Temperature-jump relaxation kinetic studies

The formation of a one host-two guests inclusion-complex could proceed by way of two main mechanisms (/) dimerization of the guest, followed by inclusion and (2) stepwise inclusion of two guest molecules. In order to distinguish between these two possibilities, several temperature-jump relaxation kinetic studies have been carried us-... 

A large programme utilizing temperature-jump relaxation methods for the study of tautomerism in aqueous solution has led the Dubois group to determine the kinetic and thermodynamic parameters of the equilibrium (130a) (130b) (78T2259). The tautomeric... 

Kao and Tsien studied the Ca +-binding kinetics of fura-2 and azo-1 by temperature-jump relaxation methods. In 140 mM KCl at 20°C, the respective association and dissociation rate constants for fura-2 were 6x10 M s and 97 s these kinetic properties were insensitive to hydrogen ion concentration over the pH range from 7.4 to 8.4. Azo-1 was studied in 140 mM KCl At 10°C, azo-... 

Studies on the kinetic behaviour of nucleoside and nucleotide complexes are less common than those on structural aspects. This arises because of the rapid rates of the formation and dissociation reactions, requiring NMR or temperature-jump relaxation measurements. The number of species that can coexist in solution also hinders interpretation. The earlier kinetic studies have been reviewed by Frey and Stuehr.127 Two important biological reactions of the nucleotides are phosphoryl and nucleotidyl group transfers. Both reactions are catalytic nucleophilic reactions and they both require the presence of a divalent metal ion, in particular Mg2+. Consequently, one of the main interests has been in understanding the catalytic mechanism of the metal ion involvement. This has mainly involved studies on related non-enzymic reactions.128... 

Temperature-jump relaxation and the stopped-flow methods are suitable to follow the concentration changes over extremely short time intervals. Such studies have indicated that immune reaction kinetics resemble other biological systems in which ligands are bound to proteins (Weber, 1975) in that the binding strength of small molecules is largely dictated by the constant. The association rate constants ka, are very similar for various antibody-antigen systems, i.e., for... 

Further support for the existence in solution of near equal amounts of the 7H and 9H protomers of purine is provided by carbon-13 resonance data in which the disposition of the acidic proton can be correlated with the magnitude of the shift changes of the C-4 and C-5 bridgehead atoms. Use of the 7- and 9- methyl homologs as reference compounds and extrapolation of the results to the 7H and 9H purines by applying a- and j -substituent parameter corrections gives 40% for the 7H tautomer in dimethyl sulfoxide and an estimate of 58% in water. " Data obtained from a temperature-jump relaxation technique used to study the rapid kinetics of 7H 9H prototropy of adenine in aqueous solution has given values for the equilibrium constant K = C7H/C9H = 0.28 at 20°) and the 7H isomer population ( 22%). This... 

Activation parameters are more and more frequently being reported as important features of temperature jump relaxation method kinetic studies. This is true in spite of the fact that the restricted temperature range accessible to a Joule heating temperature jump apparatus and the usual 10% uncertainties in measured relaxation times are not favorable characteristics for achieving precise values of AH and AS. ... 

Nickel(II) is one of the least reactive of the labile metal ions and the most amenable as regards kinetic investigation. Indeed, more than a hundred complex formations have been studied. Although some complexes require fast reaction techniques like temperature-jump relaxation, many systems have been studied adequately by more normal flow methods. The mechanisms of ligand replacement in Ni(II) complexes have been reviewed a number of times, notably by Wilkins [77]. 

A Joule heating temperature jump (T-jump) relaxation method study (8) of the kinetics of complexation of monovalent cations in methanol by dibenzo-30-crown-10 particularly intrigued us. Chock had found the rate of complexation of several monovalent cations (Na, K+,NHi +,etc.) to be almost diffusion controlled and essentially too fast for precise determination by T-jump equipment then available to him. He also noted an even faster relaxation process that was completely inaccessible. This latter relaxation process Chock ascribed to a conformational change of the dibenzo-30-crown-10 between two ligand conformers one of which is more suitable for complexing the cation. Such an inference is entirely consistent with known, rapid conformational equilibria in solutions of valinomycin (2), for example. 

The complexity of the binding dynamics of 1 with DNA became apparent in subsequent temperature jump experiments, where three relaxation processes were observed.112 The fastest relaxation process had a small amplitude (< 14%) and its kinetics were uncoupled from the second and third relaxation processes. This fast process was assigned to the binding of 1 to a minor site with a k+ value of 1.5x10 M s and a value of 6.9 x 10 s. This assignment was problematic because of the possible interference of artifacts for temperature jump experiments when the fluorescence detection is not performed at the magic angle,29 and this kinetic component was not observed in later studies.94,120... 

Temperature jump studies on the binding dynamics of 5 with ct-DNA and T2 Bacteriophage DNA showed two lifetimes in the relaxation kinetics.117 The observed... 

The non-linear dependence of the relaxation process on the DNA concentration was also observed in stopped-flow experiments and the same mechanism, i.e. fast pre-equilibrium followed by a slow intercalation step, was proposed." This latter study did not report values for the individual rate constants. The mechanism proposed in Scheme 4 was employed in subsequent studies despite the criticism on the accuracy for the data related to the fast kinetic component (see below). The original temperature jump study also showed that the relaxation kinetics depend on the structure of the DNA.117 The slower intercalation rate for 5 with T2 Bacteriophage DNA when compared to ct-DNA was ascribed to the glucosylation of the former DNA (Table 3). 

Until 1984, all of the stopped-flow and temperature-jump kinetic studies of alpha cyclodextrin inclusion-complex formation were explainable in terms of a single-step, binding mechanism. According to this mechanism, the observed rate constant, kobs, (for stopped-flow) and the reciprocal relaxation time, 1/t, (for temperature-jump) should show a linear dependence on the edpha cyclodextrin concentration. Sano and coworkers, however, in the case of the iodide-alpha cyclodextrin interaction, and Hersey and Robinson,in the case of various azo dye-alpha cyclodextrin interactions (see Fig. 7), found that certain guest species exhibit a limiting value of kobs and 1/t at high concentrations of alpha cyclodextrin. This behavior can most simply be explained in terms of a mechanism of the type,... 

The apparatus s step change from ambient to desired reaction conditions eliminates transport effects between catalyst surface and gas phase reactants. Using catalytic reactors that are already used in industry enables easy transfer from the shock tube to a ffow reactor for practical performance evaluation and scale up. Moreover, it has capability to conduct temperature- and pressure-jump relaxation experiments, making this technique useful in studying reactions that operate near equilibrium. Currently there is no known experimental, gas-solid chemical kinetic method that can achieve this. 

The kinetics and dynamics of crvptate formation (75-80) have been studied by various relaxation techniques (70-75) (for example, using temperature-jump and ultrasonic methods) and stopped-flow spectrophotometry (82), as well as by variable-temperature multinuclear NMR methods (59, 61, 62). The dynamics of cryptate formation are best interpreted in terms of a simple complexation-decomplexation exchange mechanism, and some representative data have been listed in Table III (16). The high stability of cryptate complexes (see Section III,D) may be directly related to their slow rates of decomplexation. Indeed the stability sequence of cryptates follows the trend in rates of decomplexation, and the enhanced stability of the dipositive cryptates may be related to their slowness of decomplexation when compared to the alkali metal complexes (80). The rate of decomplexation of Li" from [2.2.1] in pyridine was found to be 104 times faster than from [2.1.1], because of the looser fit of Li in [2.2.1] and the greater flexibility of this cryptand (81). At low pH, cation dissociation apparently... 

Previous investigations of helix-coil transition kinetics, which used a variety of fast relaxation methods (electric field jump, ultrasonic absorption, dielectric relaxation and temperature jump), encountered many difficulties (12). The systems studied were long homopolymers (>200 residues) that often had hydrolyzable side chains. Controversial results have been reported, depending on the experimental technique employed, because unwanted side chain reactions or molecular reorientation were often difficult to distinguish from the helix-coil conformational change. However, as observed here, a maximum in the relaxation times was detected for these experiments ranging from 15 ps to 20 ns and was attributed to the helix-coil transition. 

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