NMR study of the stoichiometry,stability and exchange kinetics of complexation reaction between Pb2+ ion and 18-crown-6 in binary acetonitrile-water mixtures

Proton NMR was used to study the complexation reaction between lead ion and 18-crown-6 in a number of binary acetonitrile-water mixtures. Formation constant for the resulting 11 complexes in different solvent mixtures was determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and amount of water in the mixed solvent. The dissociative kinetics of the complex was studied by proton line-shape analysis. The Arrhenius plots showed a distinct isokinetic temperature at about 25°C at which the decomplexation rate is more or less independent of the solvent composition. the complexation rate and the activation parameters E _a , H and S, for the exchange have been determined and found to be strongly solvent dependent. There is actually a linear relationship between the mole fraction of acetonitrile in the mixed solvent and logarithm of the stability constant as well as activation parameters.     

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Summary Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0 mol dm^–3 LiNO₃, NaNO₃, NaCl, Na₂SO₄ or KNO₃) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)₅L]^3– with L = 4-cyanopyridine, 4,4-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed.     

A comparative kinetic and mechanistic study of glutamic acid oxidation by acid permanganate in the absence and presence of sodium dodecyl sulphate

The kinetics and mechanism of glutamic acid (GCO₂H) oxidation by acid permanganate has been carried out in the absence and presence of sodium dodecyl sulphate (SDS). The surfactant enhances the reaction rate without changing the reaction mechanism. The overall rate expression for the reduction of Mn^VII may be written:

Thin-Layer Chromatographic Separation of Cadaverine and Ornithine,and Spectrophotometric Quantification

JPC – Journal of Planar Chromatography – Modern TLC -     

A 1H NMR study of 1,4-bis(N-hexadecyl-N, N-dimethylammonium)butane dibromide/sodium anthranilate system: spherical to rod-shaped transition

The effect of addition of sodium anthranilate to 5 mM micellar solutions of gemini surfactant 1,4-bis(N-hexadecyl-N,N-dimethylammonium)butane dibromide is investigated by ¹H NMR. The solubilization site of anthranilate anion near the micellar surface is inferred. In the micelles, the An⁻ ions intercalate among the surfactant headgroups producing morphological changes.     

An Easy One-Pot Procedure for the Synthesis of <Emphasis Type="Italic">N</Emphasis>-Sulfonyl Phosphorous Ylides and Sulfonyl Iminophosphoranes

Summary. Reaction of triphenylphosphine and an electron deficient acetylenic ester in the presence of strong N–H acid such as alkyl and aryl sulfamides or acetamide produces phosphorous ylides at room temperature in CH₂Cl₂. The aryl sulfamide phosphoranes undergo a smooth transformation reaction in boiling toluene and produce iminophosphoranes.     

On the estimation of stability parameters from heat-induced conformational transition curves of proteins

A method is suggested to determine valid and authentic values of thermodynamic stability parameters of proteins from their heat-induced conformational transition curves. We show (a) that the estimate of ΔH_m ^van, the enthalpy change on denaturation at T_m, the midpoint of denaturation, is significantly less than ΔH_m ^cal, the value obtained by the calorimetric measurements, if the analysis of the conformational transition curve uses the conventional method which assumes a linear temperature-dependence of the pre- and post-transition baselines; and (b) that there exists an excellent agreement between ΔH_m ^van and ΔH_m ^cal values of proteins, if the analysis of thermal denaturation curves assumes that the temperature-dependence of pre- and post-transition baselines is described by a parabolic function. The latter analysis is supported by our observations that the temperaturedependencies of the absorption and circular dichroism properties of protein groups are indeed nonlinear. It is observed that the estimate of ΔC_p, the constant-pressure heat capacity change is independent of the model used to describe the temperaturedependence of the pre- and post-transition baselines. An important conclusion is that for proteins which exhibit a two-state character, all stability parameters are measured with the same error as that observed with a calorimeter.