Mechanical catalysis: methods of enzymatic, homogeneous, and heterogeneous catalysis

This book discusses the fundamental processes at work in mechanical catalysis, the origin of its general and physical features, the way it has evolved in many enzymes, and how it relates to catalysis in man-made systems. It ties together the thirty-plus existing theories of enzymatic catalysis, covers design issues in the creation of biomimetic catalysts (including requirements, problems, approaches, and solutions), explains the difference between energy- and time-dependent catalysis, and interfaces with the hot ideas of complexity and complex systems science. This book has large implications and could revolutionizeour understanding of catalysis. INDICE: Glossary. The Contributors. Chapter 1: Introduction. Thermodynamic("Energy-Dependent") and Mechanical ("Time-Dependent") Processes. What are they and how they Manifest in Chemistry and catalysis? The Aims, Structure, and Key Findings of this Series (Gerhard F. Swiegers). 1.1 Thermodynamic (Energy-Dependent ) and Mechanical (Time Dependent ) Processes. 1.2 What is a Thermodynamic Process? 1.3 What is a Mechanical Process? 1.4 The Difference between an Energy-Dependent (Thermodynamic) and a Time-Dependent (Mechanical) Processes. 1.5 Time- and Energy-Dependence in Chemistry and Catalysis. 1.6 The Aims, Structure, and Major Findings of this Series. 1.7 References. Chapter 2: Background. Heterogeneous, Homogeneous, and Enzymatic Catalysis. A Shared Terminology and Conceptual Platform. The Alternative of Time-Dependence in Catalysis (Gerhard F. Swiegers). 2.1 Introduction: The Problem of Conceptually Unifying Heterogeneous, Homogeneous, and Enzymatic Catalysis. 2.2 Background: What is Heterogeneous, Homogeneous, and Enzymatic Catalysis? Trends in Catalysis Science.. 2.3 Distinctions Within Homogeneous Catalysis: Single- and Multi-Centered Homogeneous Catalysis. 2.4 The Distinction between Single- / Multi-Site Catalysts and Single- / Multi-Centered Catalysts in Heterogeneous Catalysis. An Important Convention Used in this Series. 2.5 The Alternative of Time-Dependence in Catalysis. 2.6 References . Chapter 3: Theory. A Conceptual Description of Energy-Dependent ("Thermodynamic") and Time-Dependent ("Mechanical") Processes in Chemistry and Catalysis (Gerhard F. Swiegers). 3.1 Introduction. 3.2 Theoretical Considerations: Common Processes in Uncatalyzed Reactions. 3.3 Theoretical Considerations: Common Processes in Catalyzed Reactions. 3.4 Conclusions: Energy-and Time-Dependent Catalysis. 3.5 Acknowledgements. 3.6 References . Chapter 4: Time-Dependence in Heterogeneous Catalysis. Sabatier's Principle Describes Two Independent Catalytic Realms: Time-Dependent ("Mechanical") Catalysis and Energy-Dependent ("Thermodynamic") Catalysis (Gerhard F. Swiegers). 4.1 Introduction. 4.2 Sabatier's Principle in Heterogeneous Catalysis. 4.3 Exceptions toSabatier's Principle . 4.4 Sabatier's Principle in Homogeneous Catalysis. 4.5Conclusions. Sabatier's Principle Describes Two Independent Catalytic Domains: Energy- and Time-Dependent Catalysis. 4.6 Acknowledgements. 4.7 References .Chapter 5: Time-Dependence in Homogeneous Catalysis. 1. Many Enzymes Display the Hallmarks of Time-Dependent ("Mechanical") Catalysts. Non-Biological Homogeneous Catalysts are Typically Energy-Dependent ("Thermodynamic") Catalysts (Robin Brimblecombe, Jun Chen, Junhua Huang, Ulrich T. Mueller-Westerhoff, and Gerhard F. Swiegers). 5.1 Introduction. 5.2 Historical Background: Are Enzymes Generally Energy-Dependent or Time-Dependent Catalysts? 5.3 The Methodology ofthis Chapter: Identify, Contrast, and Rationalize the Common Processes Present in Biological and Non-Biological Homogeneous Catalysts. 5.4 Does Michaelis-Menten Kinetics in Enzymes indicate that they are Time-Dependent Catalysts? 5.5Other General Characteristics of Catalysis by Enzymes and Comparable Non-Biological Homogeneous Catalysts. 5.6 Rationalization of the Underlying Processes.The Mechanism of Action in Time-Dependent and Energy-Dependent Catalysts. 5.7All of the Generalizations Support Time-Dependence in Enzymes . 5.8 Time-Dependence in a Non-Biological Catalyst Generates the Distinctive Properties of Enzymes. 5.9 Conclusion: Many Enzymes are Time-Dependent Catalysts . 5.10 Acknowledgements. 5.11 References . Chapter 6: Time-Dependence in Homogeneous Catalysis. 2. The General Actions of Time-Dependent ("Mechanical") and Energy-Dependent ("Thermodynamic") Catalysts (Robin Brimblecombe, Jun Chen, Junhua Huang, Ulrich T. Mueller-Westerhoff, and Gerhard F. Swiegers). 6.1 Introduction. 6.2 Time- and Energy-Dependent, Multi-Centered Homogeneous Catalysts. 6.3 The Action of Energy-Dependent, Multi-Centered Homogeneous Catalysts. 6.4 The Action ofTime-Dependent, Multi-Centered Homogeneous Catalysts. 6.5 The Importance of Recognizing Time-Dependent Catalysis. 6.6 Time-Dependent Catalysis is Very Different to Energy-Dependent Catalysis and Therefore Appears Unfamiliar . 6.7 Conclusions for Biology. 6.8 Conclusions for Homogeneous Catalysis. 6.9 The "Ideal" Homogeneous Catalyst. 6.10 Conclusions for the Conceptual Unity of the Field of Catalysis . 6.11 Acknowledgements. Chapter 7: Unifying the Many Theories of Enzymatic Catalysis. Theories of Enzymatic Catalysis Fall into Two Camps: Energy-Dependent ("Thermodynamic") and Time-Dependent ("Mechanical") Catalysis (Gerhard F. Swiegers). 7.1 Introduction. 7.2 Theories of Enzymatic Catalysis. 7.3 Theories Explaining Enzymatic Catalysis fall into Two Camps: Energy-Dependent and Time-Dependent Catalysis. 7.4 Studies Verifying Pauling's Theory in Model Systems are Correct, but Describe Energy-Dependent and not Time-Dependent Catalysis. 7.5 The Anomaly Described in the Spatiotemporal Hypothesis Arises, in Part, from the Onset of Time-Dependence. 7.6 Acknowledgements. 7.7 References . Chapter 8: Synergy in Heterogeneous, Homogeneous, and Enzymatic Catalysis. The "Ideal" Catalyst (Gerhard F. Swiegers). 8.1 Introduction. 8.2 Synergy inHeterogeneous Catalysts. 8.3 Single-Centered Non-Biological Homogeneous Catalysts and their "Mutually-Enhancing" Synergies. 8.4 Multi-Centered, Energy-Dependent Homogeneous Catalysts and their Functionally-Complementary Synergies. 8.5 Enzymes and their Functionally-Convergent Synergies . 8.6 Biomimetic Chemistry and its Pseudo-Convergent Synergies. 8.7 The Spectrum of Synergistic Actionin Homogeneous Catalysis. 8.8 Synergy in Catalysis is Conceptually Related toOther Synergistic Processes in Human Experience . 8.9 References . Chapter 9:A Conceptual Unification of Heterogeneous, Homogeneous, and Enzymatic Catalysis (Gerhard F. Swiegers). 9.1 Introduction. 9.2 Diffusion-Controlled and Reaction-Controlled Catalysis. 9.3 The Diversity of Catalytic Action in Heterogeneous Catalysts. 9.4 The Diversity of Catalytic Action in Non-Biological Homogeneous Catalysts. 9.5 The Diversity of Catalytic Action in Enzymes. 9.6 Heterogeneous Catalysis and Enzymatic Catalysis has, effectively, involved Combinatorial Experiments that have Produced Time-Dependent Catalysts. Non-Biological Homogeneous Catalysis has not. 9.7 Homogeneous and Enzymatic Catalysts are the 3-DEquivalent of 2-D Heterogeneous Catalysts. 9.8 A Conceptual Unification of Heterogeneous, Homogeneous, and Enzymatic Catalysis. 9.9 References. Chapter 10:The Rational Design of Time-Dependent ("Mechanical") Homogeneous Catalysts. ALiterature Survey of Multi-Centered Homogeneous Catalysis (Junhua Huang, and Gerhard F. Swiegers). 10.1 Introduction. 10.2 The Rational Design of Time-Dependent Homogeneous Catalysts. 10.3 Elements of Rational Design in Multi-Centered Catalysis. 10.4 A Review of Non-Biological, Multi-Centered Molecular Catalysts Described in the Chemical Literature. 10.5 Acknowledgements. 10.6 References . Chapter 11: Time-Dependent ("Mechanical") Non-Biological Catalysis. 1. A Fully-Functional Mimic of the Water-Oxidizing Center (WOC) in Photosystem II (PSII) (Robin Brimblecombe, G. Charles Dismukes, Greg A. Felton, Leone Spiccia, and Gerhard F. Swiegers). 11.1 Introduction. 11.2 The Physical and Chemical Properties of the Cubanes 1a-b . 11.3 Nafion Provides a Means of Solubilizing and Immobilizing Hydrophobic Metal Complexes. 11.4 Photoelectrochemical Cells and Dye-Sensitized Solar Cells for Water-Splitting. 11.5 Photocatalytic Water Oxidation by Cubane 1b Doped into a Nafion Support. 11.6 The Challenge of Dye-Sensitized Water-Splitting. 11.7 The Mechanism of the Catalysis. 11.8 Conclusions. 11.9 References. Chapter 12: Time-Dependent ("Mechanical") Non-Biological Catalysis. 2. Highly-Efficient, "Biomimetic" Hydrogen-Generating Electrocatalysts. Jun Chen, Junhua Huang, Gerhard F. Swiegers, Chee O. Too, and Gordon G. Wallace). 12.1 Introduction. 12.2 Monomer and Polymer Preparation. 12.3 Catalytic Experiments. 12.4 Conclusions: A Combinatorial "Statistical Proximity" Catalyst was Obtained as a Bulk, Hybrid Homogeneous-Heterogeneous Catalyst. 12.5 Acknowledgements. 12.6 References. Chapter 13: Time-Dependent ("Mechanical") Non-Biological Catalysis. 3. A Readily-Prepared, Convergent, Oxygen-Reduction Electrocatalyst (Jun Chen, Gerhard F. Swiegers, Gordon G. Wallace, and Weimin Zhang). 13.1 Introduction. 13.2 Co-Facial Diporphyrin Oxygen Reduction Catalysts.13.3 Vapor-Phase Polymerization of Pyrrole as a Means of Immobilizing High Concentrations of Monomeric Catalytic groups at an Electrode Surface. 13.4 Preparation and Catalytic Properties of PPy-3. 13.5 PPy-3 as a Fuel Cell Catalyst. 13.6 Conclusions. 13.6 References. Appendix A. Why Is Saturation Not Observed in Catalysts that Display Conventional Kinetics. Appendix B. Graphical Illustration of the Processes Involved in the Saturation of Molecular Catalysts.

• ISBN: 978-0-470-26202-3
• Editorial: John Wiley & Sons
• Encuadernacion: Cartoné
• Páginas: 352
• Fecha Publicación: 10/10/2008
• Nº Volúmenes: 1
• Idioma: Inglés