Kinetics of the oxidation of aliphatic aldehydes by Os(VIII) in alkaline solution

Kinetics of oxidation of six aliphatic aldehydes by Os(VIII) in alkaline solutions have been studied. The reaction is of first order with respect to each of the aldehyde and Os(VIII). The pseudo-first order rate constants decreased with an increase in the concentration of hydroxyl ions. The oxidation of deuterioacetaldehyde (MeCDO) exhibited a substantial primary kinetic isotope effect. Separate rate constants for the oxidation of hydrate and free aldehyde forms have been evaluated. The aldehyde hydrate is postulated as the active reductant. Ionic strength has no noticable effect on the rate. The rate-determining step is, therefore, postulated to be a bimolecular reaction between the aldehyde hydrate and [OsO₄(OH)₂]^?2. The value of the limiting rate constant exhibited an excellent correlation with Taft σ* values; reaction constant being negative. A mechanism involving transfer of a hydride ion from the aldehyde hydrate to Os(VIII) has been proposed.     

Minimal supersymmetric Higgs bosons with extra dimensions as the source of reheating and all matter

We consider the possibility that the dark energy responsible for inflation is deposited into extra dimensions outside of our observable Universe. Reheating and all matter can then be obtained from the minimal supersymmetric standard model flat direction condensate involving the Higgs bosons Hu and Hd, which acquires large amplitude by virtue of quantum fluctuations during inflation. The reheat temperature is TRH < or = 10(9) GeV so that there is no gravitino problem. We find a spectral index ns 1 with a very weak dependence on the Higgs potential.     

Adiabatic density perturbations and matter generation from the minimal supersymmetric standard model

We propose that the inflaton is coupled to ordinary matter only gravitationally and that it decays into a completely hidden sector. In this scenario both baryonic and dark matter originate from the decay of a flat direction of the minimal supersymmetric standard model, which is shown to generate the desired adiabatic perturbation spectrum via the curvaton mechanism. The requirement that the energy density along the flat direction dominates over the inflaton decay products fixes the flat direction almost uniquely. The present residual energy density in the hidden sector is typically shown to be small.     

Improved microcombustion technique for nitrogen estimation in heterocyclic compounds

Summary An improved microcombustion technique is described for nitrogen estimation in heterocyclic compounds by use of a modified Dumas filling.

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Zusammenfassung Eine verbesserte Mikroverbrennungstechnik für Stickstoffbestimmungen in heterocyklischen Verbindungen unter Verwendung einer modifizierten Dumas-Füllung wurde beschrieben.

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Communication No. 1663 from the Central Drug Research Institute, Lucknow, India.     

Magnetic ordering versus lattice distortion in very narrow bands

A simple criterion for antiferromagnetic ordering versus lattice distortion in very narrow band materials is obtained. The model describing these narrow band materials contains the Hubbard Hamiltonian, short ranged interatomic Coulomb and exchange interactions, and the electron-phonon interaction.     

Two exact models of charged dust collapse

Liang studied three classes of irrotational dust collapse models with high symmetries. Here the charged analogs of the models with spherical and plane symmetry are considered. Contrary to Liang's result that the plane-symmetric model with positive mass cannot have a static exterior we find that the corresponding charged model may have bounce and a static exterior.     

Axially symmetric stationary electrovac solutions

Perjes and Israel and Wilson have given independently a new class of solutions of the sourcefree Einstein-Maxwell equations, which can be interpreted as the external gravitational and electromagnetic fields of a spinning source with unit specific charge. Starting from Zipoy's solutions in oblate and prolate spheroidal coordinates for the source-free gravitational field we generate some axially symmetric stationary solutions of the source-free Einstein-Maxwell equations by using Perjes' method. All these solutions become Euclidean at infinity. The asymptotic behavior and the singularity of the solutions are studied in order to gain some insight into the nature of the source. The solution in prolate spheroidal coordinates is found to contain closed timelike lines.     

Kinetics and mechanism of the oxidation of substituted benzaldehydes by benzyltrimethylammonium chlorobromate

The oxidation of 35 monosubstituted benzaldehydes by benzyltrimethylammonium chlorobromate (BTMACB) in aqueous acetic acid leads to the formation of the corresponding benzoic acids. The reaction is first order with respect to both benzaldehyde and BTMACB. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of benzyltrimethylammonium chloride or potassium bromide on the reaction rate. The oxidation of [(2)H]benzaldehyde (PhCDO) indicated the presence of a substantial kinetic isotope effect. The effect of solvent composition indicated that the reaction rate increases with an increase in the polarity of the solvent. The rates of oxidation of meta- and para-substituted benzaldehydes were correlated in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho-substituted benzaldehydes was correlated with the tetraparametric LDRS equation. The oxidation of para-substituted benzaldehydes is more susceptible to the delocalization effect, whereas the oxidation of ortho-and meta-substituted compounds displayed a greater dependence on the field effect. The positive value of eta suggests the presence of an electron-deficient reaction center in the rate-determining step. The reaction is subjected to steric hindrance by the ortho substituents.