Vinyl radical induced Michael additions: Total synthesis of (±)-seychellene

A new strategy for the total synthesis of (±)-seychellene which involves (i) a regiospecific construction of a bicyclo(2.2.2)octene moiety having a methyl group at the bridgehead and (ii) a vinyl radical induced intramolecular Michael addition is described.

Electron field emission from sp (2)-induced insulating to metallic behaviour of amorphous carbon (a-C) films

The influence of concentration and size of sp (2) cluster on the transport properties and electron field emissions of amorphous carbon films have been investigated. The observed insulating to metallic behaviour from reduced activation energy derived from transport measurement and threshold field for electron emission of a-C films can be explained in terms of improvements in the connectivity between sp (2) clusters. The connectivity is resulted by the cluster concentration and size. The concentration and size of sp (2) content cluster is regulated by the coalescence of carbon globules into clusters, which evolves with deposition conditions.

Polymorphism in a TADDOL analogue induced by the presence of a chiral impurity

Crystallization of a TADDOL analogue results in an orthorhombic P2(1)2(1)2(1) form while the presence of a minute amount of a chiral impurity in the crystallization is found to be responsible for crystallization in a monoclinic P2(1) form.

Biochemical, histopathological and ultrastructural changes in rat liver induced by r-( + )-pulegone, a monoterpene ketone

Biochemical, histopathological and ultrastructural changes occurring at different time points after intraperitoneal administration of a single dose of pulegone (300 mg/kg) were studied. Significant decreases in the level of liver microsomal cytochrome P-450 (67%), heme (37%), aminopyrine N-demethylase (60%) and glucose-6-phosphatase (58%), were noticed 24 hr after pulegone treatment. Alanine amino transferase (ALT) levels increased in a time dependent manner, following exposure of rats to pulegone. Light microscopic studies of liver tissues showed dilation of central veins and distention of sinusoidal spaces 6 hr after pulegone treatment. Initial centrilobular necrosis was noticed at 12 hr. Centrilobular necrosis became severe at 18 hr and nuclear changes included karyorrhexis and karyolysis. Midzonal and periportal degenerative changes in addition to centrilobular necrosis was observed 24 hr after pulegone administration. Electron microscopic changes showed severe degeneration of endoplasmic reticulum, swelling of mitochondria and nuclear changes, 24 hr after administration of pulegone. The time course profile of the hepatocytes after treatment with pulegone indicates that endoplasmic reticulum is the organelle most affected, following which other degenerative changes occur ultimately leading to cell death.

A study on boundary-layer transition induced by free-stream turbulence

Boundary-layer transition at different free-stream turbulence levels has been investigated using the particle-image velocimetry technique. The measurements show organized positive and negative fluctuations of the streamwise fluctuating velocity component, which resemble the forward and backward jet-like structures reported in the direct numerical simulation of bypass transition. These fluctuations are associated with unsteady streaky structures. Large inclined high shear-layer regions are also observed and the organized negative fluctuations are found to appear consistently with these inclined shear layers, along with highly inflectional instantaneous streamwise velocity profiles. These inflectional velocity profiles are similar to those in the ribbon-induced boundary-layer transition. An oscillating-inclined shear layer appears to be the turbulent spot-precursor. The measurements also enabled to compare the actual turbulent spot in bypass transition with the simulated one. A proper orthogonal decomposition analysis of the fluctuating velocity field is carried out. The dominant flow structures of the organized positive and negative fluctuations are captured by the first few eigenfunction modes carrying most of the fluctuating energy. The similarity in the dominant eigenfunctions at different Reynolds numbers suggests that the flow prevails its structural identity even in intermittent flows. This analysis also indicates the possibility of the existence of a spatio-temporal symmetry associated with a travelling wave in the flow.

Microstructural changes induced by ternary additions in a hypo-eutectic titanium-silicon alloy

Hypo-eutectic Ti-6.5 wt % Si alloy modified by separate additions of misch metal and low surface tension elements (Na, Sr, Se and Bi) has been examined by microscopic study and thermal analysis. Addition of third element led to modification of microstructure with apparently no significant enhancement of tensile ductility, with the exception of bismuth. Bismuth enhanced the ductility of the alloy by a factor of two and elastic-plastic fracture toughness to 9 MPa m–1/2 from a value of almost zero. The improved ductility of bismuth modified alloy is attributed to the reduced interconnectivity of the eutectic suicide, absence of significant suicide precipitation in the eutectic region and increase in the volume fraction of uniformly distributed dendrites. These changes are accompanied by a decrease in the temperature of eutectic solidification.

Mixed Convection Induced in a Gas Flowing Past a Hot Horizontal Flat Plate

A boundary layer analysis of mixed convective motion over a hot horizontal flat plate is performed under the conditions of steady flow and low speed. Use of the Howarth-Dorodnytsyn transformation makes it possible to dispense with the usual Boussinesq approximation, and variable gas properties are accounted for via the assumption that dynamic viscosity and thermal conductivity are proportional to the absolute temperature. The formulation presented enables the entire mixed convection regime to be described by a single set of equations. Finite difference solutions when the Prandtl number is 0.72 are obtained over the entire range of the mixed convection parameter ξ from 0 (free convection) to 1 (forced convection) and heating parameter ▵ values from 2 to 12. The effects of both ξ and ▵on the velocity profiles, the temperature profiles, and the variation of skin friction and heat transfer functions are clearly illustrated in tables and graphs.

MNDO study of coupled strained hydrocarbons: Additivity of exocyclic C---C bond contraction induced by different ring systems

MNDO geometry optimizations were carried out on a series of symmetrically and unsymmetrically coupled strained ring hydrocarbons, R1-R1 and R1–R2 (R1=methyl, cyclopropyl, 1-bicyclo[1.1.0]butyl, 1-bicyclo[1.1.1]pentyl, prismyl, cubyl, 6-tricyclo [3.1.1.03,6]heptyl, and tetrahedryl groups; R2=methyl and cyclopropyl). The remarkable contraction of the C---C bond connecting the strained rings found experimentally in a few cases was reproduced correctly by the calculations. A linear correlation was found between the bond length shortening and the bond angle widening at the corresponding carbon atoms for all the structures considered. The reduction in C---C bond lengths due to various ring systems is additive. The additivity indicates that inter-ring interactions which effect the central bond length are absent and confirms the common electronic origin of bond contraction in these systems, viz. enhanced s-character in the exocyclic bonds of strained rings.

Jahn-Teller effect induced phase transitions in CsCuCl3

Occurence of the three Jahn-Teller effect induced phase transitions of CsCuCl3 at 423, 510 and 535 K has been established and the nature of the transitions examined by X-ray crystallography, far infrared spectroscopy and other techniques.

Jahn-Teller effect induced phase transitions in CsCuCl3

Occurence of the three Jahn-Teller effect induced phase transitions of CsCuCl3 at 423, 510 and 535 K has been established and the nature of the transitions examined by X-ray crystallography, far infrared spectroscopy and other techniques.

Time-Resolved Resonance Raman Studies on Proton-Induced Electron-Transfer Reaction from Triplet Excited State of 2-Methoxynaphthalene to Decafluorobenzophenone

In this paper time-resolved resonance Raman (TR3) spectra of intermediates generated by proton induced electron-transfer reaction between triplet 2-methoxynaphthalene ((ROMe)-R-3) and decafluorobenzophenone (DFBP) are presented The TR3 vibrational spectra and structure of 2-methoxynaphthalene cation radical (ROMe+) have been analyzed by density functional theory (DFT) calculation It is observed that the structure of naphthalene ring of ROMe+ deviates from the structure of cation radical of naphthalene