Chemical Physics of Redox Metalloenzyme Catalysis

Chemical Step
5.3 Collision of Reactants. Steric and Electrostatic Factors
5.4 Orientational Effects
5.5 Elementary Acts of Chemical Reactions
5.5.1 General Principles
5.5.2 Adiabatic Reactions. Activation Energy and Entropy
5.5.3 Inner-Sphere Non-Adiabatic Reactions. Quantum- Mechanical Selection Rules
5.5.4 Outer-Sphere Non-Adiabatic Reactions. Long-Range Tunnelling Processes
5.5.5 Synchronization of Nuclei in an Electronic Concerted Reaction
5.6 Activation of the Substrate in the Coordination Sphere of a Transition Metal. Specific Feature of the Structure of Clusters
5.7 The Principle of "Optimal Motion" in Elementary Acts of Chemical and Enzymatic Processes

6 Iron-Containing Proteins
6.1 Heme Proteins
6.1.1 Myoglobins and Hemoglobins
6.1.2 Cytochromes
6.1.3 Peroxidases
6.1.4 Catalase
6.1.5 Cytochrome P-450
6.2 Non-Heme Proteins
6.2.1 Ferredoxins
6.2.2 Iron-Sulphur Enzymes
6.2.3 Transport and Storage of Non-Heme Model Proteins

7 Iron- and Molybdenum-Containing Oxidoreductases
7.1 Xanthine Oxidase
7.1.1 General
7.1.2 Kinetics and Mechanism of the Xanthine Oxidase Reaction
7.2 Other Molybdenum-Containing Oxidoreductases
7.3 Nitrogenase
7.3.1 General
7.3.2 Kinetics and Mechanism of Nitrogenase Reactions
7.3.3 The Structure of Metal-Containing Active Sites
7.3.4 The ATPase Site

8 Copper-Containing Enzymes
8.1 Blue Copper-Containing Enzymes
8.1.1 Ceruloplasmin
8.1.2 Laccase and Ascorbate Oxidase
8.2 Copper-Containing Monooxygenases and Oxidases
8.3 Electron and Dioxygen Carriers

9 Electron-Transport and Energy-Transformation Systems
9.1 The Mitochondrial Respiratory Chain
9.2 Electron-Transfer and Water-Oxidation Systems in Photosynthesis
9.2.1 The Primary Photoelectron-Transport During Bacterial and Plant Photosynthesis
9.2.2 The Role of Manganese in the Photo-Oxidation of Water to O2
9.3 The Microsomal Oxidation System
9.4 The Methane-Hydroxylating System

10 Energy, Entropy and Molecular-Dynamic Relationships in Enzyme Catalysis
10.1 Relationships Between the Energy and Entropy Parameters of Enzymatic Processes
10.1.1 Experimental Data
10.1.2 Theoretical Treatment
10.2 Molecular-Dynamic Properties of Proteins and Enzymes
10.2.1 General
10.2.2 Methods of Studying the Intramolecular Dynamics of Proteins
10.2.3 Experimental Data on the Intramolecular Dynamics of Proteins
10.2.4 Theoretical Conception of the Intramolecular Dynamics of Proteins
10.2.5 Intramolecular Dynamics and Functional Properties of Proteins

11 Mechanisms of the Elementary Acts of Redox and Coupled Processes Involving Metalloenzymes and Carriers
11.1 One-Electron Transfer
11.1.1 Theoretical Concepts. General
11.1.2 Electron Transfer and Spin Exchange
11.1.3 Methods of Quantitative Estimation of the Electron-Transfer Parameters in Proteins
11.1.4 Experimental Data on One-Electron Transfer in Metalloenzymes
11.1.5 Electron Transfer in Photoseparation of Charges in Photosynthesis
11.2 Multi-Electron Mechanisms of Redox Reactions
11.2.1 General Principles
11.2.2 Two-Electron Reduction of Dioxygen
11.2.3 Oxidation and Hydroxylation Reactions Involving Heme Enzymes
11.2.4 The Four-Electron Mechanisms of Dinitrogen Reduction and Water Oxidation
11.3 The Chemical Mechanism of the ATPase Reaction in Energy-Conversion Systems
11.4 Conclusions
- References