Comprehensive Treatise of Electrochemistry

1. The Origin of Electrical Potential in Biological Systems.- 1. Electrical Potential of Biomolecules.- 1.1. Electrostatic Potential.- 1.2. Electrical Potential Due to Molecular Polarization.- 1.3. Potential Due to Electron Transfer Reaction.- 2. Electrical Potential at Biomolecular Interfaces.- 2.1. Equilibrium Interfacial Electrical Potentials.- 2.2. Nonequilibrium Interfacial Potential.- 3. Transmembrane Potential across Cell Membranes.- 3.1. Resting Membrane Potential.- 3.2. Excitation Potential.- 4. Molecular Interaction in Biological Systems.- 4.1. Short-range Repulsive Interactions.- 4.2. London Dispersion (van der Waals) Interactions.- 4.3. Electrical Double Layer Interaction and DLVO Theory.- 4.4. DLVO Theory Applied to Biological Systems.- 2. Electrochemistry of Low Molecular Weight Organic Compounds of Biological Interest.- 1. Introduction.- 2. Catecholamines.- 3. Phenothiazines.- 4. ?-Tocopherol and ?-Tocopherylquinone.- 5. Purines.- 6. Conclusions.- References.- 3. Electrochemistry of Biopolymers.- 1. Introduction.- 2. Proteins.- 2.1. Electrochemical Classification.- 2.2. Polyelectrolyte Behavior in Solution.- 2.3. Polyelectrolyte Behavior at Electrodes.- 2.4. Kinetics of Denaturation.- 2.5. Complexes with Dyes and Drugs.- 3. Polysaccharides.- 3.1. Adsorption.- 3.2. Electron Exchange.- 4. Nucleic Acids.- 4.1. Electrochemical Classification.- 4.2. Polyelectrolyte Behavior in Solution.- 4.3. Polyelectrolyte Behavior at Electrodes.- 4.4. Kinetics of Denaturation.- 4.5. Complexes with Dyes and Drugs.- 5. Nucleoproteins.- 5.1. Principles of Interactions.- 5.2. DNA-Histone Complexes.- 5.3. An Electrostatic Model.- 6. Outlook.- References.- 4. Bioelectrocatalysis.- 1. Introduction.- 2. Physicochemical Properties of Enzymes.- 2.1. Classification of Enzymes and Their Structure.- 2.2. The Mechanism of Enzymatic Catalysis.- 2.3. The Structure and Functions of Proteins—Electron Carriers and Enzymes.- 3. Methods of Immobilization of Enzymes.- 3.1. Immobilization by Adsorption.- 3.2. Immobilization by Inclusion into the Space Lattice of Gels.- 3.3. Chemical Methods of Immobilization.- 3.4. Properties of Immobilized Enzymes.- 4. Electrochemical Properties of Protein Macromolecules and Their Active Groups.- 4.1. Electrochemical Properties of Active Groups.- 4.2. Redox Transformations of Proteins and Enzymes on Electrodes.- 5. Methods of Conjugation of Electrochemical and Enzymic Reactions.- 6. The Use of Enzymes to Accelerate Electrochemical Reactions.- 6.1. Hydrogen Reaction.- 6.2. Oxygen Reaction.- 6.3. Oxidation of Organic Compounds.- 7. Mechanism of Bioelectrocatalysis.- 7.1. Maximum Rates of Bioelectrocatalytic Reactions.- 7.2. The State of Adsorptionally Immobilized Enzymes.- 7.3. Electron Transfer in the Mediatorless Method of Bioelectrocatalysis.- 8. Prospects for Practical Utilization of Bioelectrocatalysis.- References.- 5. Electrochemical Aspects of Bioenergetics.- 1. Introduction.- 2. Interfacial Properties of Electrodes and Biological Membranes.- 2.1. The Metal Electrode/Aqueous Solution Interface.- 2.2. The Semiconductor Electrode/Aqueous Solution Interface.- 2.3. Biological Membranes.- 3. Thermodynamic Studies of Biological Molecules.- 3.1. Optically Transparent Thin-Layer Electrochemistry.- 3.2. Indirect Coulometric Titrations at Optically Transparent Electrodes.- 4. Kinetics and Mechanisms of Biological Electron Transfer Reactions.- 4.1. Homogeneous Electron Transfer Kinetic Studies.- 4.2. Heterogeneous Electron Transfer Kinetic and Mechanistic Studies.- 5. Conclusions.- References.- 6. Electrochemical Aspects of Metabolism.- 1. Introduction.- 1.1. Objectives.- 1.2. Scope.- 2. The Living Cell as an Electrochemical System.- 2.1. Structural Analogies between Living Cells and Electrochemical Devices.- 2.2. Examples of Electrochemical Phenomena in Living Systems.- 2.3. Mechanisms of Electric Field Generation and Charge Conduction.- 2.4. Coordination of Proton and Metabolic Flux.- 3. Electrochemical Regulation of Metabolism.- 3.1. Some Unanswered Questions.- 3.2. Current Concepts of Metabolic Regulation.- 3.3. Influence of Cellular Electric Fields on Metabolic Processes.- 3.4. Mechanisms of “Reversed Electron Transfer”.- 3.5. Regulation of Energy Flow and Heat Production.- 4. Electrochemical Processes and Disease.- 4.1. The Free Radical Theory of O2 Toxicity.- 4.2. The Rate and Function of Superoxide Production.- 4.3. Possible Roles of Superoxide in Hormonal and Neuromuscular Signal Transmission.- 4.4. Possible Mechanisms by which Superoxide Brings About Cell Damage and Promotes Lipid Peroxidation.- 4.5. Conclusion.- References.- 7. Electrochemistry of the Nervous Impulse.- 1. Introduction.- 1.1. Historical Background.- 1.2. The Nerve Cell.- 1.3. Excitation Phenomenon.- 1.4. Hodgkin-Huxley Equations.- 2. Electrochemical models of the Nerve Fiber.- 2.1. Lillie-Bonhoeffer Model.- 2.2. Teorell’s Electrokinetic Model.- 3. Excitation Propagation.- 3.1. Reduced Hodgkin-Huxley Equations.- 3.2. Ionic Current Generator Model.- 3.3. Activity Wave in a Neuron Net.- 4. Ionic Transport across Membranes.- 4.1. Electrodiffusion Equation.- 4.2. Bilayer Lipid Membranes.- 4.3. Induced Ionic Transport.- 5. Channels in Biomembranes.- 5.1. Facts and Hypotheses.- 5.2. Conductance Control by Electric Field.- 5.3. Open Channels: Selectivity and Conductance.- 6. Conclusions.- References.- 8. Electrochemical Approach for the Solution of Cardiovascular Problems.- 1. Introduction.- 1.1. Definition of Terms—Thrombosis, Thromboembolic Disease, Atherosclerosis, and Blood Clotting.- 1.2. Evidence for Electrochemical Mechanisms in Cardiovascular Phenomena.- 2. Hematological and Electrochemical Aspects of Blood Coagulation Mechanisms.- 2.1. The Hematologists’ View of the Blood Coagulation Sequence.- 2.2. The Role of Blood Cells, Particularly Platelets, in Blood Coagulation.- 2.3. Electrosorption and Electron Transfer Reactions of Some Blood Coagulation Factors at Metal-Electrolyte Interfaces.- 2.4. Adsorption Reactions of Some Blood Coagulation Factors at Insulator-Solution Interfaces.- 3. An Electrokinetic Approach for the Characterization of the Blood Vessel Walls and of Blood Cells and for the Selection of Anticoagulant Drugs.- 3.1. Surface Charge Characteristics of Blood Vessel Walls Using Streaming Potential and Electroosmosis Techniques.- 3.2. Surface Charge Characteristics of Blood Cells Using Mainly Electrophoresis and to a Limited Extent Sedimentation Potential Techniques.- 3.3. Correlations between Effects of Drugs on the Surface Charge Characteristics of the Vascular System and their Pro- or Antithrombogenic Properties.- 4. An Electrochemical Approach for the Selection of Vascular and Heart Valve Prostheses.- 4.1. Electronically Conducting Materials.- 4.2. Insulator Materials.- 5. Conclusions.- References.- 9. Electrochemical Techniques in the Biological Sciences.- 1. Electroanalytical Techniques.- 1.1. Bioelectrodes.- 1.2. Analytical Applications of Bioelectrodes.- 2. Electrophysiology.- 2.1. Measurement of Transmembrane Potential.- 2.2. Stimulation of Excitable Cells.- 2.3. Control of Membrane Potential (Voltage Clamping).- 2.4. Iontophoresis.- 2.5. EEG, EMG, ECG.- 3. Electrobiology.- 3.1. Stimulation of Nonexcitable Cells.- 3.2. In Vivo Electrokinetic Potentials.- 3.3. Microbial Electrochemistry.- References.