Photochemical Oxidation of Thioketones: Steric and Electronic Aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Measurement of Turbulence and pitch of the airstream in the 5'* 7' tunnel of Indian Institute of Science

Abstract is not available.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

Study of turbid media with light: Recovery of mechanical and optical properties from boundary measurement of intensity autocorrelation of light

We discuss the inverse problem associated with the propagation of the field autocorrelation of light through a highly scattering object like tissue. In the first part of the work, we reconstructed the optical absorption coefficient mu(u) and particle diffusion coefficient D-B from simulated measurements which are integrals of a quantity computed from the measured intensity and intensity autocorrelation g(2)(tau) at the boundary. In the second part we recover the mean square displacement (MSD) distribution of particles in an inhomogeneous object from the sampled g(2)(tau) measure on the boundary. From the MSD, we compute the storage and loss moduli distributions in the object. We have devised computationally easy methods to construct the sensitivity matrices which are used in the iterative reconstruction algorithms for recovering these parameters from the measurements. The results of the reconstruction of mu(a), D-B, MSD and the viscoelastic parameters, which are presented, show reasonable good position and quantitative accuracy.

Pressure-induced electronic and structural transformations in bulk gese2 glass

The pressure dependence of the electrical of the electrical resistivity of bulk GeSe2 glass shows a semiconductor-to-metal transition at 7 GPa pressure. The high pressure phase is examined using he x-ray diffractometer and is found to be crystalline, with a face-centered cubic structure having a =4.06A. The electrical conductivity has also been studied as a function of temperature at various pressures.

Surface electronic structure of the high-Tc oxides

Electron energy loss spectroscopy (EELS) has been employed to monitor surface conductivity changes in YBa2Cu3O7 as a function of temperature. Concomitant use of x-ray photoelectron spectroscopy (XPS) establishes that the formation of oxygen dimers with lowering of temperature is accompanied by a simultaneous increase of surface conductivity.

Chlorinated Hypoelectronic Dimetallaborane Clusters: Synthesis, Characterization, and Electronic Structures of (eta(5)-C5Me5W)(2)B5HnClm (n=7, m=2 and n=8, m=1)

Pyrolysis of (eta(5)-C5Me5WH3)B4H8, 1, in the presence of excess BHCl2 center dot SMe2 in toluene at 100 degrees C led to the isolation of (eta(5)-C5Me5W)(2)B5H9, 2, and B-Cl inserted (eta(5)-C5Me5W)(2)B5H8Cl, 3, and (eta(5)-C5Me5W)(2)B5H7Cl2, (four isomers). All the Chlorinated tungstaboranes were isolated as red and air and moisture sensitive solids. These new compounds have been characterized in solution by H-1, B-11, C-13 NMR, and the structural types were unequivocally established by crystallographic analysis of compounds 3, 4, and 7. Density functional theory (DFT) calculations were carded out on the model molecules of 3-7 to elucidate the actual electronic structures of these chlorinated species. On grounds of DFT calculations we demonstrated the role of transition metals, bridging hydrogens, and the effect of electrophilic substitution of hydrogens at B-H vertices of metallaborane structures.

Molecular vibrations, electronic structure and conformation of diprotonated thiocarbohydrazide

The infrared spectra of diprotonated species of thiocarbohydrazide and its perdeuterated derivative have been examined in the crystalline state. A complete vibrational assignment with a full normal coordinate treatment based on a Urey—Bradley type intramolecular potential Function supplemented with a valence force function for the out of plane and torsional modes is proposed and the origin of the amide II band splittings is explained. A CNDO/2 study of diprotonated thiocarbohydrazide and its neutral molecule is undertaken and the changes in the molecular electronic structures and conformations consequent to protonation are determined and briefly discussed. The magnitude of the N—N+H3 torsional barrier is estimated to be 21 kJ mol− (5.0 kcal mol−1) whereas the barrier for the C—N group is found to be 92 kJ mol−1 (22.0 kcal mol−1).

Dosage Compensation And Sex Determination In Drosophila - Mechanism Of Measurement Of The X/A Ratio

We propose a molecular mechanism for the intra-cellular measurement of the ratio of the number of X chromosomes to the number of sets of autosomes, a process central to both sex determination and dosage compensation in Drosophila melanogaster. In addition to the two loci, da and Sxl, which have been shown by Cline (Genetics, 90, 683, 1978)and others to be involved in these processes, we postulate two other loci, one autosomal (ω) and the other, X-linked (π). The product of the autosomal locus da stimulates ω and initiates synthesis of a limited quantity of repressor. Sxl and π ,both of which are X-linked, compete for this repressor as well as for RNA polymerase. It is assumed that Sxl has lower affinity than π for repressor as well as polymerase and that the binding of polymerase to one of these sites modulates the binding affinity of the other site for the enzyme. It can be shown that as a result of these postulated interactions transcription from the Sxl site is proportional to the X/A ratio such that the levels of Sxl+ product are low in males, high in females and intermediate in the intersexes. If, as proposed by Cline, the Sxl- product is an inhibitor of X chromosome activity, this would result in dosage compensation. The model leads to the conclusion that high levels of Sxl+ product promote a female phenotype and low levels, a male phenotype. One interesting consequence of the assumptions on which the model is based is that the level of Sxl+ product in the cell, when examined as a function of increasing repressor concentration, first goes up and then decreases, yielding a bell-shaped curve. This feature of the model provides an explanation for some of the remarkable interactions among mutants at the Sxl, da and mle loci and leads to several predictions. The proposed mechanism may also have relevance to certain other problems, such as size regulation during development, which seem to involve measurement of ratios at the cellular level.

Measurement of resistivity and dielectric constant of beach-sand minerals

Resistivity and dielectric constant are important parameters which influence the separation of particles in a drum-type electrostatic separator. The paper provides details of the measurement of the parameters and data on the magnitude of resistivity and dielectric constant of the minerals of beach sand.

Self Assembly and Electronic Structure of ZnO Nanocrystals

In this paper, we report the synthesis and self assembly of various sizes of ZnO nanocrystals. While the crystal structure and the quantum confinement of nanocrystals were mainly characterized using XRD and UV absorption spectra, the self assembly and long range ordering were studied using scanning tunneling microscopy after spin casting the nanocrystal film on the highly oriented pyrolytic graphite surface. We observe self assembly of these nanocrystals over large areas making them ideal candidates for various potential applications. Further, the electronic structure of the individual dots is obtained from the current-voltage characteristics of the dots using scanning tunneling spectroscopy and compared with the density of states obtained from the tight binding calculations. We observe an excellent agreement with the experimentally obtained local density of states and the theoretically calculated density of states.

Electronic Structure of some Substituted azolidines.CNDO/2, NMR and vibratational spectoroscopic studies

The 1H and 13C chemical shifts, characteristic vibrational frequencies and force constants for some substituted azolidines are correlated with the results of the CNDO/2 calculations. The influence of the exo and endo heteroatoms on the electronic structure of the heterocyclic ring are discussed.

Conformational Analysis and Electronic Structure of Monothiodiacetamide: Normal Coordinate Analysis and Molecular Orbital Study

The infrared spectra of monothiodiacetamide (MTDA, CHaCONHCSCH3) and its N-deuterated compound in solution, solid state and at low temperature are measured. Normal coordinate analysis for the planar vibrations of MTDAd o and -dl have been performed for the two most probable cis-trans-CONHCSor -CSNHCO-conformers using a simple Urey-Bradley force function. The conformation of MTDA derived from the vibrational spectra is supported by the all valence CNDO/2 molecular orbital method. The vibrational assignments and the electronic structure of MTDA are also given.