Kinetics and mechanism of the oxidation of n-acetyl l-cysteine by 2,6-dichloroindophenol in methanol–water medium

The principal reactants interact in a molar ratio of 2:1 forming dihydroindophenol and the corresponding disulfide. The order of reaction is unity with respect to each reactant, namely, N-acetyl L-cysteine and indophenol. The rate shows an inverse linear relation with hydroxyl ions. It is not influenced by the variation in the initial concentration of indophenol. The rate increases on adding the salts possessing a cholinergic effect and the neutral electrolytes, as well as on increasing the dielectric constant of the medium. The products, namely, N-acetyl L-cystine (disulfide) and the leuco dye, do not influence the rate. A low energy and a highly negative entropy of activation (4.11 kcal/mol and -60.49 e.u., respectively) suggest the formation of an outer sphere complex as the rate-determining step.     

Origin of the high-and low-frequency K-satellites of 31Ga, 32Ge and 33As

The origin of the high- and low-frequency K-satellites of ³¹Ga, ³²Ge, ³³ As is explain on the basis of Hayasi's theory of quasi-stationary states. It is shown that the same QSS difference gives rise to a particular satellite of either type in all the elements. The results are compared with those of multiple ionisation theory.     

Forbidden hyperfine transitions in electron spin resonance of Mn2+ in NaCl single crystal

Forbidden hyperfine transitions are observed in the electron spin resonance spectrum of divalent Mn⁵⁵ ion in NaCl single crystal for a particular associated pair. From the measurements of the M = + 1/2 → ?1/2, Δm = ± 1 transitions the parametersQ′ and Q″ of the nuclear electric quadrupole part of the spin-Hamiltonian H_o = Q′ [I_z ² ? 1/3 I (I + 1)] + Q″ (I_x ²?I_y ²) are found to be + 1.70 × 10^?4 cm.^?1 and +0.16 × 10^?4 cm.^?1 respectively.     

Crystal field contribution to Mössbauer isomer shift

The crystal field hamiltonian H_c = B₂⁰Y₂⁰ + B₂²(Y₂² + Y₂^?2) commonly used in the study of electron-spin resonance is employed to obtain new contributions to the ⁵⁷Fe³⁺ isomer shift in the Mössbauer effect. A numerical estimate of the shift is also presented.     

Ferroelectric soft-mode contribution to zero-field splitting: Paramagnetic resonance investigation of phase transition in Mn2+-doped NaNO2

The contribution of the ferroelectric soft-mode to the zero-field splitting is calculated and separated from the thermal contribution arising from the splitting due to the electron-phonon interaction. The predicted effect is compared with the measured values in Mn²⁺-doped NaNO₂.     

Anharmonic properties of rocksalt structure solids

An effort has been made for obtaining the anharmonic properties of rocksalt structure solids starting from primary physical parameters viz. nearest-neighbor distance and hardness parameter assuming long- and short-range potentials at elevated temperatures. The elastic energy density for a deformed crystal can be expanded as power series of strains for obtaining coefficients of quadratic, cubic and quartic terms which are known as the second-, third- and fourth-order elastic constants, respectively. When the values of the higher-order elastic constants are known for a crystal, many of the anharmonic properties of the crystal can be treated within the limit of the continuum approximation in a quantitative manner. In this study, higher-order elastic constants are computed up to their melting temperature for rocksalt structure solids, which are alkali cyanides, sodium and potassium halides. The first order pressure derivatives of second- and third-order elastic constants, the second-order pressure derivatives of second-order elastic constants and partial contractions are also evaluated at different temperatures for these substances. The results thus obtained are compared with experimental data and found in well agreement with present values.     

Studies on long lasting optical properties of Eu2+ and Dy3+ doped di-barium magnesium silicate phosphors

Di-bariummagnesium silicate phosphors doped with europiumand dysprosium were prepared under a weak reducing atmosphere. X-ray diffraction pattern of the sample was also done that confirmed the proper preparation of the phosphor. Scanning electron microscope (SEM) images confirmed that the sample has regular surface and uniform grain size distribution. Comparative studies of phosphorescence decay of Ba₂MgSi₂O₇:Eu²⁺, Dy³⁺ phosphors with different concentration of Dy³⁺ were done. The phosphor with 0.5/1.5 mol% of Eu/Dy, exhibited optimum green color afterglow properties. This emission is expected to arise due to transition of Eu²⁺ ions from any of the sublevels of 4f⁶5d¹ configuration to ⁸S_7/2 level of the 4f⁷ configuration. For a suitable trap depth, the trap concentration is expected to be proportional to the concentration of Dy³⁺. These traps are responsible for holding the charge career for a reasonable time, subsequently for increasing the time of afterglow. Hence, optimum Dy³⁺ concentration produces the longer afterglow duration with higher intensity of luminescence signals. Trap depth were also calculated using thermoluminescence glow curve which was indicative of formation of traps suitable for long afterglow.     

Synthesis,characterisation, and biological activity of three new amide prodrugs of lamotrigine with reduced hepatotoxicity

Lamotrigine (LTG) is an antiepileptic drug used for the prevention of convulsions. Except several known side effects, hepatic dysfunction is also reported. Hepatotoxic side effects occur due to the dichlorophenyl moiety which develops an abnormally low level of glutathione. Depletion of glutathione causes oxidative stress and hepatic cell damage. The goal of the present study was to test the action and side effects of the three compounds synthesised and compared to LTG. Three amide prodrugs of LTG were synthesised by its reaction with N-acetylamino acids, viz, glycine, glutamic acid, and methionine. Purified synthesised prodrugs were subjected to thin layer chromatography, melting point, solubility and partition coefficients determination and characterised by UV, FTIR, ¹H and ¹³C NMR spectroscopy. The synthesised prodrugs were subjected to in vitro hydrolysis and to anticonvulsant and hepatotoxic activity studies. Significant reduction in hepatotoxicity and comparable anticonvulsant activities were obtained in all synthesised prodrugs as compared to LTG.     

Ion-water clusters, bulk medium effects, and ion hydration

Thermochemistry of gas-phase ion-water clusters together with estimates of the hydration free energy of the clusters and the water ligands are used to calculate the hydration free energy of the ion. Often the hydration calculations use a continuum model of the solvent. The primitive quasichemical approximation to the quasichemical theory provides a transparent framework to anchor such efforts. Here we evaluate the approximations inherent in the primitive quasichemical approach and elucidate the different roles of the bulk medium. We find that the bulk medium can stabilize configurations of the cluster that are usually not observed in the gas phase, while also simultaneously lowering the excess chemical potential of the ion. This effect is more pronounced for soft ions. Since the coordination number that minimizes the excess chemical potential of the ion is identified as the optimal or most probable coordination number, for such soft ions the optimum cluster size and the hydration thermodynamics obtained with and without account of the bulk medium on the ion-water clustering reaction can be different. The ideas presented in this work are expected to be relevant to experimental studies that translate thermochemistry of ion-water clusters to the thermodynamics of the hydrated ion and to evolving theoretical approaches that combine high-level calculations on clusters with coarse-grained models of the medium.