Riassunto
As a result of the pioneering efforts of Eigen, de Maeyer, Norrish and Porter, the kinetics of fast reactions in solution can now be studied using chemical relaxation methods, as well as many other fast reactions techniques. These methods have been applied successfully in many branches of the natural sciences. The simultaneous growth in the number of investiga tors and the diversity of their research interests has inevitably led to communication problems. The purpose of the NATO Advanced Study Institute entitled "New Applications of Chemical Relaxation Spectrometry and Other Fast Reaction Methods in Solution", was to create a forum so that research scientists working in different areas concerned with fast reactions could interact. This meeting was held at the Llandinam Building, University College of Wales, Aberystwyth from September 10th-20th, 1978. In addition to lectures on techniques and theory, two days of the NATO Advanced Study Institute, were spent discussing the current state of the art in this field. This two day meeting was also run under the auspices of the Chemical Society, Fast Reactions in Solution Group. The papers in this volume are the result of the contribu tions given in the Aberystwyth meeting. We have attempted to make this volume useful for the non-expert and a comprehensive introduction to theory, as well as the instrumentation used in the studies are discussed in detail.
Contenuti
The Study of Fast Reactions in Solution.- Fast Continuous Flow.- Computer-Controlled Repetitive Operation of a Stopped-Flow Spectrophotometer with a Magnetic Valve in Place of the Stopping Syringe.- Stopped-Flow Measurements in the Infrared: Simulated Rapid Scan Spectra: Some Observations on the Reactions of Metal Carbonyl Compounds with Halogen.- Solvent-Jump Method.- Conventional and U.V. Flash Temperature-Jump.- Laser Temperature Jump.- Laser T-Jump Arrangement with Time Resolution in the Second to Picosecond Range.- Highly Sensitive and Very Fast Chemical Relaxation Temperature-Jump Apparatuses.- High-Resolution Temperature Jump Measurements Using Cooling-Correction.- Circular Dichriosm Measurements at Millisecond Time Resolution: Stopped-Flow CD and Temperature-Jump CD Systems.- Recent Developments and Applications of Pressure-Jump Methods.- Electric Field Methods.- Destriau-Effect in Aqueous Solution.- Dielectric Relaxation.- Ultrasonic Relaxation Techniques.- Optical Ultasonic Techniques.- Light Scattering Study of Ultrasonic Relaxation in Liquid Furan-Cyclohexane Mixtures.- Brillouin Scattering Spectrometry.- Data Capture and Processing in Chemical Relaxation Measurements.- A Mocroprocessor Based System to Collect, Display, and Evaluate Stopped-Flow and Other Kinetic Data.- An Automatic Self-Scaling Transient Recorder.- Applications of Kinetic Polychromators to Fast Reaction Techniques.- Picosecond Time Resolved Fluorescence Spectroscopy.- Fourier Transform Photoacoustic Spectroscopy.- A Textbook Example of Complex Kinetics.- Thermodynamics of Relaxation Methods.- Relaxation Amplitudes in Concentration Jump Experiments. Application to Anthocyanins.- Equilibrium Studies on the Self-Association of Drugs in Aqueous Solution.- Relaxation Spectra Associated with Multistep Processes.- Ultrasonic Relaxation Studies of the Kinetics of Stacking, Conformational Transitions and Proton Transfers in Aqueous Solutions of Molecules and Macromolecules of Biological Interest.- Raman Laser Temperature Jump Study of Solvent Effects on Simple Stacking Systems.- The Kinetics of Micelle Formation.- A Treatment of the Kinetics of Mixed Micelles.- Solubilization of Acridine Orange by Triton-305.- Kinetic Studies of Synthetic Polymer/Surfactant Complexes.- Ultasonic Investigation of the Solubilization of an Alcohol in Viscoelastic Micelle Forming Systems.- Reaction Kinetics in Aqueous Micellae Systems: The Mechanism of the Reaction Between Ni2+ (aq) and Neutral Bidentate Ligands of Differing Hydrophobicities in the Presence of Sodium Dodecyl Sulphate Micelles.- Kinetics and Mechanism of Metal-Complex Formation in Aqueous Micellar and Inverse-Micellar Systems.- Application of a Metal Ion/Murexide Indicator System to the Study of Micellar Phenomena.- The Application of Fast-Reaction Methods to Reactions of Transition-Metal Ions and Complexes.- Kinetic Studies on the Complex Formation of Nickel(II) Ions with Pyridine-2-Azo-p-Dimethylamine (Pada) in Nonaqueous Solvents at Pressures from 1 Bar to 2 kBar.- Kinetics of the Reaction of Imidazoles With Iron(III) Porphyrin Chlorides.- The Application of a Dye-Laser Photochemical Relaxation Technique to the Study of Metal-Ligand Substitution Reactions in Aqueous and Micellar Solutions.- The Kinetics of the Formation of the BeSO4 Complex in H2O-Dmso Mixtures.- Vibrational and Ultrasonic Relaxation Spectra of Some Sodium Salts in Dimethylacetamide.- Microwave Dielectric Relaxation of Lithium Salts in Media of Low Permittivity at t = 25°C.- Crown Ether Reaction Kinetics.- Estimation of the Ration of Solvent Separated to Contact Ion Pairs by High Field Conductivity Measurements.- Dynamic Aspects of Ionic Aggregation in Low Polar Media.- Exchang Kinetics of Complexes of Diamagnetic Cations with Nonamethylimidodiphosphoramide, Studied by NMR.- Polysaccharide Conformation and Interactions in Solutions and Gels.- Biological Application: Kinetics of the Interaction Between Proflavine and DNA.- Interaction between Poly(Styrene Sulfonic Acid) and a “Bifunctional” Cationic Dye.- Temperature Jump Studies on Acridine Orange — Carboxy-Methylcellulose Complexes.- Fast Kinetics by NMR: Binding and Release of Cations by Biomolecules.- The Rectivity of Tryptophan Residues in Proteins as Studied by the Fluorescence Stopped-Flow Technique.- Anaerobic Stopped-Flow and Quenched-Flow Studies on Nitrogenase. The Coupling of MgATP Hydrolysis to Protein-Protein Electron Transfer and the Detection of a Dinitrogen-Hydride Intermediate In N2 Reduction.- Fast Reactions in Solution Under High-Pressure: Stopped-Flow Studies on Some Biological Reactions.- Kinetic and Isotropic Studies of Acid-Base Catalysis in Peroxidase Reactions.- Temperature and Pressure Relaxation Studies of Protein Assembly: Tubulin and Glutamate Dehydrogenase.- Ultrasonic Absorption Detection of Structural Fluctuations in Viral Capsids. A Discussion of the Presently Available Evidence.- The Mechanism of Sound Absorption in Solutions of Nucleotides and Nucleosides.- Elementary Steps in the Nucleophilic Addition of Amines to Olefins.- The Transition State of the Acid Catalyzed Alkoxide on Departure from Meisenheimer Complexes.- The Role of Meisenheimer Complexes in Aromatic Nucleophilic Substitution Reactions.- The Kinetics and Mechanism of the Reactions of Cyclo-1,5-Octadienechloroamineiridium(I) with 2,2?-Bipyridyl and 1,10-Phenanthroline.- The Kinetics of Donor-Acceptor Complex Formation, Studied by a Microwave Temperature-Jump Method.- Tunnelling in H-Transfer Reactions: Application of Fast-Reaction Methods.- Kinetic Study of Hydrogen Tunnelling In Meso-Tetraphenyl Porphine by Nmr-Lineshape Analysis And Selective T1? — Relaxation Time Measurements.- Hydrogen and Deuterium Atom Transfer Reactions from Substituted Phenols to Galvinoxyl.- Thermodynamics and Kinetics of Intramolecular Proton-Transfers; Temperature-Jump Studies.- High Field Perturbation and Chemical Relaxation of 2,4,6-Trichlorophenol and Triethylamine Mixtures in Cyclohexane.- Electron Transfer Reactions.- Combined Stopped-Flow/Continuous-Flow Arrangement for Kinetic Measurements in the Second to Microsecond Range: Investigation of Electron-Transfer Reactions with Metal-Porphyrin Complexes.- Electron-Transfer Reactions of Nitroaromatic Radical-Anions Observed by Pulse Radiolysis.- Free Radical Reactions with Pepsin Studied by Pulse Radiolysis.- Interaction of Stable Nitroxyl Radicals with Radiation-Induced Species: A Pulse Radiolytic Study.- Kinetics of Oxidation of Benzophenone Ketyl Radicals: Absolute Reaction Rates and Oscillatory Behaviour.- Time Resolved Polarization Studies Using Synchrotron Radiation.- Single-Photon Infrared Photochemistry: Wavelength and Temperature Dependence of the Quantum Yield for the Laser Induced Ionization of Water.- Molecular Motion of Polymers in Solution.- Kinetic Studies on Gas-Liquid Interface by Means of Capillary Wave Technique.- Kinetics on Adsorption-Desorption of Ions at Inorganic Oxides-H2O Interface by Means of Relaxation Techniques.- List of Participants.
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