Kinetic and thermodynamic studies

This order corresponds to numerous results of kinetic and thermodynamic studies 113) u4) and seems to be based on energetic effects in the present case. 

Brouillard, R. and Delaporte, B., Chemistry of anthocyanin pigments. 2. Kinetic and thermodynamic study of proton-transfer, hydration, and tautomeric reactions of mal-vidin-3-glucoside, J. Am. Chem. Soc., 99, 8461, 1977. 

Biver, T., De Biasi, A., Secco, E, Venturing M., and Yarmoluk, S. (2005) Cyanine dyes as intercalating agents Kinetic and thermodynamic studies on the DNA/Cyan40 and DNA/CCyan2 systems. Biophys. J. 89, 374-383. 

The dependence of rate constants for approach to equilibrium for reaction of the mixed oxide-sulfide complex [Mo3((i3-S)((i-0)3(H20)9] 1+ with thiocyanate has been analyzed into formation and aquation contributions. These reactions involve positions trans to p-oxo groups, mechanisms are dissociative (391). Kinetic and thermodynamic studies on reaction of [Mo3MS4(H20)io]4+ (M = Ni, Pd) with CO have yielded rate constants for reaction with CO. These were put into context with substitution by halide and thiocyanate for the nickel-containing cluster (392). A review of the chemistry of [Mo3S4(H20)9]4+ and related clusters contains some information on substitution in mixed metal derivatives [Mo3MS4(H20)re]4+ (M = Cr, Fe, Ni, Cu, Pd) (393). There are a few asides of mechanistic relevance in a review of synthetic Mo-Fe-S clusters and their relevance to nitrogenase (394). 

H. H. Wittekind, B. Testa, J. Estreicher, The Reversible Proxibarbal-Valofan Isomerization. I. Kinetics and Thermodynamic Studies in Aqueous Solutions , Helv. Chim. Acta 1988, 71, 1220 - 1227 H. H. Wittekind, B. Testa, J. Estreicher, The Reversible Proxibarbal-Valofan Isomerization. II. Kinetic Studies in a Biphasic Octanol/Water System , Helv. Chim. Acta 1988, 71, 1228 - 1234. 

A number of ex situ spectroscopic techniques, multinuclear NMR, IR, EXAFS, UV-vis, have contributed to rationalise the overall mechanism of the copolymerisation as well as specific aspects related to the nature of the unsaturated monomer (ethene, 1-alkenes, vinyl aromatics, cyclic alkenes, allenes). Valuable information on the initiation, propagation and termination steps has been provided by end-group analysis of the polyketone products, by labelling experiments of the catalyst precursors and solvents either with deuterated compounds or with easily identifiable functional groups, by X-ray diffraction analysis of precursors, model compounds and products, and by kinetic and thermodynamic studies of model reactions. The structure of some catalysis resting states and several catalyst deactivation paths have been traced. There is little doubt, however, that the most spectacular mechanistic breakthroughs have been obtained from in situ spectroscopic studies. 

Kinetic and Thermodynamic Studies of Ethene/CO Copolymerisation in Aprotic Solvents... 

Polyakov VA, Nelen MI, Nazarpack-Kandlousy N, Ryabov AD, Eliseev AV. Imine exchange in 0-aryl and 0-alkyl oximes as a base reaction for aqueous dynamic combinatorial libraries. A kinetic and thermodynamic study. J Phys Org Chem 1999 12 357-363. 

Nature of the Co—Mn—Br Catalyst in the Methylaromatic Compounds Process Kinetic and Thermodynamic Studies... 

Kinetic and thermodynamic studies on the nickel(II)/Hacac system have been carried out in water solution1553-1555 and NMR studies have been carried out on the adducts of Ni(acac)2 with a variety of Lewis bases.1556-1559... 

The Mechanism of Nitrite Ion Binding to Metmyoglobin Under some physiological conditions, NO can be rapidly metabolized to nitrogen species in the + 3 (NO2 ) and + 5 (NO, ) oxidation states.319 It is of chemical and biological interest to establish the similarities or differences of the interaction of NO and the nitrite ion with metMb. Earlier kinetics and thermodynamics studies of these reactions were undertaken but no firm mechanistic conclusions were reached.320 Two anionic ligands, azide and cyanide, exhibit different reactivities toward metMb, and... 

Kinetic and thermodynamic studies have been carried out to determine the parameters of these systems [35-40]. These studies of the carbonyl compound-ammonia-HCN equilibrium also demonstrate the difference in... 

The use of allylic selenides 166 in oxidation reaction leads to intermediate selenoxides 167, which can undergo [2,3]sigmatropic rearrangements to the corresponding allylic selenenates 168. These componds will lead to allylic alcohols 169 after hydrolysis (Scheme 48). This is also a versatile procedure for the synthesis of optically active allylic alcohols, provided that either an asymmetric oxidation or an optically active selenide is used for the rearrangement. Detailed kinetic and thermodynamic studies of [2,3]sigmatropic rearrangements of allylic selenoxides have also been reported.290-294... 

In aqueous solutions, lanthanide(III) ions are coordinated by water molecules. The hydration sphere of the lanthanide ions plays a vital role in the chemistry of the ion and also in several biochemical reactions involving isomorphous calcium(II) substitution reactions. The interpretation of the absorption spectra of lanthanide(III) ions in aqueous media is difficult because of the variability of the coordination number of the aquo ions along the lanthanide series. Kinetic and thermodynamic studies [206-210] on the lanthanide aquo systems led to the conclusion that the lighter lanthanides have a coordination number of 9, heavy lanthanides are octacoordinated and the middle members exist in a equilibrium mixture of octa and nonacoordinated aquo ions. 

The sensitivity of the absorption spectra of haemoproteins to the environment of the haem chromophore makes spectrophotometry a valuable tool in kinetic and thermodynamic studies. The former have been developed by Chance and his co-workers (25) to a high degree of sophistication. The standard spectrophotometric methods for the investigation of equilibria (26) are widely used in studies of haemoproteins. 

The kinetic and thermodynamic studies on the octahedral rhodium(III) complexes7 suddenly gained momentum. This field was later to give rise to the important discovery of the photosensitivity of rhodium complexes.8... 

El-Sofany, E. A., A. A. Zaki, and H. S. Mekhamer. 2009. Kinetics and thermodynamics studies for the removal of Co2+ and Cs+ from aqueous solution by sand and clay soils. Radiochim. Acta 97 23-32. 

Acid-catalysed hydrolysis is the most common method for the deprotection of acetals and a mechanism for the reaction was given in section 1.2.2. Extensive kinetic and thermodynamic studies on cyclic acetal hydrolysis (see reviews in section 2.9.4) allow several conclusions to be drawn12-15 ... 

Kinetic and thermodynamic studies of geranyl acetate production by direct geraniol acetylation with lyophilized cells of A. oryzae MIM were carried out in n-heptane [13-15]. Batch tests were performed varying the starting substrates equimolar level from 25 to 150 mM, cell concentration from 5 to 30g/l, and temperature from 30 to 95 °C. The initial rates at different initial substrate concentrations were measured and an apparent Michaelis constant KJ of 62mM and a fee value of 0.88 mmol/g/h were estimated by direct fitting of the initial rates against the initial substrate concentrations <75 mM [15]. 

Ludmann K, Gergely C, Varo G. Kinetic and thermodynamic study of the bacteriorhodopsin photocycle over a wide pH range. Biophys. J. 1998 75 3110-3119. 

To the best of our knowledge no experimental kinetic and thermodynamic studies have been performed on radical anion pericyclic processes. Interesting structural information has, however, been obtained for some [2 - - 2] cycloadducf , e.g. 4N/5e radical anions [361],... 

A variety of micropellicular packing materials has been developed for the analysis of both small and large molecules by various HPLC modes, including ion exchange (lEC), metal interaction (MIC), reversed phase (RPC) [4], and affinity chromatography (AC) [5]. Besides analytical applications, other possible utilization of micropellicular stationary phases includes fundamental kinetic and thermodynamic studies of the retention mechanisms on a well-defined surface. Nevertheless, a relatively limited variety of micropellicular... 

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