behavior modifications
• Chapter 13. Chitosan as biomaterial in drug delivery and tissue engineering
• Chapter 14. Biomedical applications carboxymethyl chitosans
• Chapter 15. Biomedical exploitation of chitin and chitosan-based matrices via ionic liquid processing
• Chapter 16. Chitin and chitosan composites for bone tissue regeneration
• Chapter 17. Drug delivery and tissue engineering applications of chitosan-based biomaterial systems
• Chapter 18. Future aspects of biomedical applications of chitin and chitosan in diseases associated with oxidative stress
• Chapter 19. Immunomodulatory activities of chitin and chitosan microparticles
• Chapter 20. Chitosan/chitin-based composites for food packaging applications
• Chapter 21. Modified release properties of glutathione-based chitosan films: Physical and functional characterization
• Chapter 22. Chitosan-based materials as templates for essential oils
• Chapter 23. Chitosan and chitosan-based biomaterials for wound management
• Chapter 24. Chitin and chitosan as promising immunostimulant for aquaculture
• Chapter 25. Chitosan-based materials for water and wastewater treatment
• Index