Polymeric and self assembled hydrogels : from fundamental understanding to applications

275 Pages·2012·6.336 MB·English

by  Xian Jun Loh, Oren A Scherman

Monographs in Supramolecular Chemistry
Edited by Xian Jun Loh and Oren A Scherman
Polymeric and Self Assembled
Hydrogels
From Fundamental Understanding to Applications
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Polymeric and Self Assembled Hydrogels
From Fundamental Understanding to Applications
Monographs in Supramolecular Chemistry
Series Editors:
Philip Gale, University of Southampton, UK
Jonathan Steed, Durham University, UK
Titles in this Series:
1: Cyclophanes
2: Calixarenes
3: Crown Ethers and Cryptands
4: Container Molecules and Their Guests
5: Membranes and Molecular Assemblies: The Synkinetic Approach
6: Calixarenes Revisited
7: Self-assembly in Supramolecular Systems
8: Anion Receptor Chemistry
9: Boronic Acids in Saccharide Recognition
10: Calixarenes: An Introduction, 2nd Edition
11: PolymericandSelfAssembledHydrogels:FromFundamentalUnderstanding
toApplications
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Polymeric and Self Assembled
Hydrogels
From Fundamental Understanding
to Applications
Edited by
Xian Jun Loh
Melville Laboratory for Polymer Synthesis,
Department of Chemistry, University of Cambridge,
Cambridge, UK
Email: [email protected], [email protected]
Oren A. Scherman
Melville Laboratory for Polymer Synthesis,
Department of Chemistry, University of Cambridge,
Cambridge, UK
Email: [email protected]
MonographsinSupramolecularChemistryNo.11
ISBN: 978-1-84973-561-2
ISSN: 1368-8642
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Preface
Polymeric and self-assembled hydrogel research is a rapidly changing field
and this book is intended to serve as a guide through the latest work, offer-
ing summaries of the current state-of-the-art cutting-edge research as well as
extensive references to the latest breakthroughs. Each chapter is an author-
itative treatise on its specific topic and can be read on its own. All the
authors invited to write the chapters in this book have many years of experi-
ence in hydrogel research and their knowledge is succinctly condensed into
this volume. Readers can be expected to be taken through the entire spec-
trum of hydrogel research as the book is structured into three major sections
covering basic fundamental research, applied and platform technologies, and
commercially viable applications.
Lookingaheadtothetopicscoveredinthebook,webeginbygivingabroad
overview of the field of polymeric hydrogels and covering some of the newest
and most exciting research in this field. Chapter 2 covers basic fundamental
research on the hydrogel properties of tetra-PEG hydrogels and on using
techniques such as small-angle neutron scattering to understand the internal
hydrogel structure.
Laboratory work inthe synthesisand characterization ofnovelhydrogels is
discussedinChapters3–5andexemplifiescutting-edgedevelopmentinthefield
of hydrogels. Chapter 3 describes the recent developments in supramolecular
approaches to the formation of hydrogels using host–guest chemistries, while
Chapter 4 highlights a unique ‘‘slide-ring’’ hydrogel based on cyclodextrin
inclusion complexes that has exceptional stretch abilities. Chapter 5 describes
the growing area of peptide hydrogels, their preparation and their potential
applications.
Practical applications are addressed in Chapters 6–8, with particular
emphasis on the fast-moving chemo-sensing and biomedical fields. Chapter 6
presentstheuseofhydrogelsinchemo-sensingapplicationsandChapter7isa
MonographsinSupramolecularChemistryNo.11
PolymericandSelfAssembledHydrogels:FromFundamentalUnderstandingtoApplications
EditedbyXianJunLohandOrenA.Scherman
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
vi Preface
complete overview of a class of physical hydrogels known as thermogelling
polymers and their applicative aspects. Chapter 8 represents an outline of the
use of hydrogels in biomedical fields.
Finally, in order to showcase commercial applications, Chapters 9 and 10
present current commercial successes of temperature-sensitive hydrogels and
hydrogel microspheresfordrugdelivery applications.Toobtainasense ofthe
vast scope of hydrogel applications, a quick snapshot is also presented in the
introduction to this book.
We would like to gratefully acknowledge the contributions of the well-
regarded academics and industrialists who have taken time out of their busy
schedulestoembarkonthisprojecttogetherwithus.ThecontributionsofSetu
Kasera and Sandra Leytheauser in the production of the book cover are
gratefully acknowledged. We would also like to acknowledge the help of the
RSC, especially Leanne Marle, Alice Toby-Brant and Katrina Harding for
their patience with us at various stages of the project. We thank Joo Gek Lim
and Moi Joo Loh who have been actively involved in all stages of the layout,
language, style and graphic editing of this book. This book would not have
beenpossiblewithouttheircollectiveinputsand,indeed,thebookisnowmuch
better because of their contributions. Finally, we hope that this volume will
serve as an indispensable reference for students, researchers, academics and
industrialists in the field of hydrogel research.
Xian Jun Loh
Oren A. Scherman
Cambridge, UK
Contents
Chapter 1 Introduction 1
Xian Jun Loh and Oren A. Scherman
1.1 Origins 1
1.2 Type of Cross-Linking 3
1.3 Cutting-edge Research 3
References 5
Chapter 2 Fabrication, Structure, Mechanical Properties,
and Applications of Tetra-PEG Hydrogels 7
Mitsuhiro Shibayama and Takamasa Sakai
2.1 Introduction 7
2.2 Fabrication 10
2.2.1 Synthesis of Precursors 10
2.2.2 Characterization 10
2.2.3 Synthesis of Tetra-PEG Gels:
Cross-End-Coupling 10
2.2.4 Gelation Kinetics 11
2.2.5 Final Conversion 13
2.3 Structure Characterization by SANS 13
2.3.1 Theoretical Background 14
2.3.2 Macromer 16
2.4 Mechanical Properties 22
2.4.1 Theoretical Background 23
2.4.2 Small Deformation 24
2.4.3 p-Controlled Gels 26
2.4.4 Large Deformation 26
2.4.5 Viscoelastic Properties 28
MonographsinSupramolecularChemistryNo.11
PolymericandSelfAssembledHydrogels:FromFundamentalUnderstandingtoApplications
EditedbyXianJunLohandOrenA.Scherman
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
viii Contents
2.5 Medical Applications 29
2.5.1 Elastic Modulus 30
2.5.2 Degradation Behavior 31
2.6 Conclusions 34
Acknowledgements 35
References 35
Chapter 3 Supramolecular Hydrogels 39
Jesu´s del Barrio, Eric A. Appel, Xian Jun Loh and
Oren A. Scherman
3.1 Introduction 39
3.2 Supramolecular Polymeric Hydrogels Based On
Host–Guest Inclusion Complexes 41
3.2.1 Hydrogels from Cyclodextrins 41
3.2.2 Hydrogels from Cucurbiturils 54
3.3 Hydrogels Based On Non-Covalent Interactions
Other Than Host–Guest Inclusion Complexes 60
3.3.1 Hydrogen Bonding Interactions 60
3.3.2 Ionic Interactions 60
3.3.3 Metal–Ligand Interactions 61
3.4 Conclusions 62
References 63
Chapter 4 Synthesis and Properties of Slide-Ring Gels 72
Kazuaki Kato and Kohzo Ito
4.1 Introduction 72
4.2 Synthesis of Slide-Ring Materials 74
4.3 Homogeneous and Isotropic Networks under
Deformation 76
4.4 Abnormal Mechanical Properties and Theoretical
Descriptions 77
4.5 Functionalization by Modification of the Cyclic
Components 79
4.6 Significance of the Diversification of the Backbone
Polymers 79
4.7 Organic–Inorganic Hybrid Slide-Ring Materials 80
4.8 A Breakthrough Synthesis of Polyrotaxanes for the
Diversification of Backbones 84
4.9 Viscoelastic Relaxation Reflecting the Sliding
Dynamics and the Mobility of the CDs 85
4.10 Conclusions 89
References 90
Contents ix
Chapter 5 Peptide and Protein Hydrogels 93
Lawrence J. Dooling and David A. Tirrell
5.1 Introduction 93
5.2 Peptide and Protein Structure 94
5.2.1 Peptide and Protein Synthesis 94
5.2.2 Higher-Order Structure and Hydrogel
Assembly 95
5.3 Hydrogels from Oligopeptides 97
5.3.1 b-Sheet Peptide Hydrogels 97
5.3.2 a-Helical Coiled-Coil Oligopeptide
Hydrogels 100
5.3.3 Collagen Mimetic Peptide Hydrogels 102
5.3.4 Peptide Amphiphile Hydrogels 104
5.4 Hydrogels from Recombinant Proteins 105
5.4.1 Self-Assembling, Multidomain Artificial
Proteins 105
5.4.2 Biomimetic Recombinant Proteins: Elastins
and Silks 109
5.4.3 Multifunctional Protein Hydrogels 110
5.5 Hydrogels from Peptide–Polymer and
Protein–Polymer Hybrids 111
5.5.1 Peptides as Physical and Chemical
Cross-Linkers 112
5.5.2 Synthetic Hydrogels Containing Functional
Protein Domains 113
5.6 Future Directions and Challenges 114
5.6.1 Immune Response to Peptide and Protein
Hydrogels 114
5.6.2 New Methods for Peptide Synthesis 115
5.6.3 Spatially Patterned Hydrogels and Epitopes
Beyond RGD 116
Acknowledgments 117
References 117
Chapter 6 Chemomechanical Hydrogels: Selective Response towards
External Effector Molecules 125
Hans-Jo¨rg Schneider
6.1 Introduction 125
6.2 Basic Mechanisms: Water Content Changes 126
6.3 Speed and Sensitivity of Response 128
6.4 Covalent Interactions: Glucose-Sensitive
Hydrogels 130
6.5 Inorganic Ions as Effectors 131