Chitin and chitosan: proceedings of the second International Conference on Chitin and Chitosan, July 12-14, 1982, Sapporo, Japan

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Chitin and Chitosan

Wiley Series in Renewable Resources Series Editor: Christian V. Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium

Titles in the Series: Wood Modification: Chemical, Thermal and Other Processes Callum A. S. Hill Renewables‐Based Technology: Sustainability Assessment Jo Dewulf, Herman Van Langenhove Biofuels Wim Soetaert, Erik Vandamme Handbook of Natural Colorants Thomas Bechtold, Rita Mussak Surfactants from Renewable Resources Mikael Kjellin, Ingegärd Johansson Industrial Applications of Natural Fibres: Structure, Properties and Technical Applications Jörg Müssig Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power Robert C. Brown Biorefinery Co‐Products: Phytochemicals, Primary Metabolites and Value‐Added Biomass Processing Chantal Bergeron, Danielle Julie Carrier, Shri Ramaswamy Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals Charles E. Wyman Bio‐Based Plastics: Materials and Applications Stephan Kabasci Introduction to Wood and Natural Fiber Composites Douglas D. Stokke, Qinglin Wu, Guangping Han Cellulosic Energy Cropping Systems Douglas L. Karlen Introduction to Chemicals from Biomass, 2nd Edition James H. Clark, Fabien Deswarte Lignin and Lignans as Renewable Raw Materials: Chemistry, Technology and Applications Francisco G. Calvo‐Flores, Jose A. Dobado, Joaquín Isac‐García, Francisco J. Martín‐Martínez

Sustainability Assessment of Renewables‐Based Products: Methods and Case Studies Jo Dewulf, Steven De Meester, Rodrigo A. F. Alvarenga Cellulose Nanocrystals: Properties, Production and Applications Wadood Hamad Fuels, Chemicals and Materials from the Oceans and Aquatic Sources Francesca M. Kerton, Ning Yan Bio‐Based Solvents François Jérôme and Rafael Luque Nanoporous Catalysts for Biomass Conversion Feng-Shou Xiao and Liang Wang Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power, 2nd Edition Robert C. Brown

Forthcoming Titles: The Chemical Biology of Plant Biostimulants Danny Geelen, Lin Xu Biorefinery of Inorganics: Recovering Mineral Nutrients from Biomass and Organic Waste Erik Meers, Gerard Velthof Waste Valorization: Waste Streams in a Circular Economy Sze Ki Lin, Chong Li, Guneet Kaur, Xiaofeng Yang Process Systems Engineering for Biofuels Development Adrián Bonilla-Petriciolet, Gade Pandu Rangaiah Biobased Packaging: Material, Environmental and Economic Aspects Mohd Sapuan Salit, Rushdan Ahmad Ilyas

Chitin and Chitosan: Properties and Applications Edited by

LAMBERTUS A.M. VAN DEN BROEK Wageningen Food & Biobased Research Wageningen The Netherlands

CARMEN G. BOERIU Wageningen Food & Biobased Research Wageningen The Netherlands

This edition first published 2020 © 2020 John Wiley & Sons Ltd All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions. The right of Lambertus A.M. van den Broek and Carmen G. Boeriu to identified as the authors of the editorial material in this work has been asserted in accordance with law. Registered Offices John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK Editorial Office The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, UK For details of our global editorial offices, customer services, and more information about Wiley products visit us at www.wiley.com. Wiley also publishes its books in a variety of electronic formats and by print‐on‐demand. Some content that appears in standard print versions of this book may not be available in other formats. Limit of Liability/Disclaimer of Warranty In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to the use of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert or instructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage and for added warnings and precautions. While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Library of Congress Cataloging‐in‐Publication data applied for ISBN: 9781119450436 Cover Design: Wiley Cover Images: © GiroScience/Shutterstock; Education globe © Ingram Publishing/Alamy Stock Photo Set in 10/12pt Times by SPi Global, Pondicherry, India

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Contents List of Contributors

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Series Preface

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Prefacexxiii 1 Sources of Chitin and Chitosan and their Isolation 1 Leen Bastiaens, Lise Soetemans, Els D’Hondt, and Kathy Elst 1.1  Chitin and Chitosan 2 1.1.1  Chemical Structure 2 1.1.2  Different Crystalline Forms of Chitin 2 1.2  Sources of Chitin and Chitosan 5 1.2.1  Sources of Chitin 5 1.2.2  Sources for Chitosan 10 1.3  Isolation of Chitin 11 1.3.1  Technology Principles 11 1.3.2  Isolation of Chitin from Crustaceans 13 1.3.3  Isolation of Chitin from Insects 16 1.3.4  Isolation of Chitin from Other Biomass Types 16 1.4  Production of Chitosan 19 1.4.1  Conversion of Chitin to Chitosan 19 1.4.2  Chitosan Extracted from Fungi 24 1.5  Towards Commercial Applications 25 1.6 Outlook 28 References28 2 Methods of Isolating Chitin from Sponges (Porifera) 35 Sonia Ż ółtowska, Christine Klinger, Iaroslav Petrenko, Marcin Wysokowski, Yvonne Joseph, Teofil Jesionowski, and Hermann Ehrlich 2.1 Introduction 35 2.2  Brief Overview of Classical Methods of Isolating Chitin from Invertebrates38

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2.3  The Modern Approach to Chitin Isolation from Sponges 40 2.3.1 Methods of Isolating Chitin from Glass Sponges (Hexactinellida) 41 2.3.2 Methods of Isolating Chitin from  Demosponges (Demospongiae) 43 2.4  Prospective Applications of Poriferan Chitin 49 2.4.1 Poriferan Chitin and Modern Bioinspired Materials Science 49 2.4.2 Chitinous 3D Scaffolds of Sponge Origin for  Tissue Engineering 51 2.5 Outlook 54 Acknowledgment54 References54 3 Physicochemical Properties of Chitosan and its Degradation Products 61 Karolina Gzyra‐Jagieła, Bożenna Pęczek, Maria Wis ́niewska‐Wrona, and Natalia Gutowska 3.1  Physicochemical Properties of Chitosan 62 3.1.1 Determination of Molar Mass 62 3.1.2 Determination of the Deacetylation Degree 67 3.1.3 Determination of Dynamic Viscosity 70 3.1.4 Determination of Nitrogen 70 3.1.5 Determination of Ash Content 71 3.1.6 Determination of Heavy Metal Content 71 3.1.7 Determination of Water Retention Value (WRV) 72 3.1.8 Determination of Solubility in Hydrochloric Acid 72 3.1.9 Determination of Water Content 72 3.1.10  Determination of Protein Content 73 3.1.11  Quantitative Determination of Chitosan by Ninhydrin 73 3.2  Products of Degradation and their Application 74 3.3 Outlook 77 References77 4 New Developments in the Analysis of Partially Acetylated Chitosan Polymers and Oligomers81 Stefan Cord‐Landwehr, Anna Niehues, Jasper Wattjes, and Bruno M. Moerschbacher 4.1 Introduction 82 4.2  Chitosan Oligomers 83 4.2.1 Degree of Polymerisation (DP), Fraction and Pattern of Acetylation (FA and PA)83 4.3  Chitosan Polymers 86 4.3.1 Molecular Weight (MW) / Degree of Polymerisation (DP) and its Dispersity (ÐMW / ÐDP)86 4.3.2 Fraction of Acetylation (FA) and its Dispersity (ÐFA)87 4.3.3 Pattern of Acetylation (PA)89 4.4 Outlook 91 References92

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5 Chitosan‐Based Hydrogels 97 Zhengke Wang, Ling Yang, and Wen Fang 5.1 Introduction 97 5.2  Chitosan‐Based Multilayered Hydrogels 98 5.2.1  Periodic Precipitation 99 5.2.2  Alternating Process 100 5.2.3  Induced by Electrical Signals 100 5.2.4  Layer‐by‐Layer (LbL) Assembly 101 5.2.5  Sequential Curing 101 5.3  Chitin/Chitosan Physical Hydrogels Based on Alkali/Urea Solvent System 103 5.3.1  Chitin Hydrogels Based on Alkali/Urea Solvent System 104 5.3.2  Chitosan Hydrogels Based on Alkali/Urea Solvent System 104 5.4  Chitosan‐Based Injectable Hydrogels 108 5.4.1  Physical Association Networks 108 5.4.2  Chemical Association Networks 110 5.4.3  Double‐Network Hydrogels 116 5.5  Chitosan‐Based Self‐Healing Hydrogels 119 5.5.1  Physical Interactions 119 5.5.2  Dynamic Chemical Bonds 121 5.6  Chitosan‐Based Shape Memory Hydrogels 125 5.6.1  Water‐/Solvent‐Triggered Shape Recovery 126 5.6.2  pH‐triggered Shape Recovery 126 5.6.3  Ultrasound Triggered Shape Recovery 126 5.6.4  Self‐Actuated Shape Memory Hydrogels 127 5.6.5  Chitosan‐Based Hydrogels with Triple Shape Memory Effect 127 5.7  Superabsorbent Chitosan‐Based Hydrogels 131 5.7.1  Cross‐Linked Chitosan‐Based Hydrogels 132 5.7.2  Hydrogels by Graft Copolymerization 133 5.7.3  Chitosan‐Based Composite Hydrogels 134 5.7.4  Pure Chitosan‐Based Materials 135 5.8 Outlook 136 References136 6 Beneficial Health Effects of Chitin and Chitosan Liyou Dong, Harry J. Wichers, and Coen Govers 6.1  Immunomodulatory Effects of Chitin and Chitosan as Demonstrated with In Vitro Studies 6.2  Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Animal Studies 6.2.1  Immune Modulation 6.2.2  Anti‐Pathogenic Effects 6.2.3  Anti‐Tumour Effects 6.3  Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Clinical Trials 6.3.1  Cholesterol Reduction and CVD Preventive Effects 6.3.2  Other Health Effects 6.4  Requirements to forward the Field of Study Towards the Beneficial Health Effects of Chitin and Chitosan

145 146 149 149 155 157 158 158 160 163

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6.5 Outlook 164 Acknowledgement164 References164 7 Antimicrobial Properties of Chitin and Chitosan 169 Magdalena Kucharska, Monika Sikora, Kinga Brzoza‐Malczewska, and Monika ­Owczarek 7.1  Microbiological Activity of Chitosan – The Mechanism of its Antibacterial and Antifungal Activity 169 7.2  The use of Chitin/Chitosan’s Microbiological Activity in Medicine and Pharmacy171 7.3  Microbiological Activity of Chitosan in the Food Industry 174 7.4  Microbiological Activity of Chitosan in Paper and Textile Industries 176 7.5  Microbiological Activity of Chitosan in Agriculture 177 7.6 Outlook 181 References181 8 Enzymes for Modification of Chitin and Chitosan 189 Gustav Vaaje‐Kolstad, Tina Rise Tuveng, Sophanit Mekasha, and Vincent G.H. Eijsink 8.1  CAZymes in Chitin Degradation and Modification 190 8.1.1 Chitinases 191 8.1.2  β‐N‐acetylhexosaminidases195 8.1.3  Exo‐β‐glucosaminidases195 8.1.4 Chitosanases 197 8.1.5  Lytic Polysaccharide Monooxygenases 199 8.1.6  Carbohydrate Esterases 200 8.1.7  Carbohydrate‐Binding Modules 204 8.2  Modular Diversity in Chitinases, Chitosanases and LPMOs204 8.3  Biological Roles of Chitin‐Active Enzymes 205 8.4  Microbial Degradation and Utilisation of Chitin 208 8.4.1  Chitin Degradation by Serratia marcescens209 8.4.2  Chitin Degradation by Bacteria in the Bacteroidetes Phylum211 8.4.3  Chitin Degradation by Thermococcus Kodakarensis211 8.4.4  Chitin Degradation by Fungi 212 8.5  Biotechnological Perspectives 213 8.6  Biorefining of Chitin‐Rich Biomass 214 8.7 Outlook 216 References216 9 Chitin and Chitosan as Sources of Bio‐Based Building Blocks and Chemicals229 Malgorzata Kaisler, Lambertus A.M. van den Broek, and Carmen G. Boeriu 9.1 Introduction 230 9.2  Chitin Conversion into Chitosan, Chitooligosaccharides and  Monosaccharides232

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9.2.1 Chitosan Production 232 9.2.2  Production of Chitooligosaccharides 234 9.2.3  Production of GlcNAc and GlcN from Chitin 235 9.3 Building Blocks for Polymers from Chitin and its Derivatives 238 9.3.1 Furan‐Based Monomers 238 9.3.2  Amino Alcohol and Amino Acid Building Blocks 239 9.4 Outlook 239 Acknowledgement240 References240 10 Chemical and Enzymatic Modification of Chitosan to Produce New Functional Materials with Improved Properties 245 Carmen G. Boeriu and Lambertus A.M. van den Broek 10.1 Introduction 245 10.2 Functional Chitosan Derivatives by Chemical and Enzymatic Modification246 10.2.1  Anionic Chitosan Derivatives 248 10.2.2 Hydroxyalkylchitosans 250 10.2.3  Quaternised and Highly Cationic Chitosan Derivatives 250 10.2.4  Hydroxyaryl Chitosan Derivatives 250 10.2.5  Carbohydrate‐Modified Chitosan 251 10.3  Graft Co‐Polymers of Chitosan 251 10.4  Cross‐Linked Chitosan and Chitosan Polymer Networks 254 10.5 Outlook 254 References255 11 Chitosan‐Based Drug Delivery Systems Cristian Peptu, Andra Cristina Humelnicu, Razvan Rotaru, Maria Emiliana Fortuna, Xenia Patras, Mirela Teodorescu, Bogdan Ionel Tamba, and Valeria Harabagiu 11.1 Introduction 11.2  Beneficial Effects of Chitosan 11.2.1  Interaction with Anionic Drugs 11.2.2  Mucoadhesive Properties 11.2.3  Transfection Activity 11.2.4  Efflux Pump Inhibitory Properties 11.2.5  Permeation‐Enhancing Properties 11.3  Chitosan—an Active Polymer for Bypassing Biological Barriers 11.3.1  Skin Barrier 11.3.2  Mucosa Barrier 11.3.3  Ophthalmic Barrier 11.3.4  Blood–Brain Barrier 11.4  Chitosan‐Based DDS Formulations 11.4.1 Hydrogels 11.4.2 Micro/NPs 11.4.3 Nanofibers 11.4.4  Scaffolds and Membranes

259

260 261 263 263 263 265 265 265 266 267 269 270 271 275 275 275 275

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11.5 Outlook 276 Acknowledgment276 References276 12 The Application of Chitin and its Derivatives for the Design of Advanced Medical Devices 291 Marcin H. Struszczyk, Longina Madej‐Kiełbik, and Dorota Zielińska 12.1  Selection of the Raw Sources: Safety Criteria 291 12.1.1  Aspect of Animal Tissue‐Originated Derivatives 292 12.1.2 General Requirements for Chitinous Biopolymers Applied in Designing Medical Devices 292 12.1.3 Characterisation of the Biopolymer for Application in Wound Dressing Designing293 12.1.4  Aspect of the Sterilization of the Final Wound Dressing 295 12.2 Types of Wound Dressings Consisting of Chitin‐Derived Biopolymers Available in the Market297 12.3  Performance and Safety Assessment 297 12.4  New Ideas and Concepts 301 12.5  Risk Acceptance and Design Process Aspects 306 12.6 Outlook 308 Acknowledgements308 References308 13 Food Applications of Chitosan and its Derivatives 315 Suse Botelho da Silva, Daiana de Souza, and Liziane Dantas Lacerda 13.1 Introduction 315 13.2  Chitosan and its Derivatives as Food Additive 316 13.2.1 Antioxidant 318 13.2.2 Antimicrobial 319 13.2.3  Stabilizer and Thickener 319 13.3  Functional Ingredient and Health Beneficial Effects 320 13.4  Active Packaging 321 13.5  Enzyme Immobilization 331 13.6  Encapsulation and Delivering of Bioactive Ingredients 332 13.7  Adsorption and Chelation of Toxic and Undesirable Compounds 334 13.8 Outlook 339 References340 14 Potential of Chitosans in the Development of Edible Food Packaging 349 Véronique Coma and Artur Bartkowiak 14.1  Potential Limitations for Real Introduction into the Market 350 14.1.1  Generally Recognized as Safe (GRAS)351 14.1.2 Solubility 351 14.1.3 Source—Origin 352 14.1.4  Structure Variability 352 14.2  Films and Coatings for Food Preservation 353

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14.2.1  Definitions and Interests 353 14.2.2  Main Relevant Chitosan‐Based Material Properties 353 14.3 Specific Case of Chitosan Nanoparticles (CSNPs)357 14.3.1 CSNPs 357 14.3.2 CSNPs in Various Edible Films 358 14.3.3  Antimicrobial Activities of CSNPs in Edible Films 359 14.3.4  Toxicity Studies of CSNPs360 14.4 Applications to Sensitive Real Food Products 360 14.4.1  Fruits and Vegetables 361 14.4.2  Meat and Meat Products 362 14.4.3  Fish and Seafood Products 362 14.5 Conclusions 364 References364 15 The Use of Chitosan‐Based Nanoformulations for Controlling Fungi During Storage of Horticultural Commodities 371 Silvia Bautista‐Baños, Zormy Nacary Correa‐Pacheco, and Rosa Isela Ventura‐­Aguilar 15.1 Introduction 372 15.2 Importance of Fruits and Vegetables 372 15.3 Storage Disorders and Diseases of Horticultural Products 374 15.4 Plant Fungi Inhibition by Chitosan Application 375 15.5 Chitosan Integrated with Other Alternative Methods for Controlling Postharvest Fungi 376 15.6 Chitosan‐Based Formulations 376 15.7 Physiological Response and Quality Retention of Horticultural Commodities to Chitosan Coating Application 376 15.8 Influence of Chitosan Coatings on the Shelf Life of  Horticultural Products 378 15.9 Effects of Chitosan Coatings with Additional Compounds on Quality and Microorganisms Development 379 15.10 Integration of Chitosan Nanoparticles into Coating Formulations and their Effects on the Quality of Horticultural Commodities and Development of Microorganisms 384 15.11 Outlook 387 Acknowledgments387 References387 16 Chitosan Application in Textile Processing and Fabric Coating Thomas Hahn, Leonie Bossog, Tom Hager, Werner Wunderlich, Rudi Breier, Thomas Stegmaier, and Susanne Zibek 16.1 Chitosan in the Textile Industry 16.2 Textile Production 16.3 General Test Methods 16.4 Fibres and Yarns from Chitin and Chitosan 16.4.1  Chitin and Chitosan Solubilisation for Spinning Purposes

395 396 398 400 401 402

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16.4.2  Chitosan Spinning Processes 402 16.4.3  Mechanical Properties of Chitosan Fibres/Yarns 404 16.5  Sizing with Chitosan 406 16.5.1  Miscibility of Chitosan with Other Sizing Agents 407 16.5.2  Viscosity of Chitosan‐Containing Sizing Agents 408 16.5.3  Adhesion and Wetting 410 16.5.4  Mechanical–Physical Properties of Chitosan Films 411 16.5.5  Removal and Processing of Chitosan Sizing after Weaving 412 16.6  Chitosan as a Finishing Agent or Coating 414 16.6.1  Chitosan as a Carrier and Linker 415 16.6.2  Formation of a Durable Finish with Chitosan 416 16.6.3  Chitosan as an Active Agent 417 16.7 Outlook 419 Nomenclature420 References421 17 Chitin and Chitosan for Water Purification 429 Petrisor Samoila, Andra Cristina Humelnicu, Maria Ignat, Corneliu Cojocaru, and Valeria Harabagiu 17.1 Introduction 430 17.2  Wastewater Treatment by Adsorption 432 17.2.1  Principle of the Adsorption Process 432 17.2.2  Adsorption of Organic Compounds 434 17.2.3  Adsorption of Heavy Metals 437 17.3  Wastewater Treatment by Coagulation/Flocculation 440 17.4  Wastewater Treatment by Membrane Separation 446 17.4.1  Principle of Ultrafiltration Process 446 17.4.2  Fabrication of Ultrafiltration Blend Membranes 448 17.4.3  Chitosan‐Enhanced Ultrafiltration 450 17.5 Outlook 452 Acknowledgement452 References453 18 Chitosan for Sensors and Electrochemical Applications 461 Suse Botelho da Silva, Guilherme Lopes Batista, and Cristiane Krause Santin 18.1 Introduction 461 18.2  Chitosan: A Biopolymer with Unique Properties 462 18.3 Modification and Preparation of Chitosan‐Based Materials for Electrochemical Applications 463 18.4  The Proton Conductivity of Chitosan 465 18.5  Selected Applications 467 18.5.1  Electrochemical Sensors 467 18.5.2  Spectroscopic Sensors 470 18.5.3  Other Electrochemical Devices 471 18.6 Outlook 472 References473

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19 Marketing and Regulations of Chitin and Chitosan from Insects 477 Nathalie Berezina and Antoine Hubert 19.1  Historical Outline 477 19.2  Natural Origins of Chitin 478 19.3  Specificities of Chitin Biopolymer 479 19.4  Differences Among Chitins from Insects and Other Sources 479 19.4.1  Differences of Chemical Compositions of the Cuticles 479 19.4.2  Differences of Physical Assemblies of Chains and Molecules 480 19.5  Extraction and Purification Specificities of Chitins from Insects 480 19.5.1  Different Cuticle Structures and Contents of Insects 480 19.5.2  Chemical Extraction 480 19.5.3  Biological Extraction 481 19.5.4  Characterization and Transformation into Chitosan 481 19.6  Market Opportunities and its Regulations 482 19.6.1  Agriculture Applications 482 19.6.2  Water Treatment Applications 483 19.6.3  Material Applications 483 19.6.4  Biomedical Applications 484 19.7 Outlook 485 References485 Index491

List of Contributors Artur Bartkowiak  Center of Bioimmobilisation and Innovative Packaging Materials, Faculty of Food Sciences and Fisheries, West Pomeranian University of Technology, Szczecin, Poland Leen Bastiaens  VITO (Flemish Institute for Technological Research), Mol, Belgium Silvia Bautista‐Baños  Centro de Desarrollo de Productos Bióticos (CEPROBI), Instituto Politécnico Nacional (IPN), Yautepec, Morelos, Mexico Nathalie Berezina  Ynsect, Évry, France Carmen G. Boeriu  Wageningen Food & Biobased Research, Wageningen, The Netherlands Leonie Bossog  Textilchemie Dr. Petry GmbH, Reutlingen, Germany Suse Botelho da Silva  Food and Chemical Engineering, Polytechnic School, Unisinos University, São Leopoldo, RS, Brazil Rudi Breier  Textilchemie Dr. Petry GmbH, Reutlingen, Germany Lambertus A.M. van den Broek  Wageningen Food & Biobased Research, Wageningen, The Netherlands Kinga Brzoza‐Malczewska  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Corneliu Cojocaru  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Véronique Coma  University of Bordeaux, LCPO, UMR 5629, Centre National de la Recherche Scientifique (CNRS), Pessac, France Stefan Cord‐Landwehr  University of Münster, Institute for Biology and Biotechnology of Plants, Münster, Germany Zormy Nacary Correa‐Pacheco  CONACYT-CEPROBI, Instituto Politécnico Nacional, Yautepec, Morelos, Mexico

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Els D’Hondt  VITO (Flemish Institute for Technological Research), Mol, Belgium Liyou Dong  Food & Health Research, Wageningen Food & Biobased Research, Wageningen, The Netherlands; Food Chemistry, Wageningen University, Wageningen, The Netherlands Hermann Ehrlich  Institute of Electronics and Sensor Materials, TU Bergakademie‐ Freiberg, Freiberg, Germany Vincent G.H. Eijsink  Faculty of Chemistry, Biotechnology, and Food Science, The Norwegian University of Life Sciences (NMBU), Ås, Norway Kathy Elst  VITO (Flemish Institute for Technological Research), Mol, Belgium Wen Fang  Institute of Biomedical Macromolecules, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, China Maria Emiliana Fortuna  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Coen Govers  Food & Health Research, Wageningen Food & Biobased Research, Wageningen, The Netherlands Natalia Gutowska  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Karolina Gzyra‐Jagieła  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Tom Hager  German Institutes of Textile and Fiber Research, Denkendorf, Germany Thomas Hahn  Fraunhofer Institute of Interfacial Engineering and Biotechnology, Stuttgart, Germany Valeria Harabagiu  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Antoine Hubert  Ynsect, Évry, France Andra Cristina Humelnicu  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Maria Ignat  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Teofil Jesionowski  Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, Poznan, Poland Yvonne Joseph  Institute of Electronics and Sensor Materials, TU Bergakademie‐ Freiberg, Freiberg, Germany Malgorzata Kaisler Bioprocess Engineering Group, Wageningen University, Wageningen, The Netherlands; Wageningen Food & Biobased Research, Wageningen, The Netherlands Christine Klinger  Institute of Physical Chemistry, TU Bergakademie‐Freiberg, Freiberg, Germany

List of Contributors

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Cristiane Krause Santin  Food and Chemical Engineering, Polytechnic School, Unisinos University, São Leopoldo, RS, Brazil; itt CHIP – Unisinos Semiconductor Institute, São Leopoldo, RS, Brazil Magdalena Kucharska  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Liziane Dantas Lacerda  Food and Chemical Engineering, Polytechnic School, Unisinos University, São Leopoldo, RS, Brazil Guilherme Lopes Batista  itt CHIP – Unisinos Semiconductor Institute, São Leopoldo, RS, Brazil Longina Madej‐Kiełbik  The Institute of Security Technologies “MORATEX”, Lodz, Poland Sophanit Mekasha  Faculty of Chemistry, Biotechnology, and Food Science, The Norwegian University of Life Sciences (NMBU), Ås, Norway Bruno M. Moerschbacher  University of Münster, Institute for Biology and Biotechnology of Plants, Münster, Germany Anna Niehues  University of Münster, Institute for Biology and Biotechnology of Plants, Münster, Germany Monika Owczarek  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Xenia Patras  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Bożenna Pe ̨czek  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Cristian Peptu  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Iaroslav Petrenko  Institute of Experimental Physics, TU Bergakademie‐Freiberg, Freiberg, Germany Razvan Rotaru  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Petrisor Samoila  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Monika Sikora  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Lise Soetemans  VITO (Flemish Institute for Technological Research), Mol, Belgium Daiana de Souza  Food and Chemical Engineering, Polytechnic School, Unisinos University, São Leopoldo, RS, Brazil Thomas Stegmaier  German Institutes of Textile and Fiber Research, Denkendorf, Germany Marcin H. Struszczyk  The Institute of Security Technologies “MORATEX”, Lodz, Poland

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List of Contributors

Bogdan Ionel Tamba  A&B Pharm Corporation, Roman, Neamt ̦, Romania Mirela Teodorescu  ‘Petru Poni’ Institute of Macromolecular Chemistry, Romanian Academy, Iași, Romania Tina Rise Tuveng  Faculty of Chemistry, Biotechnology, and Food Science, The Norwegian University of Life Sciences (NMBU), Ås, Norway Gustav Vaaje‐Kolstad  Faculty of Chemistry, Biotechnology, and Food Science, The Norwegian University of Life Sciences (NMBU), Ås, Norway Rosa Isela Ventura‐Aguilar  CONACYT-CEPROBI, Instituto Politécnico Nacional, Yautepec, Morelos, Mexico Zhengke Wang  Institute of Biomedical Macromolecules, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, China Jasper Wattjes  University of Münster, Institute for Biology and Biotechnology of Plants, Münster, Germany Harry J. Wichers  Food & Health Research, Wageningen Food & Biobased Research, Wageningen, The Netherlands; Food Chemistry, Wageningen University, Wageningen, The Netherlands Maria Wis ń iewska‐Wrona  Institute of Biopolymers and Chemical Fibres, Lodz, Poland Werner Wunderlich  German Institutes of Textile and Fiber Research, Denkendorf, Germany Marcin Wysokowski  Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, Poznan, Poland; Institute of Electronics and Sensor Materials, TU Bergakademie‐Freiberg, Freiberg, Germany Ling Yang  Institute of Biomedical Macromolecules, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, China Susanne Zibek  Fraunhofer Institute of Interfacial Engineering and Biotechnology, Stuttgart, Germany Dorota Zielińska  The Institute of Security Technologies “MORATEX”, Lodz, Poland Sonia Ż ółtowska  Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, Poznan, Poland; Institute of Electronics and Sensor Materials, TU Bergakademie‐Freiberg, Freiberg, Germany

Series Preface Renewable resources, their use and modification are involved in a multitude of important processes with a major influence on our everyday lives. Applications can be found in the energy sector; paints and coatings; and the chemical, pharmaceutical, and textile industry, to name but a few. The area interconnects several scientific disciplines (agriculture, biochemistry, chemistry, technology, environmental sciences, forestry), which makes it very difficult to have an expert view on the complicated interaction. Therefore, the idea to create a series of scientific books, focusing on specific topics concerning renewable resources, has been very opportune and can help to clarify some of the underlying connections in this area. In a very fast‐changing world, trends are not only characteristic of fashion and political standpoints; science too is not free from hypes and buzzwords. The use of renewable resources is again more important nowadays; however, it is not part of a hype or a fashion. As the lively discussions among scientists continue about how many years we will still be able to use fossil fuels – opinions ranging from 50 to 500 years – they do agree that the reserve is limited, and that it is essential not only to search for new energy carriers but also for new material sources. In this respect, the field of renewable resources is a crucial area in the search for alternatives for fossil‐based raw materials and energy. In the field of energy supply, biomass‐ and renewables‐based resources will be part of the solution alongside other alternatives such as solar energy, wind energy, hydraulic power, hydrogen technology and nuclear energy. In the field of material sciences, the impact of renewable resources will probably be even bigger. Integral utilisation of crops and the use of waste streams in certain industries will grow in importance, leading to a more sustainable way of producing materials. Although our society was much more (almost exclusively) based on renewable resources centuries ago, this disappeared in the Western world in the nineteenth century. Now it is time to focus again on this field of research. However, it should not mean a ‘retour à la nature’, but should be a multidisciplinary effort on a highly technological level to perform research towards new opportunities, to develop new crops and products from renewable resources. This will be essential to guarantee an acceptable level of comfort for the growing number of people living on our planet. It is ‘the’ challenge for the coming generations of scientists to develop more sustainable ways to create prosperity and to fight poverty and hunger in the world. A global approach is certainly favoured.

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Series Preface

This challenge can only be dealt with if scientists are attracted to this area and are recognised for their efforts in this interdisciplinary field. It is, therefore, also essential that consumers recognise the fate of renewable resources in a number of products. Furthermore, scientists do need to communicate and discuss the relevance of their work. The use and modification of renewable resources may not follow the path of the genetic engineering concept in view of consumer acceptance in Europe. Related to this aspect, the series will certainly help to increase the visibility of the importance of renewable resources. Being convinced of the value of the renewables approach for the industrial world, as well as for developing countries, I was myself delighted to collaborate on this series of books focusing on the different aspects of renewable resources. I hope that readers become aware of the complexity, the interaction and interconnections, and the challenges of this field, and that they will help to communicate on the importance of renewable resources. I certainly want to thank the people of Wiley’s Chichester office, especially David Hughes, Jenny Cossham and Lyn Roberts, in seeing the need for such a series of books on renewable resources, for initiating and supporting it, and for helping to carry the project to the end. Last, but not least, I want to thank my family, especially my wife Hilde and children Paulien and Pieter‐Jan, for their patience, and for giving me the time to work on the series when other activities seemed to be more inviting. Christian V. Stevens, Faculty of Bioscience Engineering Ghent University, Belgium Series Editor, ‘Renewable Resources’ June 2005

Preface Chitin was reported for the first time about 200 years ago, in extracts of mushrooms and insects. About 40 years later, chitosan was obtained from chitin by acid treatment. These polysaccharides are among the most abundant natural biopolymers in the world. They are, for example, present in crustaceans, insects and fungi. Just before World War II, there was a huge interest in the applications of these polysaccharides as a bioplastic. However, the simultaneous upcoming of synthetic polymers and the exponential increase in high‐­ performance synthetic polymers, which outperformed their natural counterparts, resulted in a decrease of interest in chitin/chitosan materials. In the 1970s, large‐scale production of chitin and chitosan from the shells of marine organisms started, owing to the development of aquaculture and the enactment of severe environmental regulations to decrease the amount of shellfish dumping in the oceans. Nowadays there is a need to be less dependent on fossil resources. The transition to a biobased economy and the increasing societal demand for more green and environmentally friendly products urge us to look for chemicals, materials and fuels based on renewable resources. The enormous potential of chitin and chitosan on account of their abundance, unique properties and numerous applications makes them interesting biomass resources. This book, Chitin and Chitosan: Properties and Applications, shows the state‐of‐the‐art and future perspectives of chitin and chitosan materials and applications. The book presents the most recent developments in the science and technology of all related fields, from extraction and characterisation to modification, material synthesis and end‐user applications. This book comprises 19 chapters that deal with most topics related to chitin and chitosan polymers and materials. In Chapters 1–4, the sources of chitin and chitosan are described and how these biopolymers can be isolated. Next to the isolation, the analysis of the biopolymers is described. The different sources and/or isolation methods can result in different structures and properties. In Chapter 5–7, hydrogels, health effects and the anti‐microbial effects of chitin and chitosan are discussed. To improve or to modify the properties, enzymes and chemical reactions can be applied to customise these biopolymers, as shown in Chapters 8–10. The applications of chitin and chitosan in drug delivery, medical devices, agriculture, food, packaging, horticulture, textile, water purification and sensors are discussed in more detail in Chapters 11–18. And finally, Chapter 19 is devoted to the market and regulation of chitin and chitosan.

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These topics have never been addressed previously in a single book. Books, book chapters and reviews have been dedicated to the specific fields of application of chitin and chitosan materials. This book presents an overview of the latest scientific and technological advances in almost all areas of application, and show the great potential of chitin and chitosan as materials of the future. We hope that the reader will be inspired by the examples given of these biopolymers in different areas. We are confident that chitin and chitosan will become major renewable resources in the biobased circular economy. This book should be useful for scholars and those in academia, such as undergraduate and postgraduate students in the areas of agriculture, polymer and material sciences, biobased economy and life sciences. In addition, we hope this book will aid researchers and specialists from industry in the field of (bio)polymers, packaging, biomedical applications, water treatment, textiles, sensors, and agriculture and food – as well as regional and national policy‐makers. The input is from well‐known experts from all over the world. We would like to express our great gratitude to all chapter authors of this book, who have made excellent contributions. In addition, we would like to thank Sarah Higginbotham, Emma Strickland and Lesley Jebaraj from Wiley for all their help. Lambertus A.M. van den Broek and Carmen G. Boeriu Wageningen 2019

1 Sources of Chitin and Chitosan and their Isolation Leen Bastiaens, Lise Soetemans, Els D’Hondt, and Kathy Elst VITO – (Flemish Institute for Technological Research), Mol, Belgium

Chitin is a natural biomolecule that was reported for the first time in 1811 by the French professor Henri Braconnot as fungine [1] and in 1823 by Antoine Odier as chitin. Chitin consists of large, crystalline nitrogen‐containing polysaccharides made of chains of a modified glucose monosaccharide, being N‐acetylglucosamine. It is ubiquitously present in the world and has even been reported to be one of the most abundant biomolecules on earth, with an estimated annual production of 1011–1014 tons [2, 3]. Chitin serves as template for biomineralization such as calcification and silicification, providing preferential sites for nucleation, and controlling the location and orientation of mineral phases [4, 5]. This phenomenon explains the presence of chitin in solid structures in a variety of biomass such as cell walls of fungi and diatoms and in exoskeletons of Crustaceans. Chitin is present in diverse structures in at least 19 animal phyla besides its presence in bacteria, fungi, and algae [5]. Chitosan is mainly known as a partially deacetylated derivative of chitin that is more water soluble than chitin, and as such is easier to process. For this reason, chitosan—and, in some cases, even more preferably, the relatively small sized (1–10 kDa) chitosan ­oligomers—are the molecules that are envisioned for multiple applications such as agriculture; water and wastewater treatment; food and beverages; chemicals; feed; cosmetics; and personal care [6, 7]. In addition, chitosan oligomers have been reported as being bioactive [8], offering potential for application in, for instance, wound dressing and cosmetics. Although chitin and chitosan are versatile and promising biomaterials [9], the extraction

Chitin and Chitosan: Properties and Applications, First Edition. Edited by Lambertus A.M. van den Broek and Carmen G. Boeriu. © 2020 John Wiley & Sons Ltd. Published 2020 by John Wiley & Sons Ltd.

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Chitin and Chitosan: Properties and Applications

and purification of chitin and its conversion to chitosan (oligomers) require several process steps, and these have been mentioned as bottlenecks that hinder the wider use of the underspent chitin in the world. This chapter intends to provide more information related to (1) the structure of chitin, (2) sources of chitin and chitosan, and (3) their extraction and purification, as well as (4) the conversion of chitin into chitosan. The further conversion of chitosan to chitosan oligomers is the subject of Chapter 3.

1.1  Chitin and Chitosan 1.1.1  Chemical Structure Chitin, and its derivate chitosan, are natural polysaccharides consisting of 2 monosaccharides, N‐acetyl‐D‐glucosamine and D‐glucosamine, connected by β‐1,4‐ glycoside bonds. Depending on the frequency of the latter monosaccharides, the molecule is defined as chitin or chitosan. Chitin contains mainly N‐acetyl‐D‐glucosamine and can be transformed to chitosan by partial deacetylation of the monomer N‐acetyl‐D‐glucosamine to D‐glucosamine (see Figure 1.1) [7]. Diverse definitions of chitin and chitosan circulate in literature. Most sources mention a deacetylation degree of at least 50% [7, 10] as a criterion to define the molecule as chitosan. Others report a deacetylation degree of at least 60% or 75% for chitosan, implying that, respectively, more than 60% or 75% of the monosaccharides are D‐glucosamine moieties [11–13]. Chitin in its natural appearance is usually already a heteropolymer, with a deacetylation degree ranging between 5% and 20% [14]. The structure of chitin is very similar to that of cellulose and shares generally the same function of providing structure integrity and protection of the organism. 1.1.2  Different Crystalline Forms of Chitin Chitin usually functions as a supporting material and is composed of layers of polysaccharide sheets. Each individual sheet consists of multiple parallel‐positioned chitin chains [17], as schematically presented in Figure 1.2. Highly crystalline fibers are formed when the polymer sheets are placed next to each other and form interactions [12]. Depending on their orientation, three crystalline forms have been reported (α, β, and γ). The most abundant form is α‐chitin, which is present in almost all crustaceans, insects, fungi, and yeast cell walls [7]. In this formation, the chitin sheets (three sheets as example in Figure 1.2a), consisting of parallel chitin chains (for each sheet, two chains are presented in Figure 1.2a), are positioned in an anti‐parallel way, allowing a maximum formation of hydrogen bonding. More specifically, two intramolecular and two intermolecular bondings are formed: a first intermolecular bonding with a vertical neighbor chain (in the same sheet), and another with a horizontal neighbor chain form a different sheet  [15]. These hydrogen bounds create a remarkably high crystallinity, resulting in a more stiff and stable material. Therefore, α‐chitin is characterized as a non‐reactive and insoluble product [16]. Since this form is the most common polymorphic, α‐chitin has been extensively studied [12]. On the other hand, in β‐chitin, the chitin sheets are ordered in parallel (Figure 1.2b) with weaker intermolecular forces. This results in a softer molecule with a higher affinity

Insects

Algae

Crustaceans Chitin OH H O

H

O

H

OH

HN

H

H OH

H

H

OH

OH O

H3C

H O

H

O

H

O H

H OH

H

O

H

H OH

NH

H

NH2

OH O H

H3C

O NH

H

O

O H H

O

H3C

n

Deacetylation Chitosan Fungi

OH H O

H OH H

OH

OH O

O

H H NH2

H

H OH H

H

O H H O NH2

H OH H

Mollusks

OH O H

H

H

H OH

NH H 3C

O

O

H

O H H O NH2

n

Figure 1.1  Chemical structure of chitin and chitosan and some examples of species that contain chitin.

(a)

(b) Sheet 1 H C

HO

H C

HO

HO OH

O O

O

O

OH

NH OCH

O

NH

HO

H C

CH

H C

NH O

H CO NH

OH

NH

CH

O

OH O

O

O

NH

CH

H C

HO HO

O

O

O

NH OH OH HO HO

CH

H C

O

H CO NH O

O O O

O

CH

HO

HO HO

NH

CH

NH

HO

OH

HO

HO

n

n

HO

O

CH

OH O

HO

O O

O NH OCH

O

HO

NH

CH

HO HO

NH OCH

O

NH OH

CH

HO HO

NH

OH O O NH OCH NH

OH

OH HO

OH HO

HO

HO

Figure 1.2  Schematic representation of (a) α‐form and (b) β‐form of chitin.

O

O

O

O

CH

OH

OH

O

O NH OCH

O

OH

O

O

CH

OH

O

O O

CH

CH

NH

O O

O NH OCH

O

OH

OH

O

OH HO CH

NH

HO

OH

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NH OCH

O

O

O NH OCH

O

HO

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NH OCH

O

CH

OH OH

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O

O

O

OH

HO HO

O

O O OH

NH

CH

OH

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OH

NH OCH

NH

NH

HO

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NH OCH

O

NH

CH

O O

OH

OH

O OH

O

Chain 1

OH

NH

O NH OCH

O

OH

O

O

HO

NH OCH

O

O

O

HO

O

O

O

CH

OH

O

OH

H CO NH

OH

O

NH

HO

HO

O

NH

OH

HO

HO

HO

HO

O O

O

O NH OCH

O

OH

OH

OH

NH OCH

O

OH

O

O

O

NH OCH

O O OH

O O

O

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HO

O

O

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CH

OH

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O

OH

NH

H CO NH

NH

HO

CH

OH O

OH H C

OH

HO

NH

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O NH OCH

O

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NH OCH

O

HO

OH

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HO

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OH

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HO

HO

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H C

H C

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O

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H C

H C

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NH OCH

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OH OH HO HO

n

n

Sources of Chitin and Chitosan and their Isolation

5

for solvents and a higher reactivity. It is proven to be soluble in formic acid and can be swollen in water [15]. This chitin form is present in the squid pen, in the tubes of pogonophoran and vestimentiferan worms, and in monocrystalline spines excreted by diatoms such as Thalassiosira fluviatilis [7]. Although squid and tubes of Tevnia jerichonana both contain β‐chitin, their crystallinity differs. This implies that the crystallinity also depends on the source. Chitin obtained from squid pens is semi‐crystalline, and chitin from T. jerichonana is almost complete crystalline [7, 8, 16]. The third formation, γ‐chitin, is less common. It is considered to be a mixture or intermediate form of α‐ and β‐chitin with both parallel and antiparallel arrangements [16]. More specifically, every third chitin chain has the opposite direction to the two preceding chitin sheets [13, 15]. Very few studies have been carried out on γ‐chitin, and it has been s­ uggested that γ‐chitin may be a distorted version of the other two instead of a true third polymorphic form.

1.2  Sources of Chitin and Chitosan 1.2.1  Sources of Chitin For more than a century, scientists reported chitin to be present in a variety of organisms. Initially, zoologists named all hard yellow–brownish structures chitin, without chemical analysis, sometimes generating misleading data. Later on, it was accepted that the presence of chitin could only be demonstrated after chemical tests. Hymann (1958), for instance, used an iodine‐based color test to study the presence of chitin in different sea animals. Later on, more sophisticated techniques such as Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), mass spectroscopy (MS), X‐ray diffraction (XRD), and Raman spectroscopy were used [18]. Quantification of chitin is challenging and only reported in more recent publications. Currently, quantitative data on chitin contents are still incomplete, and available numbers need to be interpreted with care. Not only are different quantification methods used, but also varying parts of the biomass are considered (whole organism versus chitin‐rich part of the organisms). Nowadays, it is estimated that a large portion of chitin produced in the biosphere is present in the oceans [19, 20]. It can be found in aquatic species belonging to phyla such as Cnidaria (corals [21, 22]), Entoprocta [23], Phoronida (horseshoe worms [18]), Ectoprocta [18], Brachiopoda (lamp shells [18]), Bryozoa [19], Porifera (sponges [5, 24]), and Mollusca (squid [8, 23], cuttlefish [26], and clams [8]). Further, chitin has also been detected in fungi (mushrooms and yeasts [1]), algae (diatoms [27], coralline algae [28], green algae [29, 30]), Onychophora (velvet worms), and protozoa [31]. The most easily accessible sources of chitin, however, are the exoskeletons of Arthropoda, which includes insects [32–35], arachnids (spiders [36] and scorpions [37]), myriapods (millipedes and centipedes [38]), as well as Crustaceans (shrimp, krill, crab, and lobster [8, 9, 18, 37]). Table 1.1 lists examples of chitin‐containing sources, along with available compositional data. The amount of chitin varies with species type, the biomass part considered, and even with seasons and growth stages [40]. Values ranging from