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Chitin and Chitosan

Properties and Applications

van den Broek, Lambertus A. M. / Boeriu, Carmen G. (Editor)

Wiley Series in Renewable Resources

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1. Edition January 2020
536 Pages, Hardcover
Wiley & Sons Ltd

ISBN: 978-1-119-45043-6
John Wiley & Sons

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Offers a comprehensive guide to the isolation, properties and applications of chitin and chitosan

Chitin and Chitosan: Properties and Applications presents a comprehensive review of the isolation, properties and applications of chitin and chitosan. These promising biomaterials have the potential to be broadly applied and there is a growing market for these biopolymers in areas such as medical and pharmaceutical, packaging, agricultural, textile, cosmetics, nanoparticles and more.

The authors - noted experts in the field - explore the isolation, characterization and the physical and chemical properties of chitin and chitosan. They also examine their properties such as hydrogels, immunomodulation and biotechnology, antimicrobial activity and chemical enzymatic modifications. The book offers an analysis of the myriad medical and pharmaceutical applications as well as a review of applications in other areas. In addition, the authors discuss regulations, markets and perspectives for the use of chitin and chitosan. This important book:
* Offers a thorough review of the isolation, properties and applications of chitin and chitosan.
* Contains information on the wide-ranging applications and growing market demand for chitin and chitosan
* Includes a discussion of current regulations and the outlook for the future

Written for Researchers in academia and industry who are working in the fields of chitin and chitosan, Chitin and Chitosan: Properties and Applications offers a review of these promising biomaterials that have great potential due to their material properties and biological functionalities.

List of Contributors xvii

Series Preface xxi

Preface xxiii

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

References 28

2 Methods of Isolating Chitin from Sponges (Porifera) 35
Sonia {óBtowska, 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 Invertebrates 38

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

Acknowledgment 54

References 54

3 Physicochemical Properties of Chitosan and its Degradation Products 61
Karolina Gzyra-JagieBa, Bo|enna P'czek, Maria Wi[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

References 77

4 New Developments in the Analysis of Partially Acetylated Chitosan Polymers and Oligomers 81
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 (?MW / ?DP) 86

4.3.2 Fraction of Acetylation (FA) and its Dispersity (?FA) 87

4.3.3 Pattern of Acetylation (PA) 89

4.4 Outlook 91

References 92

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

References 136

6 Beneficial Health Effects of Chitin and Chitosan 145
Liyou Dong, Harry J. Wichers, and Coen Govers

6.1 Immunomodulatory Effects of Chitin and Chitosan as Demonstrated with In Vitro Studies 146

6.2 Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Animal Studies 149

6.2.1 Immune Modulation 149

6.2.2 Anti-Pathogenic Effects 155

6.2.3 Anti-Tumour Effects 157

6.3 Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Clinical Trials 158

6.3.1 Cholesterol Reduction and CVD Preventive Effects 158

6.3.2 Other Health Effects 160

6.4 Requirements to forward the Field of Study Towards the Beneficial Health Effects of Chitin and Chitosan 163

6.5 Outlook 164

Acknowledgement 164

References 164

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 Pharmacy 171

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

References 181

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 ß-N-acetylhexosaminidases 195

8.1.3 Exo-ß-glucosaminidases 195

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 LPMOs 204

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 marcescens 209

8.4.2 Chitin Degradation by Bacteria in the Bacteroidetes Phylum 211

8.4.3 Chitin Degradation by Thermococcus Kodakarensis 211

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

References 216

9 Chitin and Chitosan as Sources of Bio-Based Building Blocks and Chemicals 229
Malgorzata Kaisler, Lambertus A.M. van den Broek, and Carmen G. Boeriu

9.1 Introduction 230

9.2 Chitin Conversion into Chitosan, Chitooligosaccharides and Monosaccharides 232

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

Acknowledgement 240

References 240

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 Modification 246

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

References 255

11 Chitosan-Based Drug Delivery Systems 259
Cristian Peptu, Andra Cristina Humelnicu, Razvan Rotaru, Maria Emiliana Fortuna, Xenia Patras, Mirela Teodorescu, Bogdan Ionel Tamba, and Valeria Harabagiu

11.1 Introduction 260

11.2 Beneficial Effects of Chitosan 261

11.2.1 Interaction with Anionic Drugs 263

11.2.2 Mucoadhesive Properties 263

11.2.3 Transfection Activity 263

11.2.4 Efflux Pump Inhibitory Properties 265

11.2.5 Permeation-Enhancing Properties 265

11.3 Chitosan--an Active Polymer for Bypassing Biological Barriers 265

11.3.1 Skin Barrier 266

11.3.2 Mucosa Barrier 267

11.3.3 Ophthalmic Barrier 269

11.3.4 Blood-Brain Barrier 270

11.4 Chitosan-Based DDS Formulations 271

11.4.1 Hydrogels 275

11.4.2 Micro/NPs 275

11.4.3 Nanofibers 275

11.4.4 Scaffolds and Membranes 275

11.5 Outlook 276

Acknowledgment 276

References 276

12 The Application of Chitin and its Derivatives for the Design of Advanced Medical Devices 291
Marcin H. Struszczyk, Longina Madej-KieBbik, and Dorota ZieliDska

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 Designing 293

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 Market 297

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

Acknowledgements 308

References 308

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

References 340

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

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 CSNPs 360

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

References 364

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

Acknowledgments 387

References 387

16 Chitosan Application in Textile Processing and Fabric Coating 395
Thomas Hahn, Leonie Bossog, Tom Hager, Werner Wunderlich, Rudi Breier, Thomas Stegmaier, and Susanne Zibek

16.1 Chitosan in the Textile Industry 396

16.2 Textile Production 398

16.3 General Test Methods 400

16.4 Fibres and Yarns from Chitin and Chitosan 401

16.4.1 Chitin and Chitosan Solubilisation for Spinning Purposes 402

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

Nomenclature 420

References 421

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

Acknowledgement 452

References 453

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

References 473

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

References 485

Index 491
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