Handbook of Biopolymer-Based Materials E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch

Seitenzahl: 1687

Veröffentlichungsjahr: 2013

Beschreibung

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 fi eld of eco-friendly biomaterials for advanced technologies.

Leseprobe

Contents

Cover

Related Titles

Title Page

Copyright

Foreword

List of Contributors

Chapter 1: Biopolymers: State of the Art, New Challenges, and Opportunities

1.1 Introduction

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

1.3 Biopolymers: An Endless Source of Applications

1.4 Topics Covered by the Book

1.5 Conclusions

References

Chapter 2: General Overview of Biopolymers: Structure, Properties, and Applications

2.1 Introduction

2.2 Plant Cell Wall Polysaccharides

2.3 Biocomposites

2.4 Future Outlook

References

Chapter 3: Biopolymers from Plants

3.1 Introduction

3.2 Lipid and Phenolic Biopolymers

3.3 Carbohydrate Biopolymers: Polysaccharides

3.4 Isoprene Biopolymers: Natural Rubber

3.5 Concluding Remarks

Acknowledgments

References

Chapter 4: Bacterial Biopolymers and Genetically Engineered Biopolymers for Gel Systems Application

4.1 Introduction

4.2 Microbial Polysaccharides as Biopolymers

4.3 Microbial Biopolymers as Drug Delivery Vehicle

4.4 Polyanhydrides

4.5 Recombinant Protein Polymer Production

4.6 Recombinant Genetically Engineered Biopolymer: Elastin

4.7 Collagen as an Ideal Biopolymer

4.8 Biopolymers for Gel System

4.9 Hydrogels of Biopolymers for Regenerative Medicine

4.10 Supermacroporous Cryogel Matrix from Biopolymers

4.11 Biopolymers Impact on Environment

4.12 Conclusion

Acknowledgments

References

Chapter 5: Biopolymers from Animals

5.1 Introduction

5.2 Chitin and Hyaluronic Acid in the Living World

5.3 Milestones in Chitin History

5.4 From Trehalose to Chitin

5.5 Chitin Synthase

5.6 Regulation of Chitin Synthesis in Fungi

5.7 Organization of Chitin in the Fungal Cell Wall

5.8 Organization of Chitin in the Arthropod Cuticle

5.9 Chitin-Organizing Factors

5.10 Secretion and Cuticle Formation

5.11 Transcriptional Regulation of Cuticle Production

5.12 Chitin Synthesis Inhibitors

5.13 Noncuticular Chitin in Insects

5.14 Chitin as a Structural Element

5.15 Application of Chitin

5.16 Conclusion

References

Chapter 6: Polymeric Blends with Biopolymers

6.1 Introduction

6.2 Starch-Based Blends

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

6.4 Future Perspectives

References

Chapter 7: Macro-, Micro-, and Nanocomposites Based on Biodegradable Polymers

7.1 Introduction

7.2 Biodegradable Polymers

7.3 Biocomposites

7.4 Nanobiocomposites

References

Chapter 8: IPNs Derived from Biopolymers

8.1 Introduction

8.2 Types of IPNs

8.3 IPNs Derived from Biopolymers

8.4 Manufacture of IPNs

8.5 Characterization of IPNs

8.6 Applications of IPNs

8.7 Conclusions

References

Chapter 9: Associating Biopolymer Systems and Hyaluronate Biomaterials

9.1 Introduction

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

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

9.4 Conclusions

References

Chapter 10: Polymer Gels from Biopolymers

10.1 Introduction

10.2 Experimental Methods

10.3 Polymerization and Gelation Kinetics

10.4 Sol–Gel Transition and Universality Discussion

10.5 Imprinting the Gels

10.6 Heterogeneity of Hydrogels

10.7 Ionic p-Type and n-Type Semiconducting Gels

10.8 Conclusions

References

Chapter 11: Conformation and Rheology of Microbial Exopolysaccharides

11.1 Introduction

11.2 Conformation of Polysaccharides

11.3 Secondary Solid-State Structures for Microbial Polysaccharides

11.4 Conformation in Solution: Solution Properties and Applications

11.5 Gelling Properties in the Presence of Salts

11.6 Conclusions

References

Chapter 12: Sulfated Polysaccharides in the Cell Wall of Red Microalgae

12.1 Introduction

12.2 Sulfated Polysaccharides from Red Microalgae – General Overview

12.3 Sulfated Polysaccharides of Red Microalgal Cell Walls: Chemical Aspects

12.4 Proteins in the Cell Wall of Red Microalgae

12.5 Rheology of Red Microalgal Polysaccharide Solutions

12.6 Modifications of the Sulfated Polysaccharides

12.7 Red Microalgal Sulfated Polysaccharide Bioactivities

References

Chapter 13: Dielectric Spectroscopy and Thermally Stimulated Current Analysis of Biopolymer Systems

13.1 Introduction

13.2 Theory and Principle of Dielectric Analyses

13.3 Characterization of Biopolymers

13.4 Conclusion

References

Chapter 14: Solid-State NMR Spectroscopy of Biopolymers

14.1 Introduction

14.2 NMR of Biological Polymers

14.3 Methods for the Study of Biological Polymers

14.4 Solid-State NMR Experiments Employed for the Analysis of Biopolymers

14.5 Application of Solid-State NMR to Biopolymers

14.6 Conclusions

References

Chapter 15: EPR Spectroscopy of Biopolymers

15.1 Introduction

15.2 Theoretical Background

15.3 Biopolymers

15.4 Conclusion

References

Chapter 16: X-Ray Photoelectron Spectroscopy: A Tool for Studying Biopolymers

16.1 Introduction

16.2 XPS Basics

16.3 Cellulose

16.4 Starch

16.5 Chitin and Chitosan

16.6 Gums

16.7 Complementary Techniques

16.8 Conclusions

References

Chapter 17: Light-Scattering Studies of Biopolymer Systems

17.1 Introduction

17.2 Static Scattering

17.3 Dynamic Light Scattering

17.4 Cross-Correlation Dynamic Light Scattering

17.5 Turbidimetry

17.6 Diffusive Wave Spectroscopy

17.7 Micro Rheology Using DLS and DWS

17.8 Conclusion

References

Chapter 18: X-Ray Scattering and Diffraction of Biopolymers

18.1 Basics

18.2 Practical Consideration

18.3 Examples

18.4 Conclusions

References

Chapter 19: Large-Scale Structural Characterization of Biopolymer Systems by Small-Angle Neutron Scattering

19.1 Introduction

19.2 Basic Principles of SANS

19.3 Experimental Examples

19.4 Proteins

19.5 Polynucleic Acids (DNA and RNA)

19.6 Polysaccharide-Based Biopolymers

19.7 Summary

Acknowledgments

References

Chapter 20: Microscopy of Biopolymer Systems

20.1 Introduction

20.2 Emerging Techniques in Biopolymer Microscopy

20.3 Microstructure and Application of Biopolymers

20.4 Biopolymeric Microstructure for Medical Applications

20.5 Summary

Acknowledgments

References

Chapter 21: Rheo-optical Characterization of Biopolymer Systems

21.1 Introduction

21.2 Mechanism and Equipment of Rheo-optics

21.3 Rheo-optical Applications for Biopolymers

21.4 Conclusions

Acknowledgments

References

Chapter 22: Rheological Behavior of Biopolymer Systems

22.1 Introduction

22.2 Rheological Behavior of Polysaccharide Systems

22.3 Rheological Behavior of Protein Systems

22.4 Rheological Behavior of Mixture Systems

22.5 Conclusions

References

Chapter 23: Physical Gels of Biopolymers: Structure, Rheological and Gelation Properties

23.1 Introduction

23.2 Gel Organization at Different Scales

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

23.4 Gel and Sol–Gel Transition Applications

23.5 Conclusion

References

Chapter 24: Interfacial Properties of Biopolymers, Emulsions, and Emulsifiers

24.1 Introduction

24.2 Surface-Active Polysaccharides

24.3 Biopolymer Blends in Emulsions

24.4 Concluding Remarks

References

Chapter 25: Modeling and Simulation of Biopolymer Systems

25.1 Introduction

25.2 Why Modeling (and Simulating)?

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

25.4 Which Validation for a Model?

25.5 Methodology

25.6 Application to Biopolymer Systems

25.7 Conclusions

Nomenclature

References

Chapter 26: Aging and Biodegradation of Biocomposites

26.1 Introduction

26.2 Biodegradation of Biopolymers

26.3 Recycling of Biopolymer-Embedded Biocomposites

26.4 Future Vision

References

Chapter 27: Biopolymers for Health, Food, and Cosmetic Applications

27.1 Introduction

27.2 Biopolymers for Health Applications

27.3 Biopolymers for Food Applications

27.4 Biopolymers for Cosmetic Applications

Acknowledgment

References

Index

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Foreword

Our industrialized world is driven in large part by petroleum. It is an important source of energy and materials, and many of the products that we depend upon for day-to-day living are derived from it. However, the cost of oil and gas has increased dramatically over the past decade and this upward spiral is expected to continue due to increased demand, finite quantities, and unreliable supply chains. Beyond the monetary cost, our petroleum-based economy comes at a significant environmental price that cannot be sustained. As a consequence, research scientists, university professors, university students, technology developers in industry, and government policy makers focus their interest in the future prospects for a world less dependent on fossil fuels, taking steps to reduce greenhouse gas emissions, and efficiently addressing the significant challenges associated with plastic wastes in the global environment. It is now widely recognized that more cost-effective and environmentally benign alternatives to petroleum and the products derived from it will be required in order to realize a future with a sustainable economy and environment. Since you have this book in your hands, chances are that you are one of these actors. The bio-derived polymers discussed in this book and their applications provide part of the solution to these problems.

This book examines the current state of the art, new challenges, opportunities, and applications in the field of biopolymers. It is organized in two volumes morphology, structure, and properties (Chapters 1–12), and characterization and applications (Chapters 13–27). This book summarizes in an edited format and in a comprehensive manner many of the recent technical research accomplishments in the area of biopolymers and their blends, composites, IPNs, and gels from macro- to nanoscale. The handpicked selection of topics and expert contributors make this survey of biopolymers an outstanding resource reference for anyone involved in the field of eco-friendly biomaterials for advanced technologies. It surveys processing–morphology–property relationship of biopolymers, their blends, composites, and gels. The influence of experimental conditions and preparation techniques (processing) on the generation of micro- and nanomorphologies and the dependence of these morphologies on the properties of the biopolymer systems are discussed in detail. The application of various theoretical models for the prediction of the morphologies of these systems is discussed. This book also illustrates the use of biopolymers in health, medicine, food, and cosmetics.

There are already a number of fine texts that comprehensively cover the subject of biopolymers in great detail, but the content of this book is unique. For the first time, a book deals with processing, morphology, dynamics, structure, and properties of various biopolymers and their multiphase systems. It covers an up-to-date record on the major findings and observations in the field of biopolymers.

Grenoble, Institute of Technology

February 26, 2013

Alain Dufresne

List of Contributors

Esra Alveroglu

Istanbul Technical University

Department of Physics

Maslak

34469 Istanbul

Turkey

Shoshana (Malis) Arad

Ben-Gurion University of the Negev

Department of Biotechnology Engineering

POB 653 Beer-Sheva 84105

Israel

Robin Augustine

Mahatma Gandhi University

Centre for Nanoscience and Nanotechnology

Priyadarshini Hills

Kottayam 686560

Kerala

India

Rachel Auzély-Velty

Université Joseph Fourier

Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS)

601 rue de la Chimie

38041 Grenoble

France

Luc Avérous

Université de Strasbourg

BioTeam/ICPEES-ECPM, UMR 7515

25 rue Becquerel

67087 Strasbourg Cedex 2

France

Deepa Bhanumathy Amma

Bishop Moore College

Department of Chemistry

Mavelikara 690110

Kerala

India

Deborah Blanchard

Université Joseph Fourier

Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS)

601 rue de la Chimie

38041 Grenoble

France

Ana Maria Botelho do Rego

Technical University of Lisbon

Institute of Nanoscience and Nanotechnology

Centro de Química-Física Molecular

Av. Rovisco Pais

1049-001 Lisboa

Portugal

Sami Boufi

University of Sfax

Faculté des Sciences de Sfax

Laboratoire des Sciences des

Matériaux et Environnement

BP 1171-3000 Sfax

Tunisia

Denis Bouyer

Université de Montpellier

Institut Européen des Membranes

2, Place Eugene Bataillon

34967 Montpellier

Cedex 2

France

Christophe Chassenieux

LUNAM Université du Maine

IMMM UMR CNRS 6283

Dept. Polymères, Colloïdes, Interfaces

1 Avenue Olivier Messiaen

72085 Le Mans Cedex 9

France

Mindong Chen

Nanjing University of Information Science & Technology

Department of Chemistry

Nanjing 210044

China

Wenguo Cui

The First Affiliated Hospital of Soochow University

Department of Orthopedics

188 Shizi Street

Suzhou, Jiangsu 215006

China

and

Soochow University

Orthopedic Institute

708 Renmin Road

Suzhou, Jiangsu 215007

China

Uro Cvelbar

Joef Stefan Institute

F4 Plasma Laboratory

Jamova 39

1000 Ljubljana

Slovenia

Jany Dandurand

Université Paul Sabatier

CIRIMAT UMR CNRS 5085

Physique des Polymères 3R1B2

118 route de Narbonne

31062 Toulouse cedex 02

France

Jacques Desbrieres

Université de Pau et des Pays de l'Adour

IPREM

Helioparc Pau Pyrenees

2 Avenue P. Angot

64053 Pau Cedex 09

France

Marli Miriam de Souza Lima

Universidade Estadual de Maringa

Pharmacy Departement LAFITEC

Av. Colombo, 5790 - Zona 07

CEP 87020-900 Maringa

Parana, Brasil

Dominique Durand

LUNAM Université du Maine

IMMM UMR CNRS 6283

Dept. Polymères, Colloïdes, Interfaces

1 Avenue Olivier Messiaen

72085 Le Mans Cedex 9

France

Tao Feng

Shanghai Institute of Technology

Department of Food Science and Technology

School of Perfume and Aroma Technology

120 Caobao Road

Shanghai 200235

China

Ana Maria Ferraria

Technical University of Lisbon

Institute of Nanoscience and Nanotechnology

Centro de Química-Física Molecular

Av. Rovisco Pais

1049-001 Lisboa

Portugal

Chris Ford

University of Southampton

School of Biological Sciences

Highfield Campus

Southampton SO17 1BJ

UK

Tim J. Foster

University of Nottingham

School of Biosciences

Division of Food Sciences

Sutton Bonington Campus

Loughborough Leicestershire LE12 5RD

UK

Ali Gelir

Istanbul Technical University

Department of Physics

Maslak

34469 Istanbul

Turkey

Anne George

Medical College Kottayam

Department of Anatomy

Gandhinagar

Kottayam 686008

Kerala

India

and

Center of Excellence for Polymer Materials and Technologies

Tehnoloski Park 24

1000 Ljubljana

Slovenia

Hero Jan Heeres

University of Groningen

Department of Chemical Engineering

Nijenborgh 4

9747 Groningen

The Netherlands

Antonio Heredia

Facultad de Ciencias

Departamento de Biología Molecular y Bioquímica

Campus de Teatinos, s/n

29071 Málaga

Spain

Ferenc Horkay

National Institute of Child Health and Human Development NICHD

13 South Dr Room 3W16, MSC 5772

Bethesda Md 20892-5772

USA

Changmin Hu

Shanghai Jiao Tong University

School of Biomedical Engineering and Med-X Research Institute

1954 Hua Shan Road

Shanghai 200030

China

Parameswaranpillai Jyotishkumar

INSPIRE Faculty

Department of Polymer Science and Rubber Technology

Cochin University of Science and Technology, Kochi-682022

Vassilis Kiosseoglou

Aristotle University of Thessaloniki

School of Chemistry

Laboratory of Food Chemistry and Technology

54124 Thessaloniki

Greece

Vanja Kokol

University of Maribor

Faculty of Mechanical Engineering

Institute for Engineering Materials and Design

Smetanova ul. 17

2000 Maribor

Slovenia

Ashok Kumar

Indian Institute of Technology Kanpur

Department of Biological Sciences and Bioengineering

Kanpur 208016

Uttar Pradesh

India

Rakesh Kumar

Birla Institute of Technology, Mesra.

Patna Campus

Department of Applied Chemistry

P.O. - B. V. College, Patna - 800014, Bihar

India

Colette Lacabanne

Université Paul Sabatier

CIRIMAT UMR CNRS 5085

Physique des Polymères 3R1B2

118 route de Narbonne

31062 Toulouse cedex 02

France

Oshrat Levy-Ontman

Sami Shamoon College of Engineering

Department of Chemical Engineering

Beer-Sheva 84100

POB 950

Israel

Dagang Liu

Nanjing University of Information Science & Technology

Department of Chemistry

Nanjing 210044

Ningliu Rd 219

China

Fei Lu

Nanjing University of Information Science & Technology

Department of Chemistry

Nanjing 210044

China

Phedra Marius

University of Southampton

School of Biological Sciences

Highfield Campus

Southampton SO17 1BJ

UK

Siji K. Mary

Bishop Moore College

Department of Chemistry

Mavelikara 690110

Kerala

India

Camille Michon

AgroParisTech

UMR1145 Ingénierie Procédés Aliments

Agro

Paristech/Inra/Cnam

1 avenue des Olympiades

91300 MASSY

France

Bernard Moussian

University of Tübingen

Interfaculty Institute for Cell Biology

Department of Animal Genetics

Auf der Morgenstelle 28

72076 Tübingen

Germany

Miran Mozeti

Joef Stefan Institute

F4 Plasma Laboratory

Jamova 39

1000 Ljubljana

Slovenia

and

Center of Excellence for Polymer Materials and Technologies

Tehnoloski Park 24

1000 Ljubljana

Slovenia

Taco Nicolai

LUNAM Université du Maine

IMMM UMR CNRS 6283

Dept. Polymères, Colloïdes, Interfaces

1 Avenue Olivier Messiaen

72085 Le Mans Cedex 9

France

Yoshiharu Nishiyama

Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS), BP53, 38041 Grenoble cedex 9,

France

Adamantini Paraskevopoulou

Aristotle University of Thessaloniki

School of Chemistry

Laboratory of Food Chemistry and Technology

54124 Thessaloniki

Greece

Francesco Picchioni

University of Groningen

Department of Chemical Engineering

Nijenborgh 4

9747 Groningen

The Netherlands

Eric Pollet

Université de Strasbourg

LIPHT-ECPM, EAc (CNRS) 4379

25 rue Becquerel

67087 Strasbourg Cedex 2

France

Laly A. Pothen

Bishop Moore College

Department of Chemistry

Mavelikara 690110

Kerala

India

Rajakumari Rajendran

Mahatma Gandhi University

Centre for Nanoscience and Nanotechnology

Priyadarshini Hills

Kottayam 686560

Kerala

India

Manuel Rei Vilar

Université Paris Diderot

ITODYS UMR CNRS 7086

Bat. Lavoisier

15 rue J. A. De Baïf

75025 Paris cedex 13

France

Tania Ródenas

Instituto de Tecnología Química UPV-CSIC

Universidad Politécnica de Valencia-Consejo Superior de Investigaciones Científicas

Av. Los Naranjos, s/n

46022, Valencia (Spain)

Maria J. Sabater

Instituto de Tecnología Química UPV-CSIC

Universidad Politécnica de Valencia-Consejo Superior de Investigaciones Científicas

Av. Los Naranjos, s/n

46022, Valencia (Spain)

Khaleelulla Saheb Shaik

University of Tübingen

Interfaculty Institute for Cell Biology

Department of Animal Genetics

Auf der Morgenstelle 28

72076 Tübingen

Germany

Valérie Samouillan

CIRIMAT UMR CNRS 5085

Physique des Polymères 3R1B2

118 route de Narbonne

31062 Toulouse cedex 02

France

Prasanth Kumar Sasidharan Pillai

Bishop Moore College

Department of Chemistry

Mavelikara 690110

Kerala

India

Deepti Singh

Indian Institute of Technology Kanpur

Department of Biological Sciences and Bioengineering

Kanpur 208016

Uttar Pradesh

India

Janez Štrancar

Jožef Štefan Institute

Department of Solid State Physics

EPR Center

Laboratory of Biophysics

Jamova 39

1000 Ljubljana

Slovenia

Garrick F. Taylor

University of Southampton

School of Biological Sciences

Highfield Campus

Southampton SO17 1BJ

UK

Sabu Thomas

Mahatma Gandhi University

Centre for Nanoscience and Nanotechnology

Priyadarshini Hills

Kottayam 686560

Kerala

India

Donglin Tian

Nanjing University of Information Science & Technology

Department of Chemistry

Nanjing 210044

China

Carlos Torres

Catholic University of Peru

Department of Mechanical Engineering

Av. Universitaria 1801, San Miguel

Lima 32

Peru

Fernando G. Torres

Catholic University of Peru

Department of Mechanical Engineering

Av. Universitaria 1801, San Miguel

Lima 32

Peru

Omar Paul Troncoso

Catholic University of Peru

Department of Mechanical Engineering

Av. Universitaria 1801, San Miguel

Lima 32

Peru

Frank van Mastrigt

University of Groningen

Department of Chemical Engineering

Nijenborgh 4

9747 Groningen

The Netherlands

Philip T.F. Williamson

University of Southampton

Faculty of Natural & Environmental Sciences

Highfield Campus

Southampton SO17 1BJ

UK

Charles Winkworth-Smith

University of Nottingham

School of Biosciences

Division of Food Sciences

Sutton Bonington Campus

Loughborough, Leicestershire LE12 5RD

UK

Ran Ye

Biosystems Engineering & Soil Science

University of Tennessee

2506 E.J. Chapman Drive

Knoxville

TN 37996-4531

USA

Yasar Yilmaz

Istanbul Technical University

Department of Physics

Maslak

34469 Istanbul

Turkey

1

Biopolymers: State of the Art, New Challenges, and Opportunities

Christophe Chassenieux, Dominique Durand, Parameswaranpillai Jyotishkumar, Sabu Thomas

1.1 Introduction

The term “biopolymers” usually describes polymers produced in a natural way by living species. Their molecular backbones are composed of repeating units of saccharides, nucleic acids, or amino acids and sometimes various additional chemical side chains contributing also to their functionalities.

If the largest part of biopolymers is extracted from biomass, such as polysaccharides from cellulose and proteins from collagen or milk, biopolymers can also be produced from biomonomers using conventional chemical processes as polylactic acid, or directly in microorganisms or genetically modified organisms, as polyhydroxyalkanoates. The genetic manipulation of microorganisms brings a tremendous potentiality for the biotechnological production of biopolymers with tailored properties quite suitable for high-value medical applications such as tissue engineering and drug delivery.

Throughout history, biopolymers have been mainly used by mankind as food, or for making clothing and furniture. Since the industrial time, fossil fuels such as oil are the greatest source in the development and manufacture of almost every commercial product, such as the plastic, which is currently used at a very large scale. But these fuels are not unlimited resources, and environmental concerns over all aspects of using fossil fuels for production and energy must be taken into account. We must act in a sustainable manner, which means that the resources must be consumed at a rate such that they can be restored by natural cycles of our planet. Therefore, today, the renewable nature of biopolymers leads them to a renaissance and a new interest. In the last 20 years, this interest in sustainable products has driven the development of new biopolymers from renewable feedstocks. Biopolymers have to compete with polymers derived from fossil fuel not only because of their functional properties but also in terms of cost. In this respect, biopolymers are competitive when the price of oil is high and the price of feedstocks, such as starch from corn, is low.

In addition, the biodegradability of biopolymers gives them a specific advantage for the environmental concerns, for example, single-use packaging in food, automotive, or electronics industries [1].

The bionanocomposites deserve a special attention because they form a fascinating interdisciplinary area that brings together biology, materials science, and nanotechnology. Generally, polymer nanocomposites are the result of the combination of polymers and inorganic/organic fillers at the nanometer scale. The extraordinary versatility of these new materials comes from the large choice of biopolymers and fillers available, such as clays, cellulose whiskers, and metal nanoparticles. These new materials have been elaborated thanks to the development of new powerful techniques such as electrospinning [2]. In these materials, the interaction between fillers at the nanometer scale acts as a bridge in the polymer matrix that leads to the enhancement of the mechanical properties of nanocomposites with respect to conventional microcomposites [3]. But, bionanocomposites also add a new dimension because they are biocompatible and/or biodegradable materials. So, they are gradually absorbed and/or eliminated by the body. Their degradation is mainly due to hydrolysis or mediated by metabolic processes. Therefore, nanocomposites present a great interest for biomedical technologies such as tissue engineering, medical implants, dental applications, and controlled drug delivery. Nevertheless, the spread out of these valuable bionanocomposites in our everyday life can only be achieved provided they are easily accessible to consumers in terms of volume. Cellulose whiskers may soon be a challenge for nanoclays that are being used as traditional nanofillers for many applications [4], since they are now produced on an industrial scale.

Food products are also usually made of nanostructured materials based on biopolymers, and the elaboration of nanoparticles based on proteins and/or polysaccharides has recently revolutionized the world of biocompatible and degradable natural biological materials [5]. Therefore, the toolbox that micro- and nanotechnologies offer provides new opportunities for product and process innovations in the food industry. The control of the process and functionality at the nanoscale leads to more sustainable food production. This approach allows the development of nutrient delivery systems with healthy and/or less caloric value nutrients, sensors, and diagnostic devices that can monitor and ensure the safety of food products throughout the food chain. At least, various enhanced packaging concepts extend the shelf life of fresh products or indicate quality deterioration of the packaged product. However, for consumers, the general feeling toward foods that are associated with these new technologies and more particularly nanotechnologies is not totally positive. Thus, it is imperative to develop a good communication of the applications of nanotechnologies that allows the consumers to make an informed decision whether or not they would like to have the benefits of certain applications of nanotechnologies, or whether they do not accept certain risks.

All these driving forces act as stimuli to develop new materials based on biopolymers, and there are many opportunity areas such as industrial, medical, food, consumer products, and pharmaceutical applications for which biopolymers act as stabilizers, thickeners, binders, dispersants, lubricants, adhesives, drug-delivery agents, and so on.

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

If, for over half a century, the study of biopolymers has been nearly the reserved field of biochemists and molecular biologists, during the last decade the soft matter physics community has seized this research field. Its purpose is not only for pure intellectual curiosity but also for modeling and understanding various mechanisms involved in the soft matter field, and for the consequences that a better understanding of these biopolymers might lead to. In fact, the fundamental physics underlying the biopolymer behavior and the techniques applied for their study are often similar. With the development of new powerful X-ray sources, new microscopies (cryo-TEM, ultra speed confocal scanning laser microscopy), and the advent of single-molecule techniques [6], polymer physicists are now strongly active in this field and there exists a strong collaboration between biologists and physicists.

For example, biologists can create specific mutations to design molecules for specific studies of the role played by specific groups located at precise points along the chain, for understanding by example the influence of a particular residue on the folding–unfolding process of biopolymer and its influence on the mechanical properties, which can be measured by pulling with an AFM tip [7]. Also, the understanding of the biological molecular machines allows designing synthetic molecules to perform analogous tasks [8].

More generally, most biological macromolecular assemblies are predominantly made from mixtures of stiff biopolymers, and our cells, muscles, and connective tissue owe their remarkable mechanical properties to these complex biopolymer networks. The understanding of their incessant assembly, disassembly, restructuring, active and passive mechanical deformation needs a lot of theoretical modeling efforts because if flexible polymer behavior is well depicted in litterature, the stiffness of these biopolymers and the resulting anisotropic networks that lead to smart mechanical and dynamical properties are far from being understood.

The proteins, which are the major biomacromolecules in our body and play a fundamental role in making our body work, give us another example. As it is well known, proteins have a strong tendency to self-assemble after denaturation and this quasiuniversal mechanism, valuable for all the proteins, can lead to three generic structures, particulate gels around the isoelectric point, isolated amyloid fibrils, and spherulites far away from the isoelectric point [9,10]. Therefore, proteins have appeared as good model systems for understanding and modeling various self-assembling mechanisms, and more particularly the competition between processes of aggregation, gelation, and phase separation that play a major role in the self-assembly of most complex systems. So, a good control of the macroscopic phase separation during the protein self-assembly by kinetically trapping the structure at a particular stage of the process allows to create a large variety of new arrested structures. The linear and nonlinear rheological behaviors of these matrices and the transport properties of various probes inside are still actively investigated for understanding the relationships between these properties and the structures of the matrices. Such fundamental researches also have societal and medical interests because the aggregation of misfolded protein molecules into so-called amyloid fibrils is directly implicated in many diseases such as Alzheimer's disease. More pleasant, the food industry also utilizes the self-assembling ability of proteins such as the beta-lactoglobulin, a major protein component of milk, to texture foods such as yogurt by forming gels.

The mixtures of biopolymer are well known to display very rich phase behaviors. The understanding of the underlying physics of these phase behavior and of the rheology–morphology relationships of the resulting phases also constitutes a challenge of interest and importance. Such mixtures can also be used as efficient stabilizers for gas bubbles generated using high-throughput devices [11]. Since biomedical applications are targeted, the stability of the bubbles and their monodispersity are key points to be addressed, which can be achieved efficiently by combining biopolymer/protein mixtures and microfluidics.

Functional biopolymer nanoparticles or microparticles formed by heat treatment of globular protein–ionic polysaccharide electrostatic complexes under appropriate conditions are another example of the high potential of biopolymer mixtures [12]. Such biopolymer particles can be used as encapsulation and delivery systems, fat mimetics, lightening agents, or texture modifiers.

1.3 Biopolymers: An Endless Source of Applications

The trend observed for physics also holds for chemistry since biopolymers have become new building blocks from the point of view of macromolecular chemistry in the last decade. This fact owes much to the emergence of new polymerization techniques such as controlled radical polymerization (CRP) and to “Click” chemistry. Processing of these chemical alternatives allows a very good control of the macromolecular architecture, the molar mass distribution, and the functionality of the macromolecules. Block copolymers involving a biopolymer block are nowadays of an easier access, rendering possible the study of their self-assembly in bulk and/or in a selective solvent of one of the blocks. The specificities of the biopolymer block in terms of bioactivity, biocompatibility, and biodegradability allow targeting application fields such as pharmaceutical science for which the self-assemblies (polymersomes, micellar aggregates, microgels, etc.) are used as drug delivery systems with potential targeting properties [13]. In bulk, it should also be said that block copolymers based on a biopolymer block are pretty promising. Actually, the strong segregation force exhibited by most biopolymer blocks with respect to synthetic ones results in an efficient microphase separation despite the small polymerization degrees of each of the blocks. Well-organized thin films with periodicity as small as 5 nm have been obtained for the first time for which applications to soft electronics are expected [14].

1.4 Topics Covered by the Book

This book reviews the recent accomplishments obtained in terms of preparation, characterization, and applications of biopolymers. In the first chapters, general overviews and descriptions of the main concepts and issues regarding the most important biopolymer families are introduced. The synthesis of various biopolymers through the processing of genetic engineering tools or by nature itself is described in Chapters 4, 5, and 11. In each case, the impact of different synthetic conditions on the characteristics of the macromolecules is described in close correlation with their potential from the applicative point of view.

In the same way, Chapters 6–10 focus on the use of biopolymers as material. Each chapter focuses on one type of material such as polymer blends, macro- to nanocomposites, interpenetrated networks (IPN), or hydrogels. In most cases, the elaboration of biomaterials can be rationalized through a modelization approach as depicted in Chapter 24. The resulting practical cases of biopolymer used in our everyday life are described in Chapter 26. Their main advantages in terms of biodegradation, recycling, and life cycle are discussed in Chapter 25.

Biopolymers display interesting properties, not only in bulk but also in solution and at interfaces, as shown in Chapter 23.

The remaining chapters mainly focus on an experimental technique that can be used for gathering information on biopolymers from the point of view of their structure, dynamics, at different length and timescales in bulk or at interfaces. In each case, the background for understanding the technique is given, practical cases are described, and the limits of the technique are discussed. In Chapter 12, the ability of dielectric techniques to access the molecular mobility and chain dynamics of biopolymers and biological systems is addressed. These studies can be nicely complemented at other timescale by running NMR or EPR measurements as shown in Chapters 13 and 14.

Chapters 16–19 describe the use of scattering techniques and of microscopy for investigating the structure of biopolymers at several but complementary length scales. Structural but also mechanical properties of the biopolymers may also be derived from rheological measurements as described in Chapters 20–22. When an accurate knowledge of the chemical composition of the extreme layer of biopolymer surfaces is needed, XPS analysis can be used as detailed in Chapter 15.

1.5 Conclusions

Academic researchers involved in the biopolymer areas often work across various disciplines, physics, soft matter, chemistry, biochemistry, and biology and have developed skills that enable them to transfer their knowledge from one field to another. Thus, these skills should enable them to face some great challenges including the understanding of the physics of life, the nanoscale design of functional smart materials, the directed assembly of extended structures with targeted properties, and the emergence of physics far from equilibrium. The gap between nature and scientist know-how regarding “tailor-made” biopolymers is still wide, and a biomimetic approach of biopolymer synthesis may need tremendous development of specific genetic engineering tools. Furthermore, one should really have concerns regarding the life cycle of materials involving biopolymers, which are not always their single component, in order to avoid what we are currently facing with their actual homologues based on fossil fuels.

References

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9. Durand, D., Gimel, J.C., and Nicolai, T. (2002) Aggregation, gelation and phase separation of heat denatured globular proteins. Physica A – Stat. Mech. Appl., 304 (1–2), 253–265.

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2

General Overview of Biopolymers: Structure, Properties, and Applications

Charles Winkworth-Smith and Tim J. Foster

2.1 Introduction

Biopolymer research is at the intersection of two new major branches of science, that of nanotechnology and environmental sciences. As the awareness of global warming increases and the cost of oil continues to rise, renewable biomaterials are gaining importance. This is being undertaken from a strong baseline as there has been significant research over the past four decades investigating the properties of these materials and looking for areas of exploitation in their use in structuring products. There are a number of industrial uses of biopolymers, ranging from coatings and adhesives, and the increased use in blends in the area of bioplastics, to cosmetics, personal care, pharmaceutical, and food products. The functionality in these products depends on a number of factors: the solvent type/quality and amount; the role of the biopolymer, that is, surface activity in emulsions and foams or the bulk structuring through imparting viscosity or gelation; the process employed to create the structure; and the interaction with other formulation materials. Underpinning the precise functionality is knowledge of the biopolymer structure. The biopolymers in most use are polysaccharides and proteins, and therefore their constituent sugars and amino acids, their sequence, and contribution to hydrodynamic three-dimensional structure in the solvent determine the overall polymeric functionality. Both classes of biopolymers are reviewed in detail in good “handbooks” designed to provide the reader with enough theoretical background of the individual types of polysaccharides or proteins to be able to understand their functionality and how they can be used [1,2]. In this chapter, we will provide an overview of these materials, some very recent and exciting developments, a focus on a particularly underutilized yet highly abundant polysaccharide, and an outlook for the future.