BIOINSPIRATION AND BIOMIMICRY IN CHEMISTRY -- CONTENTS -- Foreword: Jean-Marie Lehn -- Foreword: Janine Benyus -- Preface -- Contributors -- 1. Introduction: The Concept of Biomimicry and Bioinspiration in Chemistry -- 1.1 What is Biomimicry and Bioinspiration? -- 1.2 Why Seek Inspiration from, or Replicate Biology? -- 1.2.1 Biomimicry and Bioinspiration as a Means of Learning from Nature and Reverse-Engineering from Nature -- 1.2.2 Biomimicry and Bioinspiration as a Test of Our Understanding of Nature -- 1.2.3 Going Beyond Biomimicry and Bioinspiration -- 1.3 Other Monikers: Bioutilization, Bioextraction, Bioderivation, and Bionics -- 1.4 Biomimicry and Sustainability -- 1.5 Biomimicry and Nanostructure -- 1.6 Bioinspiration and Structural Hierarchies -- 1.7 Bioinspiration and Self-Assembly -- 1.8 Bioinspiration and Function -- 1.9 Future Perspectives: Drawing Inspiration from the Complex System that is Nature -- References -- 2. Bioinspired Self-Assembly I: Self-Assembled Structures -- 2.1 Introduction -- 2.2 Molecular Clefts, Capsules, and Cages -- 2.2.1 Organic Cage Systems -- 2.2.2 Metallosupramolecular Cage Systems -- 2.3 Enzyme Mimics and Models: The Example of Carbonic Anhydrase -- 2.4 Self-Assembled Liposome-Like Systems -- 2.5 Ion Channel Mimics -- 2.6 Base-Pairing Structures -- 2.7 DNA-RNA Structures -- 2.8 Bioinspired Frameworks -- 2.9 Conclusion -- References -- 3. Bioinspired Self-Assembly II: Principles of Cooperativity in Bioinspired Self-Assembling Systems -- 3.1 Introduction -- 3.2 Statistical Factors in Self-Assembly -- 3.3 Allosteric Cooperativity -- 3.4 Effective Molarity -- 3.5 Chelate Cooperativity -- 3.6 Interannular Cooperativity -- 3.7 Stability of an Assembly -- 3.8 Conclusion -- References -- 4. Bioinspired Molecular Machines -- 4.1 Introduction -- 4.1.1 Inspirational Antecedents: Biology, Engineering, and Chemistry.

4.1.2 Chemical Integration -- 4.1.3 Chapter Overview -- 4.2 Mechanical Effects in Biological Machines -- 4.2.1 Skeletal Muscle's Structure and Function -- 4.2.2 Kinesin -- 4.2.3 F1-ATP Synthase -- 4.2.4 Common Features of Biological Machines -- 4.2.5 Variation in Biomotors -- 4.2.6 Descriptions and Analogies of Molecular Machines -- 4.3 Theoretical Considerations: Flashing Ratchets -- 4.4 Sliding Machines -- 4.4.1 Linear Machines: Rotaxanes -- 4.4.2 Mechanistic Insights: Ex Situ and In Situ (Maxwell's Demon) -- 4.4.3 Bioinspiration in Rotaxanes -- 4.4.4 Molecular Muscles as Length Changes -- 4.5 Rotary Motors -- 4.5.1 Interlocked Rotary Machines: Catenanes -- 4.5.2 Unimolecular Rotating Machines -- 4.6 Moving Larger Scale Objects -- 4.7 Walking Machines -- 4.8 Ingenious Machines -- 4.8.1 Molecular Machines Inspired by Macroscopic Ones: Scissors and Elevators -- 4.8.2 Artificial Motility at the Nanoscale -- 4.8.3 Moving Molecules Across Surfaces -- 4.9 Using Synthetic Bioinspired Machines in Biology -- 4.10 Perspective -- 4.10.1 Lessons and Departures from Biological Molecular Machines -- 4.10.2 The Next Steps in Bioinspired Molecular Machinery -- 4.11 Conclusion -- References -- 5. Bioinspired Materials Chemistry I: Organic-Inorganic Nanocomposites -- 5.1 Introduction -- 5.2 Silicate-Based Bionanocomposites as Bioinspired Systems -- 5.3 Bionanocomposite Foams -- 5.4 Biomimetic Membranes -- 5.4.1 Phospholipid-Clay Membranes -- 5.4.2 Polysaccharide-Clay Bionanocomposites as Support for Viruses -- 5.5 Hierarchically Layered Composites -- 5.5.1 Layer-by-Layer Assembly of Composite-Cell Model -- 5.5.2 Hierarchically Organized Nanocomposites for Sensor and Drug Delivery -- 5.6 Conclusion -- References -- 6. Bioinspired Materials Chemistry II: Biomineralization as Inspiration for Materials Chemistry -- 6.1 Inspiration from Nature -- 6.2 Learning from Nature.

6.3 Applying Lessons from Nature: Synthesis of Biomimetic and Bioinspired Materials -- 6.3.1 Biomimetic Bone Materials -- 6.3.2 Semiconductors, Nanoparticles, and Nanowires -- 6.3.3 Biomimetic Strategies for Silica-Based Materials -- 6.4 Conclusion -- References -- 7. Bioinspired Catalysis -- 7.1 Introduction -- 7.2 A General Description of the Operation of Catalysts -- 7.3 A Brief History of Our Understanding of the Operation of Enzymes -- 7.3.1 Early Proposals: Lock-and-Key Theory, Strain Theory, and Induced Fit Theory -- 7.3.2 The Critical Role of Molecular Recognition in Enzymatic Catalysis: Pauling's Concept of Transition State Complementarity -- 7.3.3 The Critical Role of Approach Trajectories in Enzymatic Catalysis: Orbital Steering, Near Attack Conformers, the Proximity Effect, and Entropy Traps -- 7.3.4 The Critical Role of Conformational Motion in Enzymatic Catalysis: Coupled Protein Motions -- 7.3.5 Enzymes as Molecular Machines: Dynamic Mechanical Devices and the Entatic State -- 7.3.6 The Fundamental Origin of Machine-like Actions: Mechanical Catalysis -- 7.4 Representative Studies of Bioinspired/Biomimetic Catalysts -- 7.4.1 Important General Characteristics of Enzymes as a Class of Catalyst -- 7.4.2 Bioinspired/Biomimetic Catalysts that Illustrate the Critical Importance of Reactant Approach Trajectories -- 7.4.3 Bioinspired/Biomimetic Catalysts that Demonstrate the Importance and Limitations of Molecular Recognition -- 7.4.4 Bioinspired/Biomimetic Catalysts that Operate Like a Mechanical Device -- 7.5 The Relationship Between Enzymatic Catalysis and Nonbiological Homogeneous and Heterogeneous Catalysis -- 7.6 Selected High-Performance NonBiological Catalysts that Exploit Nature's Catalytic Principles -- 7.6.1 Adapting Model Species of Enzymes to Facilitate Machine-like Catalysis -- 7.6.2 Statistical Proximity Catalysts.

7.7 Conclusion: The Prospects for Harnessing Nature's Catalytic Principles -- References -- 8. Biomimetic Amphiphiles and Vesicles -- 8.1 Introduction -- 8.2 Synthetic Amphiphiles as Building Blocks for Biomimetic Vesicles -- 8.3 Vesicle Fusion Induced by Molecular Recognition -- 8.4 Stimuli-Responsive Shape Control of Vesicles -- 8.5 Transmembrane Signaling and Chemical Nanoreactors -- 8.6 Toward Higher Complexity: Vesicles with Subcompartments -- 8.7 Conclusion -- References -- 9. Bioinspired Surfaces I: Gecko-Foot Mimetic Adhesion -- 9.1 The Hierarchical Structure of Gecko Feet -- 9.2 Origin of Adhesion in Gecko Setae -- 9.3 Structural Requirements for Synthetic Dry Adhesives -- 9.4 Fabrication of Synthetic Dry Adhesives -- 9.4.1 Polymer-Based Dry Adhesives -- 9.4.2 Carbon-Nanotube-Based Dry Adhesives -- 9.5 Outlook -- References -- 10. Bioinspired Surfaces II: Bioinspired Photonic Materials -- 10.1 Structural Color in Nature: From Phenomena to Origin -- 10.2 Bioinspired Photonic Materials -- 10.2.1 The Fabrication of Photonic Materials -- 10.2.2 The Design and Application of Photonic Materials -- 10.3 Conclusion and Outlook -- References -- 11. Biomimetic Principles in Macromolecular Science -- 11.1 Introduction -- 11.2 Polymer Synthesis Versus Biopolymer Synthesis -- 11.2.1 Features of Polymer Synthesis -- 11.2.2 "Living" Chain Growth -- 11.2.3 Aspects of Chain Length Distribution in Synthetic Polymers: Sequence Specificity and Templating -- 11.3 Biomimetic Structural Features in Synthetic Polymers -- 11.3.1 Helically Organized Polymers -- 11.3.2 ß-Sheets -- 11.3.3 Supramolecular Polymers -- 11.3.4 Self-Assembly of Block Copolymers -- 11.4 Movement in Polymers -- 11.4.1 Polymer Gels and Networks as Chemical Motors -- 11.4.2 Polymer Brushes and Lubrication -- 11.4.3 Shape-Memory Polymers.

11.5 Antibody-Like Binding and Enzyme-Like Catalysis in Polymeric Networks -- 11.6 Self-Healing Polymers -- References -- 12. Biomimetic Cavities and Bioinspired Receptors -- 12.1 Introduction -- 12.2 Mimics of the Michaelis-Menten Complexes of Zinc(II) Enzymes with Polyimidazolyl Calixarene-Based Ligands -- 12.2.1 A Bis-aqua Zn(II) Complex Modeling the Active Site of Carbonic Anhydrase -- 12.2.2 Structural Key Features of the Zn(II) Funnel Complexes -- 12.2.3 Hosting Properties of the Zn(II) Funnel Complexes: Highly Selective Receptors for Neutral Molecules -- 12.2.4 Induced Fit: Recognition Processes Benefit from Flexibility -- 12.2.5 Multipoint Recognition -- 12.2.6 Implementation of an Acid-Base Switch for Guest Binding -- 12.3 Combining a Hydrophobic Cavity and A Tren-Based Unit: Design of Tunable, Versatile, but Highly Selective Receptors -- 12.3.1 Tren-Based Calix[6]arene Receptors -- 12.3.2 Versatility of a Polyamine Site -- 12.3.3 Polyamido and Polyureido Sites for Synergistic Binding of Dipolar Molecules and Anions -- 12.3.4 Acid-Base Controllable Receptors -- 12.4 Self-Assembled Cavities -- 12.4.1 Receptors Decorated with a Triscationic or a Trisanionic Binding Site -- 12.4.2 Receptors Capped Through Assembly with a Tripodal Subunit -- 12.4.3 Heteroditopic Self-Assembled Receptors with Allosteric Response -- 12.4.4 Interlocked Self-Assembled Receptors -- 12.5 Conclusion -- References -- 13. Bioinspired Dendritic Light-Harvesting Systems -- 13.1 Introduction -- 13.2 Dendrimer Architectures -- 13.2.1 Dendrimer as a Chromophore -- 13.2.2 Dendrimer as a Scaffold -- 13.3 Electronic Processes in Light-Harvesting Dendrimers -- 13.3.1 Energy Transfer in Dendrimers -- 13.3.2 Charge Transfer in Dendrimers -- 13.4 Light-Harvesting Dendrimers in Clean Energy Technologies -- 13.5 Conclusion -- References -- 14. Biomimicry in Organic Synthesis.

14.1 Introduction.