Chemical and Biological Applications of Relaxation Spectrometry

Chemical relaxation spectrometry involves the application of several different relaxation techniques to investigate the kinetics and mechanisms of fast chemical reactions and also dynamic molecul­ 10 ar processes that occur in liquids in the time range 1 - 10- secs. These methods have been used widely in several disciplines of the natural sciences including molecular biology, biochemistry, organic stereochemistry, detergent chemistry and inorganic chemistry. The purpose of the Advanced Study Institute was to provide a forum for scientists to discuss the role, scope and limitations of the various applications of chemical relaxation methods in order to stimulate discussion and interaction between workers in these different fields. The papers described in this volume are a summary of the contributions that were discussed at the meeting. The brief given to the authors was to attempt to prepare an article contain­ ing a good supply of references so that the book can be used not only by those starting in the field, but also by the specialist and research worker. These contributions cover a varied range of topics summarizing the achievements, the current state of knowledge and possible application in many disciplines. It is to be hoped that this volume will help to point out some new directions towards which research efforts are required and to attract new researchers with fresh points of view.

Inhalt

Ultrasonic Relaxation Spectrometry.- Dielectric Relaxation.- Dielectric Relaxation at Microwave Frequencies.- The Stopped-Flow and Temperature-Jump Techniques - Principles and Recent Advances.- The Solvent-Jump Relaxation Method Using Stopped and Continuous Flow.- A Laser Temperature Jump and Photolysis Apparatus with Repetitive Tunable Excitation.- The Problem of Inhomogeneous Heating in Laser-T-Jump Experiments.- Kinetic Studies of Metal Ion Complexation and Dye Dimerization by Laser Ultrasound and Laser T-Jump.- The Electric Field Jump Relaxation Method.- Pressure-Jump Methods.- On Data Processing, Evaluation and Precision of Relaxation Measurements.- The Analysis of Relaxation Amplitudes.- Normal Mode Analysis of Chemical Reactions.- Brief Review of the Chemical Relaxation Studies of Micellar Equilibria.- Chemical Relaxation Studies of Micellar Equilibria.- Kinetic Studies of the Rapid Reactions in n-Alkyl Sulfate Solution.- Ultrasonic Pulse Spectroscopy in Micellar Solutions.- Kinetics of Micellization from Ultrasonic Relaxation Studies - the Fast Process Described by the Two State Model.- Comments on the Fast Relaxation Process Observed in the Study of Micellization.- On the Kinetics of the Formation of NaDS Micelles.- Mechanism of Micelle Formation of Sodiumdodecylsulfate (SDS).- Kinetic Studies of the Dissociation of Nonionic Detergent Micelles.- Dynamics of Small Molecule - Micelle Interactions.- Stopped Flow and Temperature Jump Studies of Colloidal Suspensions.- An Attempt to Measure the Monomer-Micelle Exchange Frequency Using Electron Paramagnetic Resonance.- Kinetics of Step-Wise Micelle Association and Dissociation.- The Rate of Micelle Dissociation.- On the Rate of Many-Step Processes.- A Cooperative Model for Micelle Formation.- On the Mechanism of Ligand Substitution in Weak Metal Complexes in Aqueous Solutions.- Ultrasonic and Laser T-Jump Studies of the Nickel Carboxylate Complex Formation Reaction in an Aqueous Solution.- The Association of Optically Active Ions; Ultrasonic Investigation of the Association of Bis and Tris (Orthophenanthroline) Zinc (11) d-Camphorsulfonate.- Mechanism of Complex Formation in Nonaqueous Solvents.- Ligand Substitution Processes. An NMR Study. I. Solvation Shells of Diamagnetic Cations Al3+ and Be2+.- Ligand Substitution Processes. II, Solvation Shells of Paramagnetic Cations Ni2+ and Co2+.- Ultrasonic Studies of Polyion - Counterion Interactions in Polyelectrolytes Solutions.- The Use of the Temperature-Jump Method in the Study of Organic Reaction Mechanisms.- Conformational Analysis Using Ultrasonic Relaxation Spectrometry.- Ultrasonic Absorption Determination of the Thermodynamics of Fast Isomerization Processes.- A Comparison of Proton Transfer Rates in Aqueous and Nonaqueous Solutions.- Electric Field and Temperature-Jump Study of the Color Change Kinetics of Ethanolic and Aqueous Phenolphthalein.- Rates of Proton Transfers in 70% DMSO-30% Water. Mechanism of Deprotonation of Intramolecularly Hydrogen Bonded Species.- Solvent-Jump Relaxation Kinetics of the Association of Rhodamine Type Laser Dyes.- Temperature-Jump Study of the Rates of Proton Transfer and the Strength of Intramolecular Hydrogen Bonds in Peri-Substituted Naphthalenes.- Fast Proton-Transfer Reactions in Aprotic Solvents.- Ultrasonic Absorption Study of Aqueous Solutions of Nucleotides and Nucleosides.- Ultrasonic Absorption in Protein Solution.- Fast Relaxations in Human Carbonic Anhydrase Complexes with Sulfonamides.- Kinetics of Glutamate Dehydrogenase Self-Assembly.- Interaction between Cationic Dyes and Polyelectrolytes.- Kinetic Study of Cooperative Binding Reaction of Toluidine Blue to Poly-?, L-Glutamic Acid by Means of Electric Field Pulse Method.- The Thermodynamics and Kinetics of Association of Acridine Dyes in Aqueous Media: A Model System for the Study of Stacking and Charge-Effects on Self-Aggregation.- Ultrasonic Absorption Studies in Relation to Conformational Changes of Biopolymers in Solution.- Kinetic Study of Helix-Coil Transition in Aqueous Solutions of Poly-?, L-Glutamic Acid by Means of Electric Field Pulse Method.- Electric Field Jump Study of the Helix-Coil Transition of Aqueous Poly-?, L-Glutamic Acid.- Ultrasonic Relaxation in Solution of Polystyrene and N-Polyvinylpyrrolidone.- The Origin of Ultrasonic Relaxation in Polymer Solutions.- Motion in Amorphous Polymers and Viscous Liquids.