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Bioinspiration and Biomimicry in Chemistry: Reverse-Engineering Nature

Bioinspiration and Biomimicry in Chemistry: Reverse-Engineering Nature

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Can we emulate nature's technology in chemistry?

Through billions of years of evolution, Nature has generated some remarkable systems and substances that have made life on earth what it is today. Increasingly, scientists are seeking to mimic Nature's systems and processes in the lab in order to harness the power of Nature for the benefit of society.

Bioinspiration and Biomimicry in Chemistry explores the chemistry of Nature and how we can replicate what Nature does in abiological settings. Specifically, the book focuses on wholly artificial, man-made systems that employ or are inspired by principles of Nature, but which do not use materials of biological origin.

Beginning with a general overview of the concept of bioinspiration and biomimicry in chemistry, the book tackles such topics as:

  • Bioinspired molecular machines
  • Bioinspired catalysis
  • Biomimetic amphiphiles and vesicles
  • Biomimetic principles in macromolecular science
  • Biomimetic cavities and bioinspired receptors
  • Biomimicry in organic synthesis

Written by a team of leading international experts, the contributed chapters collectively lay the groundwork for a new generation of environmentally friendly and sustainable materials, pharmaceuticals, and technologies. Readers will discover the latest advances in our ability to replicate natural systems and materials as well as the many impediments that remain, proving how much we still need to learn about how Nature works.

Bioinspiration and Biomimicry in Chemistry is recommended for students and researchers in all realms of chemistry. Addressing how scientists are working to reverse engineer Nature in all areas of chemical research, the book is designed to stimulate new discussion and research in this exciting and promising field.

Foreword xvii

Jean-Marie Lehn

Foreword xix
Janine Benyus

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

1.3 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

2.3 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

4.2 Mechanical Effects in Biological Machines 78

4.3 Theoretical Considerations: Flashing Ratchets 83

4.4 Sliding Machines 86

4.5 Rotary Motors 102

4.6 Moving Larger Scale Objects 104

4.7 Walking Machines 106

4.8 Ingenious Machines 109

4.9 Using Synthetic Bioinspired Machines in Biology 111

4.10 Perspective 111

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

5.5 Hierarchically Layered Composites 129

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

6.4 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

7.4 Representative Studies of Bioinspired/Biomimetic Catalysts 177

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

7.7 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

9.5 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

10.3 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

11.3 Biomimetic Structural Features in Synthetic Polymers 330

11.4 Movement in Polymers 343

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

12.3 Combining a Hydrophobic Cavity and A Tren-Based Unit: Design of Tunable, Versatile, but Highly Selective Receptors 377

12.4 Self-Assembled Cavities 383

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

13.3 Electronic Processes in Light-Harvesting Dendrimers 403

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

14.3 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

15.4 Conclusion: Systems Chemistry may have Implications in Other Fields 468

References 470

Index 473

“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)