Chitin and Chitosan

Edited by Lambertus A.M. van den Broek, Wageningen Food & Biobased Research, The Netherlands Carmen G. Boeriu, Wageningen Food & Biobased Research, The Netherlands Series Editor Christian V. Stevens, Faculty of Bioscience Engineering, Ghent University, Belgium

• List of Contributors xviiSeries Preface xxiPreface xxiii1 Sources of Chitin and Chitosan and their Isolation 1Leen Bastiaens, Lise Soetemans, Els D’Hondt, and Kathy Elst1.1 Chitin and Chitosan 21.1.1 Chemical Structure 21.1.2 Different Crystalline Forms of Chitin 21.2 Sources of Chitin and Chitosan 51.2.1 Sources of Chitin 51.2.2 Sources for Chitosan 101.3 Isolation of Chitin 111.3.1 Technology Principles 111.3.2 Isolation of Chitin from Crustaceans 131.3.3 Isolation of Chitin from Insects 161.3.4 Isolation of Chitin from Other Biomass Types 161.4 Production of Chitosan 191.4.1 Conversion of Chitin to Chitosan 191.4.2 Chitosan Extracted from Fungi 241.5 Towards Commercial Applications 251.6 Outlook 28References 282 Methods of Isolating Chitin from Sponges (Porifera) 35Sonia Żółtowska, Christine Klinger, Iaroslav Petrenko, Marcin Wysokowski, Yvonne Joseph, Teofil Jesionowski, and Hermann Ehrlich2.1 Introduction 352.2 Brief Overview of Classical Methods of Isolating Chitin from Invertebrates 382.3 The Modern Approach to Chitin Isolation from Sponges 402.3.1 Methods of Isolating Chitin from Glass Sponges (Hexactinellida) 412.3.2 Methods of Isolating Chitin from Demosponges (Demospongiae) 432.4 Prospective Applications of Poriferan Chitin 492.4.1 Poriferan Chitin and Modern Bioinspired Materials Science 492.4.2 Chitinous 3D Scaffolds of Sponge Origin for Tissue Engineering 512.5 Outlook 54Acknowledgment 54References 543 Physicochemical Properties of Chitosan and its Degradation Products 61Karolina Gzyra‐Jagieła, Bożenna Pęczek, Maria Wiśniewska‐Wrona, and Natalia Gutowska3.1 Physicochemical Properties of Chitosan 623.1.1 Determination of Molar Mass 623.1.2 Determination of the Deacetylation Degree 673.1.3 Determination of Dynamic Viscosity 703.1.4 Determination of Nitrogen 703.1.5 Determination of Ash Content 713.1.6 Determination of Heavy Metal Content 713.1.7 Determination of Water Retention Value (WRV) 723.1.8 Determination of Solubility in Hydrochloric Acid 723.1.9 Determination of Water Content 723.1.10 Determination of Protein Content 733.1.11 Quantitative Determination of Chitosan by Ninhydrin 733.2 Products of Degradation and their Application 743.3 Outlook 77References 774 New Developments in the Analysis of Partially Acetylated Chitosan Polymers and Oligomers 81Stefan Cord‐Landwehr, Anna Niehues, Jasper Wattjes, and Bruno M. Moerschbacher4.1 Introduction 824.2 Chitosan Oligomers 834.2.1 Degree of Polymerisation (DP), Fraction and Pattern of Acetylation (FA and PA) 834.3 Chitosan Polymers 864.3.1 Molecular Weight (MW) / Degree of Polymerisation (DP) and its Dispersity (ÐMW / ÐDP) 864.3.2 Fraction of Acetylation (FA) and its Dispersity (ÐFA) 874.3.3 Pattern of Acetylation (PA) 894.4 Outlook 91References 925 Chitosan‐Based Hydrogels 97Zhengke Wang, Ling Yang, and Wen Fang5.1 Introduction 975.2 Chitosan‐Based Multilayered Hydrogels 985.2.1 Periodic Precipitation 995.2.2 Alternating Process 1005.2.3 Induced by Electrical Signals 1005.2.4 Layer‐by‐Layer (LbL) Assembly 1015.2.5 Sequential Curing 1015.3 Chitin/Chitosan Physical Hydrogels Based on Alkali/Urea Solvent System 1035.3.1 Chitin Hydrogels Based on Alkali/Urea Solvent System 1045.3.2 Chitosan Hydrogels Based on Alkali/Urea Solvent System 1045.4 Chitosan‐Based Injectable Hydrogels 1085.4.1 Physical Association Networks 1085.4.2 Chemical Association Networks 1105.4.3 Double‐Network Hydrogels 1165.5 Chitosan‐Based Self‐Healing Hydrogels 1195.5.1 Physical Interactions 1195.5.2 Dynamic Chemical Bonds 1215.6 Chitosan‐Based Shape Memory Hydrogels 1255.6.1 Water‐/Solvent‐Triggered Shape Recovery 1265.6.2 pH‐triggered Shape Recovery 1265.6.3 Ultrasound Triggered Shape Recovery 1265.6.4 Self‐Actuated Shape Memory Hydrogels 1275.6.5 Chitosan‐Based Hydrogels with Triple Shape Memory Effect 1275.7 Superabsorbent Chitosan‐Based Hydrogels 1315.7.1 Cross‐Linked Chitosan‐Based Hydrogels 1325.7.2 Hydrogels by Graft Copolymerization 1335.7.3 Chitosan‐Based Composite Hydrogels 1345.7.4 Pure Chitosan‐Based Materials 1355.8 Outlook 136References 1366 Beneficial Health Effects of Chitin and Chitosan 145Liyou Dong, Harry J. Wichers, and Coen Govers6.1 Immunomodulatory Effects of Chitin and Chitosan as Demonstrated with In Vitro Studies 1466.2 Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Animal Studies 1496.2.1 Immune Modulation 1496.2.2 Anti‐Pathogenic Effects 1556.2.3 Anti‐Tumour Effects 1576.3 Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Clinical Trials 1586.3.1 Cholesterol Reduction and CVD Preventive Effects 1586.3.2 Other Health Effects 1606.4 Requirements to forward the Field of Study Towards the Beneficial Health Effects of Chitin and Chitosan 1636.5 Outlook 164Acknowledgement 164References 1647 Antimicrobial Properties of Chitin and Chitosan 169Magdalena Kucharska, Monika Sikora, Kinga Brzoza‐Malczewska, and Monika Owczarek7.1 Microbiological Activity of Chitosan – The Mechanism of its Antibacterial and Antifungal Activity 1697.2 The use of Chitin/Chitosan’s Microbiological Activity in Medicine and Pharmacy 1717.3 Microbiological Activity of Chitosan in the Food Industry 1747.4 Microbiological Activity of Chitosan in Paper and Textile Industries 1767.5 Microbiological Activity of Chitosan in Agriculture 1777.6 Outlook 181References 1818 Enzymes for Modification of Chitin and Chitosan 189Gustav Vaaje‐Kolstad, Tina Rise Tuveng, Sophanit Mekasha, and Vincent G.H. Eijsink8.1 CAZymes in Chitin Degradation and Modification 1908.1.1 Chitinases 1918.1.2 β‐N‐acetylhexosaminidases 1958.1.3 Exo‐β‐glucosaminidases 1958.1.4 Chitosanases 1978.1.5 Lytic Polysaccharide Monooxygenases 1998.1.6 Carbohydrate Esterases 2008.1.7 Carbohydrate‐Binding Modules 2048.2 Modular Diversity in Chitinases, Chitosanases and LPMOs 2048.3 Biological Roles of Chitin‐Active Enzymes 2058.4 Microbial Degradation and Utilisation of Chitin 2088.4.1 Chitin Degradation by Serratia marcescens 2098.4.2 Chitin Degradation by Bacteria in the Bacteroidetes Phylum 2118.4.3 Chitin Degradation by Thermococcus Kodakarensis 2118.4.4 Chitin Degradation by Fungi 2128.5 Biotechnological Perspectives 2138.6 Biorefining of Chitin‐Rich Biomass 2148.7 Outlook 216References 2169 Chitin and Chitosan as Sources of Bio‐Based Building Blocks and Chemicals 229Malgorzata Kaisler, Lambertus A.M. van den Broek, and Carmen G. Boeriu9.1 Introduction 2309.2 Chitin Conversion into Chitosan, Chitooligosaccharides and Monosaccharides 2329.2.1 Chitosan Production 2329.2.2 Production of Chitooligosaccharides 2349.2.3 Production of GlcNAc and GlcN from Chitin 2359.3 Building Blocks for Polymers from Chitin and its Derivatives 2389.3.1 Furan‐Based Monomers 2389.3.2 Amino Alcohol and Amino Acid Building Blocks 2399.4 Outlook 239Acknowledgement 240References 24010 Chemical and Enzymatic Modification of Chitosan to Produce New Functional Materials with Improved Properties 245Carmen G. Boeriu and Lambertus A.M. van den Broek10.1 Introduction 24510.2 Functional Chitosan Derivatives by Chemical and Enzymatic Modification 24610.2.1 Anionic Chitosan Derivatives 24810.2.2 Hydroxyalkylchitosans 25010.2.3 Quaternised and Highly Cationic Chitosan Derivatives 25010.2.4 Hydroxyaryl Chitosan Derivatives 25010.2.5 Carbohydrate‐Modified Chitosan 25110.3 Graft Co‐Polymers of Chitosan 25110.4 Cross‐Linked Chitosan and Chitosan Polymer Networks 25410.5 Outlook 254References 25511 Chitosan‐Based Drug Delivery Systems 259Cristian Peptu, Andra Cristina Humelnicu, Razvan Rotaru, Maria Emiliana Fortuna, Xenia Patras, Mirela Teodorescu, Bogdan Ionel Tamba, and Valeria Harabagiu11.1 Introduction 26011.2 Beneficial Effects of Chitosan 26111.2.1 Interaction with Anionic Drugs 26311.2.2 Mucoadhesive Properties 26311.2.3 Transfection Activity 26311.2.4 Efflux Pump Inhibitory Properties 26511.2.5 Permeation‐Enhancing Properties 26511.3 Chitosan—an Active Polymer for Bypassing Biological Barriers 26511.3.1 Skin Barrier 26611.3.2 Mucosa Barrier 26711.3.3 Ophthalmic Barrier 26911.3.4 Blood–Brain Barrier 27011.4 Chitosan‐Based DDS Formulations 27111.4.1 Hydrogels 27511.4.2 Micro/NPs 27511.4.3 Nanofibers 27511.4.4 Scaffolds and Membranes 27511.5 Outlook 276Acknowledgment 276References 27612 The Application of Chitin and its Derivatives for the Design of Advanced Medical Devices 291Marcin H. Struszczyk, Longina Madej‐Kiełbik, and Dorota Zielińska12.1 Selection of the Raw Sources: Safety Criteria 29112.1.1 Aspect of Animal Tissue‐Originated Derivatives 29212.1.2 General Requirements for Chitinous Biopolymers Applied in Designing Medical Devices 29212.1.3 Characterisation of the Biopolymer for Application in Wound Dressing Designing 29312.1.4 Aspect of the Sterilization of the Final Wound Dressing 29512.2 Types of Wound Dressings Consisting of Chitin‐Derived Biopolymers Available in the Market 29712.3 Performance and Safety Assessment 29712.4 New Ideas and Concepts 30112.5 Risk Acceptance and Design Process Aspects 30612.6 Outlook 308Acknowledgements 308References 30813 Food Applications of Chitosan and its Derivatives 315Suse Botelho da Silva, Daiana de Souza, and Liziane Dantas Lacerda13.1 Introduction 31513.2 Chitosan and its Derivatives as Food Additive 31613.2.1 Antioxidant 31813.2.2 Antimicrobial 31913.2.3 Stabilizer and Thickener 31913.3 Functional Ingredient and Health Beneficial Effects 32013.4 Active Packaging 32113.5 Enzyme Immobilization 33113.6 Encapsulation and Delivering of Bioactive Ingredients 33213.7 Adsorption and Chelation of Toxic and Undesirable Compounds 33413.8 Outlook 339References 34014 Potential of Chitosans in the Development of Edible Food Packaging 349Véronique Coma and Artur Bartkowiak14.1 Potential Limitations for Real Introduction into the Market 35014.1.1 Generally Recognized as Safe (GRAS) 35114.1.2 Solubility 35114.1.3 Source—Origin 35214.1.4 Structure Variability 35214.2 Films and Coatings for Food Preservation 35314.2.1 Definitions and Interests 35314.2.2 Main Relevant Chitosan‐Based Material Properties 35314.3 Specific Case of Chitosan Nanoparticles (CSNPs) 35714.3.1 CSNPs 35714.3.2 CSNPs in Various Edible Films 35814.3.3 Antimicrobial Activities of CSNPs in Edible Films 35914.3.4 Toxicity Studies of CSNPs 36014.4 Applications to Sensitive Real Food Products 36014.4.1 Fruits and Vegetables 36114.4.2 Meat and Meat Products 36214.4.3 Fish and Seafood Products 36214.5 Conclusions 364References 36415 The Use of Chitosan‐Based Nanoformulations for Controlling Fungi During Storage of Horticultural Commodities 371Silvia Bautista‐Baños, Zormy Nacary Correa‐Pacheco, and Rosa Isela Ventura‐Aguilar15.1 Introduction 37215.2 Importance of Fruits and Vegetables 37215.3 Storage Disorders and Diseases of Horticultural Products 37415.4 Plant Fungi Inhibition by Chitosan Application 37515.5 Chitosan Integrated with Other Alternative Methods for Controlling Postharvest Fungi 37615.6 Chitosan‐Based Formulations 37615.7 Physiological Response and Quality Retention of Horticultural Commodities to Chitosan Coating Application 37615.8 Influence of Chitosan Coatings on the Shelf Life of Horticultural Products 37815.9 Effects of Chitosan Coatings with Additional Compounds on Quality and Microorganisms Development 37915.10 Integration of Chitosan Nanoparticles into Coating Formulations and their Effects on the Quality of Horticultural Commodities and Development of Microorganisms 38415.11 Outlook 387Acknowledgments 387References 38716 Chitosan Application in Textile Processing and Fabric Coating 395Thomas Hahn, Leonie Bossog, Tom Hager, Werner Wunderlich, Rudi Breier, Thomas Stegmaier, and Susanne Zibek16.1 Chitosan in the Textile Industry 39616.2 Textile Production 39816.3 General Test Methods 40016.4 Fibres and Yarns from Chitin and Chitosan 40116.4.1 Chitin and Chitosan Solubilisation for Spinning Purposes 40216.4.2 Chitosan Spinning Processes 40216.4.3 Mechanical Properties of Chitosan Fibres/Yarns 40416.5 Sizing with Chitosan 40616.5.1 Miscibility of Chitosan with Other Sizing Agents 40716.5.2 Viscosity of Chitosan‐Containing Sizing Agents 40816.5.3 Adhesion and Wetting 41016.5.4 Mechanical–Physical Properties of Chitosan Films 41116.5.5 Removal and Processing of Chitosan Sizing after Weaving 41216.6 Chitosan as a Finishing Agent or Coating 41416.6.1 Chitosan as a Carrier and Linker 41516.6.2 Formation of a Durable Finish with Chitosan 41616.6.3 Chitosan as an Active Agent 41716.7 Outlook 419Nomenclature 420References 42117 Chitin and Chitosan for Water Purification 429Petrisor Samoila, Andra Cristina Humelnicu, Maria Ignat, Corneliu Cojocaru, and Valeria Harabagiu17.1 Introduction 43017.2 Wastewater Treatment by Adsorption 43217.2.1 Principle of the Adsorption Process 43217.2.2 Adsorption of Organic Compounds 43417.2.3 Adsorption of Heavy Metals 43717.3 Wastewater Treatment by Coagulation/Flocculation 44017.4 Wastewater Treatment by Membrane Separation 44617.4.1 Principle of Ultrafiltration Process 44617.4.2 Fabrication of Ultrafiltration Blend Membranes 44817.4.3 Chitosan‐Enhanced Ultrafiltration 45017.5 Outlook 452Acknowledgement 452References 45318 Chitosan for Sensors and Electrochemical Applications 461Suse Botelho da Silva, Guilherme Lopes Batista, and Cristiane Krause Santin18.1 Introduction 46118.2 Chitosan: A Biopolymer with Unique Properties 46218.3 Modification and Preparation of Chitosan‐Based Materials for Electrochemical Applications 46318.4 The Proton Conductivity of Chitosan 46518.5 Selected Applications 46718.5.1 Electrochemical Sensors 46718.5.2 Spectroscopic Sensors 47018.5.3 Other Electrochemical Devices 47118.6 Outlook 472References 47319 Marketing and Regulations of Chitin and Chitosan from Insects 477Nathalie Berezina and Antoine Hubert19.1 Historical Outline 47719.2 Natural Origins of Chitin 47819.3 Specificities of Chitin Biopolymer 47919.4 Differences Among Chitins from Insects and Other Sources 47919.4.1 Differences of Chemical Compositions of the Cuticles 47919.4.2 Differences of Physical Assemblies of Chains and Molecules 48019.5 Extraction and Purification Specificities of Chitins from Insects 48019.5.1 Different Cuticle Structures and Contents of Insects 48019.5.2 Chemical Extraction 48019.5.3 Biological Extraction 48119.5.4 Characterization and Transformation into Chitosan 48119.6 Market Opportunities and its Regulations 48219.6.1 Agriculture Applications 48219.6.2 Water Treatment Applications 48319.6.3 Material Applications 48319.6.4 Biomedical Applications 48419.7 Outlook 485References 485Index 491