Kinetics and catalysis in microheterogeneous systems

Cover......Page 1
Half Title......Page 2
Series Page......Page 3
Title Page......Page 6
Copyright Page......Page 7
Preface......Page 10
Contributors......Page 12
Table of Contents......Page 16
 I. Introduction......Page 20
 II. Micelles......Page 22
 III. Reversed Micelles and Microemulsions......Page 24
 IV. Lipid Bilayer Vesicles and Multilayer Assemblies......Page 25
 V. Inorganic Colloids......Page 26
 References......Page 29
 I. Introduction......Page 32
 II. Micellar Effects on Spontaneous Reactions......Page 36
 III. Micellar Effects on Nonsolvolytic Bimolecular Reactions......Page 39
  A. Direct Estimation of Reactant Distribution......Page 41
  B. Pseudophase Ion Exchange Model......Page 44
  C. Reactive Ion Micelles......Page 46
  D. Limitations of Simple Exchange Models......Page 48
 IV. Coulombic Models of Ion Binding......Page 49
  A. Treatment of Inhibited Reactions of Coions......Page 52
  B. Comparison of PIE and PBE Models......Page 53
 V. Functional Micelles......Page 55
 VI. Rate Constants in Micellar and Aqueous Pseudophases......Page 58
 VII. Simple Predictions of Rate Effects......Page 59
 References......Page 62
3 Kinetics of Intramicellar Reactions Simulated by Stochastic and Diffusion Models......Page 68
 II. Some Properties of Micellar Systems......Page 69
  A. The Poisson Distribution......Page 70
  C. The Geometric Distribution......Page 71
  D. The Fission/Fusion Mechanism......Page 72
  E. Distribution of Electronically Excited States in Micelles......Page 73
 IV. A Basic Stochastic Model for Intramicellar Reaction Kinetics......Page 74
 V. Diffusion Models for the Case of Reactants Confined to the Interior of Micelles......Page 75
  B. The Moving Reactant Model......Page 76
 VI. Diffusion and Stochastic Models for the Case Where One Reactant is Confined to the Interior of a Sphere and the Other to the Surface......Page 78
 VII. A Diffusion Model for the Case Where all Reactants are Confined to the Surface of a Sphere......Page 79
 References......Page 80
4 Kinetics of Excited State Processes in Micellar Media......Page 82
 I. Introduction......Page 83
 II. Preliminaries......Page 84
  A. The Intramicellar Process......Page 85
  B. Solubilization: Equilibrium Distribution and Kinetics......Page 87
 III. Small Monodisperse Micelles......Page 90
  A. Stationary Probes and Quenchers......Page 91
  B. Migration and Exchange......Page 93
  A. Theory......Page 107
  B. Experimental Demonstration: The Sphere-to-Rod Transition......Page 109
  A. The Infinite Cylinder......Page 112
  B. Two-Dimensional Systems......Page 115
  C. Diffusion-Controlled Deactivation in Zero to Three Dimensions: An Experimental Comparison......Page 122
 VI. Reversed Micelles......Page 124
 VII. Conclusions......Page 127
 References......Page 128
 I. Introduction......Page 134
 II. The Way to Look at the Micellar System, and the Problem of Pictorial Representation......Page 135
 III. Geometric Models and Thermodynamics: A Strange Harmony......Page 139
 IV. The Question of the \"Overall\" and \"Water Pool\" Concentrations, and the Shortcomings of the \"Pseudophase\" Model......Page 141
 V. The Equivalent Pseudophase Model and the Enzymatic Reactions......Page 144
 VI. Enzymatic Reactions in Micelles, Microheterogeneity, and the Question of the Local ω0......Page 147
 VII. Concluding Remarks......Page 151
 References......Page 152
6 Catalysis by Enzymes Entrapped in Hydrated Surfactant Aggregates Having Various Structures in Organic Solvents......Page 154
 I. Introduction......Page 155
  A. Geometry of Surfactant Aggregates......Page 158
  B. Entrapment of Enzymes in Surfactant Aggregates of Different Structures......Page 160
 III. Catalysis by Enzymes Entrapped in Hydrated Aggregates with Lamellar, Hexagonal, and Cubic Packing of Surfactant Molecules......Page 161
  A. Regulation of Enzyme Activity by Variation of the Structural Type of the Surfactant Matrix......Page 164
  B. Regulation of Enzyme Activity by Variation of Geometric Dimensions of the Surfactant Matrix......Page 167
 IV. Catalysis by Enzymes Entrapped in Reverse Micelles Solvated by Water-Miscible Organic Solvent......Page 174
 V. Catalytic Activity-Conformational Mobility Relationships: Superactivity in Micellar Medium......Page 178
  A. Regulation of Enzyme Activity by Variation of Surfactant Concentration......Page 180
  B. Conformational Mobility and Substrate Specificity of α-Chymotrypsin......Page 185
 VI. A New Strategy for Studying Oligomeric Enzymes......Page 187
 VII. On the Role of Aqueous Microenvironment in Enzymatic Catalysis: A Critical Content of Water in Micellar Medium......Page 190
 VIII. Conclusion......Page 192
 References......Page 193
 I. Biological vs Chemical Transmembrane Charge Separation......Page 202
 II. Guiding Principles......Page 206
 III. Transverse Diffusion—Some Practical Aspects......Page 214
  A. Reactions across PC Liposomes......Page 216
  B. Reactions across DHP Vesicles......Page 219
 V. Mechanistic Footnotes to Other Chemical Systems......Page 223
 VI. Systems Utilizing Biological Molecules......Page 228
 VII. Toward Membrane-Based Technologies: Prospects and Challenges......Page 239
 References......Page 241
8 Dynamics of Lateral Charge Transport in Bilayer Assemblies of Electrochemically Active Amphiphiles......Page 246
 I. Introduction......Page 247
  A. Microhetergeneous Electrocatalytic Assemblies......Page 248
  A. Porous Aluminum Oxide: A Template for the Directional Assembly of Amphiphilic Bilayers......Page 250
  B. Dynamics of Lateral Charge Transport in Amphiphilic Bilayer Assemblies......Page 254
  C. Structural and Dynamic Effects Induced by Intercalation of Octanol......Page 257
  D. Mechanism of Lateral Charge Transport......Page 263
  A. Design of the Electrocatalytic Assembly......Page 266
  B. Electron Transport......Page 269
  C. Dynamics of the Electrocatalytic Processes......Page 270
  D. Kinetics of Ascorbic Acid Oxidation......Page 275
  A. Design and Functioning of the Electroenzymatic Assembly......Page 276
  B. Dynamics of Electron Transport......Page 278
  A. The Interdigitated Array of Microelectrodes......Page 281
  B. Steady-State Charge Transport in Bilayer Assemblies......Page 282
 References......Page 289
9 Stereochemistry of Lipid Aggregates and Their Growth and Separation Processes......Page 292
 I. Planar Lipid Sheets......Page 293
 II. Geometric Models for Micelles, Micellar Rods, and Vesicles......Page 294
 III. Orientation of Monolayered and Bilayered Vesicle Membranes......Page 296
 IV. Micellar Fibers in the Form of Rods, Helices, Twisted Ribbons, and Scrolls......Page 299
 V. Dissolution and Separation of Dyes in Lipid Aggregates......Page 308
 VII. Separation of Chiral Superstructures......Page 311
 VIII. Conclusion......Page 316
 References......Page 317
10 Redox Reactions on Colloidal Metals and Metal Oxides......Page 322
  A. Synthesis of Metal Oxide and Metal Colloids for Redox Catalysis......Page 323
  B. Characterization of Colloids......Page 327
  A. The Metal Oxide-Aqueous Solution Interface......Page 330
  B. The Metal-Aqueous Solution Interface......Page 342
  A. Introduction and Principles of Redox Reactions on Metal Colloids......Page 343
  B. Hydrogen Evolution and Redox Catalysis on Colloidal Metals......Page 348
  C. Polymeric Stabilization and Particle Size Effects......Page 353
  E. Ultrasmall Metallic Clusters......Page 354
 V. Charge Transfer Reactions on Metal Oxide Colloids......Page 357
  A. Charge Trapping and Charge Recombination in Metal Oxide Colloids......Page 361
  B. Quantum Size Effects in Metal Oxide Colloids......Page 364
  C. Thermodynamics of Charge Transfer to Metal Oxide Colloids......Page 366
  D. Interfacial Electron Transfer to/from Metal Oxide Colloids......Page 369
  E. Proton Transfer to Metal Oxide Particles......Page 373
  F. Catalytic Systems and Reductive Dissolution......Page 374
  G. Surface Modification and Interparticle Transfer......Page 379
 References......Page 380
11 Photophysics, Photochemistry and Photocatalytic Aspects of Semiconductor Clusters and Colloids......Page 394
 I. Introduction......Page 395
  A. Colloidal Suspensions in Aqueous and Nonaqueous Media......Page 396
  B. Colloidal Particles in Heterogeneous Media......Page 398
  C. Modification of Semiconductor Surface......Page 400
  A. Size Quantization Effects......Page 404
  B. Emission Characteristics......Page 406
  C. Nonlinear Optical Properties......Page 411
 IV. Trapping of Charge Carriers......Page 414
  A. Photochemical Changes Associated with Trapped Electrons......Page 415
  B. Photochemical Changes Associated with Trapped Holes......Page 417
  C. Photoelectron Emission......Page 419
  A. Photocatalytic Reduction......Page 420
  B. Photocatalytic Oxidation......Page 427
  C. Reaction with Radiolytically Generated Redox Species......Page 430
  D. Photocorrosion......Page 431
 VI. Photosensitized Charge Injection Process......Page 433
  A. Dye Sensitization......Page 434
  B. Utilization of Charge Injected into the Semiconductor......Page 440
  C. Coupled Semiconductors......Page 442
 References......Page 445
 I. Introduction......Page 456
 II. Choice of the Solid: The Attractiveness of Solids of Low Dimensionality......Page 457
 III. Choice of the Reaction to be Improved......Page 459
 IV. Brønsted Surface Acidities of Claysnsted Surface Acidities of Clays......Page 460
 V. Stabilization of Polar Intermediates and Transition States by Clay Surfaces......Page 462
  A. Oxidative Rearrangements......Page 464
  B. Supported Lewis Acids......Page 466
  C. Friedel-Crafts Alkylation......Page 468
  D. Aromatic Chlorinations Catalyzed by Suitable Zeolites......Page 471
  E. Aromatic Nitrations......Page 472
 VII. Conclusion......Page 476
 References......Page 477
 I. Introduction......Page 480
  A. Zeolite Structure......Page 481
  B. Framework Composition and Ion Exchange......Page 482
  A. Electrochemistry in/on Zeolites......Page 483
  B. Electron Transfer Catalysis......Page 487
  A. Light-Induced Electron Transfer Reactions on Zeolite Surfaces......Page 493
  B. Organic Photochemical Reactions in Zeolite Cages......Page 499
 References......Page 505
 I. Introduction......Page 510
 II. Models for Dynamically Controlled Relaxation......Page 515
  A. Direct Energy Transfer......Page 516
  B. Relaxation of a Target......Page 523
 III. Applications to Porous Systems......Page 527
 References......Page 530
Index......Page 532