Biomimetic principles in macrom
Trade Review
“As a resource for chemists, the main advantage of this book is this diversity, which makes it stand out from more specific discussions of e.g. biomimetic materials chemistry. In this sense, the book would provide a good reference to someone new to the field or as part of a reading list for a course on biomimetics and bioinspiration in chemistry. In addition, for readers who have worked in one area of biomimetic chemistry for some time, this book is broad enough to give some interesting insight into some very different chemistries.” (Angew. Chem. Int. Ed, 1 August 2013)
“As such, it holds a unique place in the literature, and would be best suited for advanced students or researchers interested in this area. Summing Up: Recommended. Graduate students, researchers/faculty, and professionals/practitioners.” (Choice, 1 August 2013)
Table of Contents
Foreword
Jean-Marie Lehn xvii
Foreword
Janine Benyus xix
Preface xxiii
Contributors xxv
1. Introduction: The Concept of Biomimicry and Bioinspiration in Chemistry 1
Timothy W. Hanks and Gerhard F. Swiegers
1.1 What is Biomimicry and Bioinspiration? 1
1.2 Why Seek Inspiration from, or Replicate Biology? 3
1.2.1 Biomimicry and Bioinspiration as a Means of Learning from Nature and Reverse-Engineering from Nature 3
1.2.2 Biomimicry and Bioinspiration as a Test of Our Understanding of Nature 4
1.2.3 Going Beyond Biomimicry and Bioinspiration 4
1.3 Other Monikers: Bioutilization, Bioextraction, Bioderivation, and Bionics 5
1.4 Biomimicry and Sustainability 5
1.5 Biomimicry and Nanostructure 7
1.6 Bioinspiration and Structural Hierarchies 9
1.7 Bioinspiration and Self-Assembly 11
1.8 Bioinspiration and Function 12
1.9 Future Perspectives: Drawing Inspiration from the Complex System that is Nature 13
References 14
2. Bioinspired Self-Assembly I: Self-Assembled Structures 17
Leonard F. Lindoy, Christopher Richardson, and Jack K. Clegg
2.1 Introduction 17
2.2 Molecular Clefts, Capsules, and Cages 19
2.2.1 Organic Cage Systems 21
2.2.2 Metallosupramolecular Cage Systems 24
2.3 Enzyme Mimics and Models: The Example of Carbonic Anhydrase 28
2.4 Self-Assembled Liposome-Like Systems 30
2.5 Ion Channel Mimics 32
2.6 Base-Pairing Structures 34
2.7 DNA–RNA Structures 36
2.8 Bioinspired Frameworks 38
2.9 Conclusion 41
References 41
3. Bioinspired Self-Assembly II: Principles of Cooperativity in Bioinspired Self-Assembling Systems 47
Gianfranco Ercolani and Luca Schiaffino
3.1 Introduction 47
3.2 Statistical Factors in Self-Assembly 48
3.3 Allosteric Cooperativity 50
3.4 Effective Molarity 52
3.5 Chelate Cooperativity 55
3.6 Interannular Cooperativity 60
3.7 Stability of an Assembly 62
3.8 Conclusion 67
References 67
4. Bioinspired Molecular Machines 71
Christopher R. Benson, Andrew I. Share, and Amar H. Flood
4.1 Introduction 71
4.1.1 Inspirational Antecedents: Biology, Engineering, and Chemistry 72
4.1.2 Chemical Integration 75
4.1.3 Chapter Overview 77
4.2 Mechanical Effects in Biological Machines 78
4.2.1 Skeletal Muscle’s Structure and Function 78
4.2.2 Kinesin 79
4.2.3 F 1 -ATP Synthase 80
4.2.4 Common Features of Biological Machines 82
4.2.5 Variation in Biomotors 83
4.2.6 Descriptions and Analogies of Molecular Machines 83
4.3 Theoretical Considerations: Flashing Ratchets 83
4.4 Sliding Machines 86
4.4.1 Linear Machines: Rotaxanes 86
4.4.2 Mechanistic Insights: Ex Situ and In Situ (Maxwell’s Demon) 89
4.4.3 Bioinspiration in Rotaxanes 93
4.4.4 Molecular Muscles as Length Changes 93
4.5 Rotary Motors 102
4.5.1 Interlocked Rotary Machines: Catenanes 103
4.5.2 Unimolecular Rotating Machines 104
4.6 Moving Larger Scale Objects 104
4.7 Walking Machines 106
4.8 Ingenious Machines 109
4.8.1 Molecular Machines Inspired by Macroscopic Ones: Scissors and Elevators 109
4.8.2 Artificial Motility at the Nanoscale 109
4.8.3 Moving Molecules Across Surfaces 110
4.9 Using Synthetic Bioinspired Machines in Biology 111
4.10 Perspective 111
4.10.1 Lessons and Departures from Biological Molecular Machines 114
4.10.2 The Next Steps in Bioinspired Molecular Machinery 115
4.11 Conclusion 116
References 116
5. Bioinspired Materials Chemistry I: Organic–Inorganic Nanocomposites 121
Pilar Aranda, Francisco M. Fernandes, Bernd Wicklein, Eduardo Ruiz-Hitzky, Jonathan P. Hill, and Katsuhiko Ariga
5.1 Introduction 121
5.2 Silicate-Based Bionanocomposites as Bioinspired Systems 122
5.3 Bionanocomposite Foams 124
5.4 Biomimetic Membranes 126
5.4.1 Phospholipid–Clay Membranes 126
5.4.2 Polysaccharide–Clay Bionanocomposites as Support for Viruses 127
5.5 Hierarchically Layered Composites 129
5.5.1 Layer-by-Layer Assembly of Composite-Cell Model 129
5.5.2 Hierarchically Organized Nanocomposites for Sensor and Drug Delivery 130
5.6 Conclusion 133
References 134
6. Bioinspired Materials Chemistry II: Biomineralization as Inspiration for Materials Chemistry 139
Fabio Nudelman and Nico A. J. M. Sommerdijk
6.1 Inspiration from Nature 139
6.2 Learning from Nature 144
6.3 Applying Lessons from Nature: Synthesis of Biomimetic and Bioinspired Materials 146
6.3.1 Biomimetic Bone Materials 147
6.3.2 Semiconductors, Nanoparticles, and Nanowires 151
6.3.3 Biomimetic Strategies for Silica-Based Materials 157
6.4 Conclusion 160
References 160
7. Bioinspired Catalysis 165
Gerhard F. Swiegers, Jun Chen, and Pawel Wagner
7.1 Introduction 165
7.2 A General Description of the Operation of Catalysts 168
7.3 A Brief History of Our Understanding of the Operation of Enzymes 169
7.3.1 Early Proposals: Lock-and-Key Theory, Strain Theory, and Induced Fit Theory 170
7.3.2 The Critical Role of Molecular Recognition in Enzymatic Catalysis: Pauling’s Concept of Transition State Complementarity 170
7.3.3 The Critical Role of Approach Trajectories in Enzymatic Catalysis: Orbital Steering, Near Attack Conformers, the Proximity Effect, and Entropy Traps 172
7.3.4 The Critical Role of Conformational Motion in Enzymatic Catalysis: Coupled Protein Motions 172
7.3.5 Enzymes as Molecular Machines: Dynamic Mechanical Devices and the Entatic State 173
7.3.6 The Fundamental Origin of Machine-like Actions: Mechanical Catalysis 174
7.4 Representative Studies of Bioinspired/Biomimetic Catalysts 177
7.4.1 Important General Characteristics of Enzymes as a Class of Catalyst 177
7.4.2 Bioinspired/Biomimetic Catalysts that Illustrate the Critical Importance of Reactant Approach Trajectories 178
7.4.3 Bioinspired/Biomimetic Catalysts that Demonstrate the Importance and Limitations of Molecular Recognition 182
7.4.4 Bioinspired/Biomimetic Catalysts that Operate Like a Mechanical Device 187
7.5 The Relationship Between Enzymatic Catalysis and Nonbiological Homogeneous and Heterogeneous Catalysis 192
7.6 Selected High-Performance NonBiological Catalysts that Exploit Nature’s Catalytic Principles 193
7.6.1 Adapting Model Species of Enzymes to Facilitate Machine-like Catalysis 194
7.6.2 Statistical Proximity Catalysts 201
7.7 Conclusion: The Prospects for Harnessing Nature’s Catalytic Principles 203
References 204
8. Biomimetic Amphiphiles and Vesicles 209
Sabine Himmelein and Bart Jan Ravoo
8.1 Introduction 209
8.2 Synthetic Amphiphiles as Building Blocks for Biomimetic Vesicles 210
8.3 Vesicle Fusion Induced by Molecular Recognition 216
8.4 Stimuli-Responsive Shape Control of Vesicles 224
8.5 Transmembrane Signaling and Chemical Nanoreactors 231
8.6 Toward Higher Complexity: Vesicles with Subcompartments 239
8.7 Conclusion 245
References 246
9. Bioinspired Surfaces I: Gecko-Foot Mimetic Adhesion 251
Liangti Qu, Yan Li, and Liming Dai
9.1 The Hierarchical Structure of Gecko Feet 251
9.2 Origin of Adhesion in Gecko Setae 252
9.3 Structural Requirements for Synthetic Dry Adhesives 253
9.4 Fabrication of Synthetic Dry Adhesives 254
9.4.1 Polymer-Based Dry Adhesives 254
9.4.2 Carbon-Nanotube-Based Dry Adhesives 278
9.5 Outlook 284
References 286
10. Bioinspired Surfaces II: Bioinspired Photonic Materials 293
Cun Zhu and Zhong-Ze Gu
10.1 Structural Color in Nature: From Phenomena to Origin 293
10.2 Bioinspired Photonic Materials 296
10.2.1 The Fabrication of Photonic Materials 297
10.2.2 The Design and Application of Photonic Materials 298
10.3 Conclusion and Outlook 317
References 319
11. Biomimetic Principles in Macromolecular Science 323
Wolfgang H. Binder, Marlen Schunack, Florian Herbst, and Bhanuprathap Pulamagatta
11.1 Introduction 323
11.2 Polymer Synthesis Versus Biopolymer Synthesis 325
11.2.1 Features of Polymer Synthesis 325
11.2.2 “Living” Chain Growth 326
11.2.3 Aspects of Chain Length Distribution in Synthetic Polymers: Sequence Specificity and Templating 328
11.3 Biomimetic Structural Features in Synthetic Polymers 330
11.3.1 Helically Organized Polymers 330
11.3.2 β-Sheets 333
11.3.3 Supramolecular Polymers 334
11.3.4 Self-Assembly of Block Copolymers 337
11.4 Movement in Polymers 343
11.4.1 Polymer Gels and Networks as Chemical Motors 343
11.4.2 Polymer Brushes and Lubrication 346
11.4.3 Shape-Memory Polymers 349
11.5 Antibody-Like Binding and Enzyme-Like Catalysis in Polymeric Networks 352
11.6 Self-Healing Polymers 355
References 362
12. Biomimetic Cavities and Bioinspired Receptors 367
Stéphane Le Gac, Ivan Jabin, and Olivia Reinaud
12.1 Introduction 367
12.2 Mimics of the Michaelis–Menten Complexes of Zinc(II) Enzymes with Polyimidazolyl Calixarene-Based Ligands 368
12.2.1 A Bis-aqua Zn(II) Complex Modeling the Active Site of Carbonic Anhydrase 369
12.2.2 Structural Key Features of the Zn(II) Funnel Complexes 371
12.2.3 Hosting Properties of the Zn(II) Funnel Complexes: Highly Selective Receptors for Neutral Molecules 372
12.2.4 Induced Fit: Recognition Processes Benefit from Flexibility 373
12.2.5 Multipoint Recognition 374
12.2.6 Implementation of an Acid–Base Switch for Guest Binding 375
12.3 Combining a Hydrophobic Cavity and A Tren-Based Unit: Design of Tunable, Versatile, but Highly Selective Receptors 377
12.3.1 Tren-Based Calix[6]arene Receptors 377
12.3.2 Versatility of a Polyamine Site 378
12.3.3 Polyamido and Polyureido Sites for Synergistic Binding of Dipolar Molecules and Anions 380
12.3.4 Acid–Base Controllable Receptors 383
12.4 Self-Assembled Cavities 383
12.4.1 Receptors Decorated with a Triscationic or a Trisanionic Binding Site 384
12.4.2 Receptors Capped Through Assembly with a Tripodal Subunit 387
12.4.3 Heteroditopic Self-Assembled Receptors with Allosteric Response 388
12.4.4 Interlocked Self-Assembled Receptors 389
12.5 Conclusion 391
References 392
13. Bioinspired Dendritic Light-Harvesting Systems 397
Andrea M. Della Pelle and Sankaran Thayumanavan
13.1 Introduction 397
13.2 Dendrimer Architectures 399
13.2.1 Dendrimer as a Chromophore 399
13.2.2 Dendrimer as a Scaffold 401
13.3 Electronic Processes in Light-Harvesting Dendrimers 403
13.3.1 Energy Transfer in Dendrimers 403
13.3.2 Charge Transfer in Dendrimers 405
13.4 Light-Harvesting Dendrimers in Clean Energy Technologies 407
13.5 Conclusion 413
References 414
14. Biomimicry in Organic Synthesis 419
Reinhard W. Hoffmann
14.1 Introduction 419
14.2 Biomimetic Synthesis of Natural Products 420
14.2.1 Potentially Biomimetic Synthesis 423
14.3 Biomimetic Reactions in Organic Synthesis 437
14.4 Biomimetic Considerations as an Aid in Structural Assignment 447
14.5 Reflections on Biomimicry in Organic Synthesis 448
References 450
15. Conclusion and Future Perspectives: Drawing Inspiration from the Complex System that Is Nature 455
Clyde W. Cady, David M. Robinson, Paul F. Smith, and Gerhard F. Swiegers
15.1 Introduction: Nature as a Complex System 455
15.2 Common Features of Complex Systems and the Aims of Systems Chemistry 457
15.3 Examples of Research in Systems Chemistry 460
15.3.1 Self-Replication, Amplification, and Feedback 460
15.3.2 Emergence, Evolution, and the Origin of Life 464
15.3.3 Autonomy and Autonomous Agents: Examples of Equilibrium and Nonequilibrium Systems 465
15.4 Conclusion: Systems Chemistry may have Implications in Other Fields 468
References 470
Index 473
