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Bio-inspired Polymers

Bio-inspired Polymers

Nico Bruns | Andreas F M Kilbinger

(2016)

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Book Details

Abstract

Many key aspects of life are based on naturally occurring polymers, such as polysaccharides, proteins and DNA. Unsurprisingly, their molecular functionalities, macromolecular structures and material properties are providing inspiration for designing new polymeric materials with specific functions, for example, responsive, adaptive and self-healing materials.

Bio-inspired Polymers covers all aspects of the subject, ranging from the synthesis of novel polymers, to structure-property relationships, materials with advanced properties and applications of bio-inspired polymers in such diverse fields as drug delivery, tissue engineering, optical materials and lightweight structural materials.

Written and edited by leading experts on the topic, the book provides a comprehensive review and essential graduate level text on bio-inspired polymers for biochemists, materials scientists and chemists working in both industry and academia.


Table of Contents

Section Title Page Action Price
Cover Cover
Contents xi
Preface vii
Chapter 1 Synthetic Aspects of Peptide– and Protein–Polymer Conjugates in the Post-click Era 1
1.1 Introduction 1
1.2 General Concepts for Bioconjugation 3
1.3 Chemical Synthesis of Peptide– and Protein–Polymer Conjugates 6
1.3.1 Coupling with Amines 6
1.3.2 Coupling with Thiols 7
1.3.3 Chemical Ligation by Oxime/Hydrazone Formation 9
1.3.4 Staudinger Ligation 11
1.3.5 Azide–Alkyne Cycloaddition 13
1.3.6 Diels–Alder (DA) Cycloaddition Reactions 15
1.3.7 Chemistry with 1,2,4-Triazoline-3,5-diones (TAD) 17
1.4 Chemoenzymatic Approaches 19
1.4.1 Transglutaminase (TGase) Catalyzed Ligation 19
1.4.2 Sortase (Srt)-mediated Ligation 20
1.4.3 Enzyme-induced Functional Group Modifications 20
1.5 Biotransformations 21
1.6 Conclusions and Future Perspectives 23
References 24
Chapter 2 Glycopolymers 31
2.1 Introduction 31
2.2 Synthesis of Glycopolymers 32
2.2.1 Synthesis of Glycopolymers via Glycomonomers 35
2.2.2 Synthesis of Glycopolymers via Post-polymerization Strategies 40
2.2.3 Synthesis of Glyco- and Block Copolymers 43
2.3 Analyzing Glycopolymers 53
2.3.1 Multivalent Binding of Glycopolymers 53
2.3.2 Binding Studies of Glycopolymers Targeting Lectins 55
2.4 Biomedical and Biotechnological Applications of Glycopolymers 58
2.5 Conclusions 60
Acknowledgments 62
References 62
Chapter 3 Synthesis of Non-natural Polymers with Controlled Primary Structures 66
3.1 Introduction 66
3.2 Sequence-controlled Polymers Prepared by Chain-growth Polymerization 68
3.2.1 Anionic Polymerization 68
3.2.2 Cationic Polymerization 70
3.2.3 Controlled Radical Polymerization 72
3.2.4 Ring-opening Polymerization 77
3.2.5 Ring-opening Metathesis Polymerization 78
3.3 Sequence-controlled Polymers Prepared by Step-growth Polymerization 79
3.3.1 Acyclic Diene Metathesis Polymerization 79
3.3.2 Click Step-growth Polymerization 81
3.3.3 Other Step-growth Approaches 81
3.3.4 Multicomponent Reactions 83
3.4 Sequence-controlled Polymers Prepared by Multi-step-growth Polymerization 86
3.4.1 Conventional Iterative Synthesis 86
3.4.2 Protecting-group-free Iterative Synthesis 87
3.4.3 Successive Radical Insertion 91
3.4.4 Convergent and Divergent Strategies 92
3.5 Use of Templates and Catalytic Molecular Machines 94
3.5.1 Template-assisted Sequence-controlled Polymerization 94
3.5.2 Rotaxane-based Catalytic Machines 96
3.6 Outlook 96
References 98
Chapter 4 Single-chain Nanoparticles 107
4.1 Introduction 107
4.2 Synthesis of SCNPs 108
4.2.1 Covalent Cross-linking Reactions 116
4.2.2 Dynamic Covalent Chemistry 118
4.2.3 Non-covalent Chemistry 120
4.2.4 Multiple Intra-chain Interactions 121
4.2.5 Outlook 123
4.3 Characterization of SCNPs 123
4.3.1 Size Exclusion Chromatography 123
4.3.2 Light Scattering 124
4.3.3 Viscometry 124
4.3.4 NMR Spectroscopy 125
4.3.5 Characterizing the Morphology of SCNPs 126
4.4 Potential Applications 130
4.4.1 Catalysis 131
4.4.2 Nano-medicine 132
4.4.3 Chemical Sensors 133
4.4.4 Self-assembly 133
4.5 Summary and Outlook 135
Acknowledgments 135
References 135
Chapter 5 Polymeric Tubular Structures 141
5.1 Introduction - Bio-inspiration 141
5.2 Tubes Based on Single Polymer Chains 143
5.2.1 Polyaramides 143
5.2.2 Phenylene Helices 150
5.2.3 Other Helical Polymers 159
5.2.4 Helical Polymers with Host-Guest Interactions 167
5.3 Engineered Polymer Nanotubes 171
5.3.1 Block Copolymer Self-assembly 171
5.3.2 DNA Origami 185
5.3.3 Metal-organic Nanotubes (MONTs) 189
5.3.4 Templated Synthesis of Polymeric Tubes 198
5.3.5 Other Methods to Form Polymeric Tubes 209
5.4 Summary 209
Acknowledgments 210
References 210
Chapter 6 Bio-inspired Polymer Membranes 221
6.1 Introduction 221
6.2 Properties of Copolymers that Form Bio-inspired Membranes 223
6.3 Bio-inspired Polymersomes (3D Membranes) 224
6.3.1 Biomolecule Surface-functionalized Vesicles 225
6.3.2 Reconstitution of Membrane Proteins into Polymer Membranes 229
6.3.3 Bio-inspired Block Copolymer/Lipid Hybrid Vesicles 232
6.3.4 Protein-polymer Nanoreactors 233
6.4 Bio-inspired Planar Polymer Membranes (2D Membranes) 235
6.4.1 Monolayer at the Water-Air Interface and Free-standing Membranes 236
6.4.2 Solid Supported Membranes 236
6.4.3 Combination of 2D Membranes with Biomolecules 240
6.4.4 Hybrid Polymer-Lipid Membranes 241
6.5 Immobilized Vesicles 244
6.6 Applications of Bio-inspired Polymer Membranes 246
6.6.1 Polymersomes 246
6.6.2 Planar Membranes 249
6.7 Conclusions and Perspectives 250
Abbreviations 250
Acknowledgments 252
References 252
Chapter 7 Polymeric Ionic Liquids with Micelle-like Topologies and Functions 259
7.1 Introduction 259
7.2 From Supramolecular Assemblies to Micelle-like Macromolecules 260
7.3 Nanostructured and Micelle-like Polymeric Ionic Liquids 265
7.4 Compartmentalized Onion-like Polymeric Ionic Liquids 270
7.5 Conclusions 278
Acknowledgments 280
References 280
Chapter 8 Biological and Bio-inspired Heterogeneous Composites: From Resilient Palm Trees to Stretchable Electronics 286
8.1 Introduction 286
8.2 The Natural Building Blocks of Plants 288
8.3 Palms as Role Models for Biological Heterogeneous Composites 289
8.3.1 Hierarchical Structure and Mechanics of Palms 290
8.3.2 Controlled Local Composition and Reinforcement Orientation 291
8.4 Bio-inspired Heterogeneous Composites 292
8.4.1 The Synthetic Building Blocks 293
8.4.2 Controlled Local Composition 293
8.4.3 Controlled Reinforcement Orientation 294
8.4.4 Functional Devices Based on Bio-inspired Heterogeneous Composites 297
8.5 Discussion 299
8.6 Remaining Challenges and Outlook 302
Acknowledgments 302
References 302
Chapter 9 Translating Mussel Adhesion: Four Uncertainties about the Interface 305
9.1 Introduction 305
9.2 Are Interfacial Films Cleared Away? 306
9.3 Do Mussels Displace Surface Water? 309
9.4 Is the pH of Adhesive Deposition the Same as Seawater pH? 313
9.5 Is Interfacial Redox the Same as Seawater Redox? 316
9.6 Summary 319
Acknowledgments 320
References 320
Chapter 10 Mussel Adhesive-inspired Polymers 322
10.1 Introduction 322
10.2 Catechol Side Chain Chemistry 323
10.2.1 Reversible Catechol Interactions 323
10.2.2 Oxidation-induced Covalent Crosslinking 325
10.2.3 Chemical Modification of Catechol 327
10.3 Preparation of Catechol Functionalized Polymers 329
10.3.1 Catechol Side Chain Protection 329
10.3.2 Direct Functionalization of Catechol 331
10.3.3 Polymerization of Catechol-modified Monomers 332
10.3.4 Catechol-functionalized Initiator 333
10.4 Application of Catechol Functionalized Polymers 334
10.4.1 Biomedical Adhesives 334
10.4.2 Drug Delivery 338
10.4.3 Coatings for Reducing Biofouling 338
10.4.4 Delivery of Therapeutic Cells 341
10.4.5 Hydrogel Actuators 341
10.4.6 Smart Adhesives 342
10.5 Future Outlook 344
10.6 Summary 344
Acknowledgments 345
References 345
Chapter 11 Self-reporting Polymeric Materials with Mechanochromic Properties 354
11.1 Introduction 354
11.2 Learning from Nature 355
11.3 Mechano-responsiveness 358
11.3.1 Mechanical Input and Methods to Measure Mechanically-induced Changes in Polymers 359
11.3.2 Mechano-responsiveness at the Molecular Level 361
11.3.3 Mechano-responsiveness at the Supramolecular Level 369
11.3.4 Mechanobiochemistry 377
11.3.5 Mechano-responsiveness at the Microscopic Level 385
11.4 Conclusions and Future Perspectives 393
Acknowledgments 395
References 395
Chapter 12 Mechanically Adaptive Nanocomposites Inspired by Sea Cucumbers 402
12.1 Introduction 402
12.2 Mechanical Morphing of the Sea Cucumber Dermis 403
12.3 Water-responsive Sea Cucumber-mimicking Nanocomposites 406
12.3.1 Stress Transfer in Mechanically Adaptive Materials 411
12.4 Mechanically Adaptive Sea Cucumber Mimics with Specific Responsiveness 413
12.4.1 pH-responsive Composites 413
12.4.2 Light-responsive Composites 414
12.5 Application of Mechanically Adaptive Nanocomposites in Cortical Implants 415
12.6 Mechanically Adaptive Nanocomposites with Other Functions 417
12.6.1 Healable Materials 417
12.6.2 Shape Memory 418
12.6.3 Actuators 420
12.7 Related Examples of Mechanically Adaptive Materials 421
12.8 Summary and Outlook 422
Acknowledgments 422
References 423
Chapter 13 Bio-inspired Polymer Artificial Muscles 429
13.1 Introduction 429
13.2 Natural Muscle 431
13.3 Types of Polymer Artificial Muscles 434
13.3.1 Polymer Coil Muscles 436
13.3.2 Dielectric Elastomer Actuators (DEAs) 444
13.3.3 Bending Type Polymer Artificial Muscles 448
13.4 Bio-inspired Applications for Polymer Artificial Muscles 452
13.5 Conclusions 454
References 455
Chapter 14 Materials for Tissue Engineering and 3D Cell Culture 460
14.1 Introduction 460
14.2 Electrospinning 461
14.3 Thermally Induced Phase Separation 466
14.4 Emulsion Templated Porous Polymers (PolyHIPEs) 471
14.5 Breath Figure Method 476
14.6 Conclusions 480
Acknowledgments 480
References 480
Chapter 15 Antimicrobial Polymers and Surfaces – Natural Mimics or Surpassing Nature? 490
15.1 Introduction 490
15.2 Classification of Antimicrobial Polymers 492
15.2.1 Considerations on the Comparability of Biological Testing of Antimicrobial Polymers 493
15.2.2 Biocide-releasing Polymers 494
15.2.3 Polymeric Biocides 495
15.2.4 Biocidal Polymers 497
15.3 Antimicrobial Surfaces 509
15.4 Anti-fouling Polymers 511
15.5 Conclusions 513
Acknowledgments 514
References 514
Chapter 16 Superwettability of Polymer Surfaces 523
16.1 Introduction 523
16.2 Self-cleaning Polymer Surfaces 525
16.2.1 Polymer Surfaces in Air 525
16.2.2 Polymer Surfaces under Water 528
16.3 Special Adhesion 530
16.3.1 Cell-adhesion 530
16.3.2 Liquid-adhesion 532
16.3.3 Air-adhesion 532
16.4 Oil/water Separation 532
16.4.1 Oil/water Separation based on Superhydrophobic Materials 533
16.4.2 Oil/water Separation based on Superhydrophilic Materials 534
16.5 Liquid Collection and Transport 535
16.5.1 Spider-silk-inspired Fog Collection System 535
16.5.2 Cactus-inspired Fog Collection System 538
16.5.3 Water Strider Legs and Extended Systems 540
16.5.4 Water Transport on SLIPS and Organogels 543
16.6 Superwetting Polymers in Functional Nanochannels and Nanopores 546
16.6.1 Superwetting Polymers in Nanochannels to Control Ion Transport 546
16.6.2 Superwetting Polymers in Nanochannels for Energy Conversion 549
16.7 Concluding Remarks 551
References 551
Chapter 17 Bio-mimetic Structural Colour using Biopolymers 555
17.1 Introduction 555
17.2 Helicoidal Structures and their Optical Response 556
17.2.1 An Intuitive Explanation of the Optical Effect 556
17.2.2 Mathematical Description 558
17.2.3 Examples 562
17.3 Helicoidal Structures in Nature 562
17.3.1 Cellulose-based Helicoidal Structures for Structural Colour 564
17.3.2 Chitin-based Helicoidal Structures for Structural Colour 566
17.4 Liquid Crystals as Helicoidal Structures 568
17.5 Helicoidal Architectures in Biomimetic Photonics 570
17.5.1 Artificial Helicoidal Cellulose Films 571
17.5.2 Cellulose as a Template - Extending Functionality 575
17.5.3 Sensors 576
17.5.4 Hydrogels and Cellulose Derivatives 576
17.5.5 Chitin 578
17.6 Conclusions 579
Acknowledgments 579
References 580
Subject Index 586