Handbook of Biopolymer–Based Materials: From Blends and Composites to Gels and Complex Networks

This first systematic scientific reference in the area of micro– and nanostructured biopolymer systems discusses in two volumes the morphology, structure, dynamics, properties and applications of all important biopolymers, as well as their blends, composites, interpenetrating networks and gels.

Selected leading researchers from industry, academia, government and private research institutions around the globe comprehensively review recent accomplishments in the field. They examine the current state of the art, new challenges, and opportunities, discussing all the synthetic routes to the generation of both micro– and nano–morphologies, as well as the synthesis, characterization and application of porous biopolymers. An outstanding resource for anyone involved in the field of eco–friendly biomaterials for advanced technologies.

Foreword XIII

List of Contributors XV

Volume 1

1 Biopolymers: State of the Art, New Challenges, and Opportunities 1
Christophe Chassenieux, Dominique Durand, Parameswaranpillai Jyotishkumar, and Sabu Thomas

1.1 Introduction 1

1.2 Biopolymers: A Niche For Fundamental Research in Soft Matter Physics 3

1.3 Biopolymers: An Endless Source of Applications 4

1.4 Topics Covered by the Book 5

1.5 Conclusions 5

References 6

2 General Overview of Biopolymers: Structures, Properties, and Applications 7
Charles Winkworth–Smith and Tim J. Foster

2.1 Introduction 7

2.2 Plant Cell Wall Polysaccharides 11

2.3 Biocomposites 23

2.4 Future Outlook 28

References 29

3 Biopolymers from Plants 37
Maria J. Sabater, Tania Rodenas, and Antonio Heredia

3.1 Introduction 37

3.2 Lipid and Phenolic biopolymers 38

3.3 Carbohydrate Biopolymers: Polysaccharides 48

3.4 Isoprene Biopolymers: Natural Rubber 67

3.5 Concluding Remarks 74

References 75

4 Bacterial Biopolymers and Genetically Engineered Biopolymers for Gel Systems Application 87
Deepti Singh and Ashok Kumar

4.1 Introduction 87

4.2 Microbial Polysaccharides as Biopolymers 90

4.3 Microbial Biopolymers as Drug Delivery Vehicle 92

4.4 Polyanhydrides 93

4.5 Recombinant Protein Polymer Production 94

4.6 Recombinant Genetically Engineered Biopolymer: Elastin 95

4.7 Collagen as an Ideal Biopolymer 97

4.8 Biopolymers for Gel System 99

4.9 Hydrogels of Biopolymers for Regenerative Medicine 99

5 Biopolymers from Animals 109
Khaleelulla Saheb Shaik and Bernard Moussian

5.1 Introduction 109

5.2 Chitin and Hyaluronic Acid in the Living World 110

5.3 Milestones in Chitin History 110

5.4 From Trehalose to Chitin 112

5.5 Chitin Synthase 115

5.6 Regulation of Chitin Synthesis in Fungi 117

5.7 Organization of Chitin in the Fungal Cell Wall 118

5.8 Organization of Chitin in the Arthropod Cuticle 119

5.9 Chitin–Organizing Factors 123

5.10 Secretion and Cuticle Formation 126

5.11 Transcriptional Regulation of Cuticle Production 128

5.12 Chitin Synthesis Inhibitors 130

5.13 Noncuticular Chitin in Insects 131

5.14 Chitin as a Structural Element 133

5.15 Application of Chitin 134

5.16 Conclusion 135

References 135
6 Polymeric Blends with Biopolymers 143
Hero Jan Heeres, Frank van Maastrigt, and Francesco Picchioni

6.1 Introduction 143

6.2 Starch–Based Blends 146

6.3 Blends with Chitosan (One Amino Group Too Much ) 158

6.4 Future Perspectives 161

References 164

7 Macro–, Micro–, and Nanocomposites Based on Biodegradable Polymers 173
Luc Averous and Eric Pollett

7.1 Introduction 173

7.2 Biodegradable Polymers 174

7.3 Biocomposites 181

7.4 Nanobiocomposites 186

References 200

8 IPNs Derived from Biopolymers 211
Fernando G. Torres, Omar Paul Troncoso, and Carlos Torres

8.1 Introduction 211

8.2 Types of IPNs 212

8.3 IPNs Derived from Biopolymers 214

8.4 Manufacture of IPNs 220

8.5 Characterization of IPNs 222

8.6 Applications of IPNs 226

8.7 Conclusions 229

References 229

9 Associating Biopolymer Systems and Hyaluronate Biomaterials 235
Deborah Blanchard and Rachel Auzely–Velty

9.1 Introduction 235

9.2 Synthesis and Self–Association of Hydrophobically Modified Derivatives of Chitosan and Hyaluronic Acid in Aqueous Solution 237

9.3 Design of Novel Biomaterials Based on Chemically Modified Derivatives of Hyaluronic Acid 248

9.4 Conclusions 271

References 271

10 Polymer Gels from Biopolymers 279
Esra Alveroglu, Ali Gelir, and Yasar Yilmaz

10.1 Introduction 279

10.2 Experimental Methods 279

10.3 Polymerization and Gelation Kinetics 281

10.4 Sol–Gel Transition and Universality Discussion 287

10.5 Imprinting the Gels 292

10.6 Heterogeneity of Hydrogels 301

10.7 Ionic p–Type and n–Type Semiconducting Gels 303

10.8 Conclusions 307

References 308

11 Conformation and Rheology of Microbial Exopolysaccharides 317
Jacques Desbrieres

11.1 Introduction 317

11.2 Conformation of Polysaccharides 318

11.3 Secondary Solid–State Structures for Microbial Polysaccharides 318

11.4 Conformation in Solution: Solution Properties and Applications 325

11.5 Gelling Properties in the Presence of Salts 336

11.6 Conclusions 345

References 345

12 Sulfated Polysaccharides in the Cell Wall of Red Microalgae 351
Shosana (Malis) Arad and Oshrat Levy–Ontman

12.1 Introduction 351

12.2 Sulfated Polysaccharides from Red Microalgae General Overview 352

12.3 Sulfated Polysaccharides of Red Microalgal Cell Walls: Chemical Aspects 354

12.4 Proteins in the Cell Wall of Red Microalgae 355

12.5 Rheology of Red Microalgal Polysaccharide Solutions 356

12.6 Modifications of Sulfated Polysaccharides 359

12.7 Red Microalgal Sulfated Polysaccharide Bioactivities 362

References 365

Volume 2

13 Dielectric Spectroscopy and Thermally Stimulated Current Analysis of Biopolymer Systems 371
Valérie Samouillan, Jany Dandurand, and Colette Lacabanne

13.1 Introduction 371

13.2 Theory and Principle of Dielectric Analyses 372

13.3 Characterization of Biopolymers 383

13.4 Conclusion 398

References 398

14 Solid–State NMR Spectroscopy of Biopolymers 403
Garrick F. Taylor, Phedra Marius, Chris Ford, and Philip T.F. Williamson

14.1 Introduction 403

14.2 NMR of Biological Polymers 404

14.3 Methods for the Study of Biological Polymers 405

14.4 Solid–State NMR Experiments Employed for the Analysis of Biopolymers 409

14.5 Application of Solid–State NMR to Biopolymers 422

14.6 Conclusions 436

References 436

15 EPR Spectroscopy of Biopolymers 443
Janez trancar and Vanja Kokol

15.1 Introduction 443

15.2 Theoretical Background 445

15.3 Biopolymers 451

15.4 Conclusion 466

References 467

16 X–Ray Photoelectron Spectroscopy: A Tool for Studying Biopolymers 473
Ana Maria Botelho do Rego, Ana Maria Ferraria, Manuel Rei Vilar, and Sami Boufi

16.1 Introduction 473

16.2 XPS Basics 474

16.3 Cellulose 483

16.4 Starch 507

16.5 Chitin and Chitosan 509

16.6 Gums 511

16.7 Complementary Techniques 513

16.8 Conclusions 525

References 526

17 Light–Scattering Studies of Biopolymer Systems 533
Taco Nicolai and Dominique Durand

17.1 Introduction 533

17.2 Static Scattering 534

17.3 Dynamic Light Scattering 545

17.4 Cross–Correlation Dynamic Light Scattering 552

17.5 Turbidimetry 556

17.6 Diffusive Wave Spectroscopy 558

17.7 Micro Rheology Using DLS and DWS 561

17.8 Conclusion 563

References 563

18 X–Ray Scattering and Diffraction of Biopolymers 567
Yoshiharu Nishiyama and Marli Miriam de Souza Lima

18.1 Basics 567

18.2 Practical Consideration 573

18.3 Examples 574

18.3.2 Polydisperse Particles 575

18.4 Conclusions 580

References 580

19 Large–Scale Structural Characterization of Biopolymer Systems by Small–Angle Neutron Scattering 583
Ferenc Horkay

19.1 Introduction 583

19.2 Basic Principles of SANS 584

19.3 Experimental Examples 591

19.4 Proteins 593

19.5 Polynucleic Acids (DNA and RNA) 595

19.6 Polysaccharide–Based Biopolymers 600

19.7 Summary 607

References 608

20 Microscopy of Biopolymer Systems 611
Changmin Hu and Wenguo Cui

20.1 Introduction 611

20.2 Emerging Techniques in Biopolymer Microscopy 612

20.3 Microstructure and Application of Biopolymers 625

20.4 Biopolymeric Microstructure for Medical Applications 638

20.5 Summary 640

References 641

21 Rheo–optical Characterization of Biopolymer Systems 645
Dagang Liu, Rakesh Kumar, Donglin Tian, Fei Lu, and Mindong Chen

21.1 Introduction 645

21.2 Mechanism and Equipment of Rheo–optics 646

21.3 Rheo–optical Applications for Biopolymers 652

21.4 Conclusions 668

References 669

22 Rheological Behavior of Biopolymer Systems 673
Tao Feng and Ran Ye

22.1 Introduction 673

22.2 Rheological Behavior of Polysaccharide Systems 674

22.4 Rheological Behavior of Mixture Systems 690

22.5 Conclusions 694

References 694

23 Physical Gels of Biopolymers: Structure, Rheological and Gelation Properties 699
Camille Michon

23.1 Introduction 699

23.2 Gel Organization at Different Scales 700

23.3 Sol Gel Transition in Polymer Gels: Determination and Applications 703

23.4 Gel and Sol Gel Transition Applications 710

23.5 Conclusion 714

References 715

24 Interfacial Properties of Biopolymers, Emulsions, and Emulsifiers 717
Adamantini Paraskevopoulou and Vassilis Kiosseoglou

24.1 Introduction 717

24.2 Surface–Active Polysaccharides 720

24.3 Biopolymer Blends in Emulsions 724

24.4 Concluding Remarks 734

References 736

25 Modeling and Simulation of Biopolymer Systems 741
Denis Bouyer

25.1 Introduction 741

25.2 Why Modeling (and Simulating)? 741

25.3 What Modeling (Transfer, Transport, Chemical Reaction, etc.)? 743

25.4 Which Validation for a Model? 744

25.5 Methodology 745

25.6 Application to Biopolymer Systems 754

25.7 Conclusions 772

Nomenclature 772

References 773

26 Aging and Biodegradation of Biocomposites 777
Siji K. Mary, Prasanth Kumar Sasidharan Pillai, Deepa Bhanumathy Amma, Laly A. Pothen, and Sabu Thomas

26.1 Introduction 777

26.2 Biodegradation of Biopolymers 785

26.3 Recycling of Biopolymer–Embedded Biocomposites 790

26.4 Future Vision 795

References 795

27 Biopolymers for Health, Food, and Cosmetic Applications 801
Robin Augustine, Rajakumari Rajendran, Uro Cvelbar, Miran Mozeti , and Anne George

27.1 Introduction 801

27.2 Biopolymers for Health Applications 802

27.3 Biopolymers for Food Applications 819

27.4 Biopolymers for Cosmetic Applications 827

References 844

Index 851

Sabu Thomas is a Professor of Polymer Science and Engineering at Mahatma Gandhi University (India) and Director of the ′School of Chemical Sciences′ and of the ′Center for Nanoscience and Nanotechnology′ of the same university. He has published over 500 research papers in peer reviewed international journals on polymer composites, nanocomposites, membrane separation, polymer blends and
alloys, and polymer recycling, has an h–index of 57 and has edited 23 books. Professor Thomas is also a Fellow of the Royal Society of Chemistry and a Fellow of the New York Academy of Sciences. His work has been awarded with the Professor Sukumar Maithy Award, the Bronze Medal of the Chemical Research Society of India (CRSI) and the Materials Research Society of India (MRSI) award, among others.

Dominique Durand is a Research Director Emeritus at the CNRS and former Director of the Polymers, Colloids and Interfaces Laboratory at the University of Maine, Le Mans (France). His research focuses on experimental studies and modeling of static and dynamic properties of complex systems, such as covalent networks, associating polymers and biopolymer gels. He is the author or co–author of over 210 research papers, reviews, and book chapters.

Christophe Chassenieux is a Professor at the University of Maine, Le Mans (France) since 2005, after being an Assistant Professor at the University Pierre et Marie Curie, Paris. His research interests encompass properties of polymer gels and self–assemblies of amphiphilic polymers. He is the co–author of 50 research articles, book chapters and patents.

Parameswaranpillai Jyotishkumar is DST INSPIRE Faculty at the Department of Polymer Science and Rubber Technology, Kerala (India). He has completed his PhD from Mahatma Gandhi University, Kottayam. Dr. Jyotishkumar′s research focuses on polymer blends, nanocomposites, and bio–nanocomposites. He is the author or co–author of 30 research articles and book chapters.