Molybdenum trioxide catalyzed oxidative cross-dehydrogenative coupling of benzylic sp(3) C-H bonds: synthesis of alpha-aminophosphonates under aerobic conditions

Molybdenum trioxide (MoO3) catalyzed efficient oxidative cross-dehydrogenative-coupling (CDC) method for C-H functionalization of N-aryl tetrahydroisoquinolines has been explored. This user-friendly method of synthesizing alpha-aminophosphonates employs 1.1 equiv of dialkyl-H-phosphonate under aerobic condition. Formation of new C-P bonds from unfunctionalized starting materials under environmentally benign conditions provides an excellent avenue for the synthesis of biologically active alpha-aminophosphonates. (C) 2012 Elsevier Ltd. All rights reserved.

Novel and efficient protocol for the syntheses of N-1 substituted thiohydantoin and a bicyclothiohydantoin under solvent-free conditions

A novel approach for the synthesis of N-1 substituted thiohydantoin has been developed to give quantitative yields of the desired products. The efficient synthesis of bis-thiohydantoin derivative and bicyclothiohydantoin has extended scope and applicability of present method. Solvent-free conditions and very easy work-up procedure make the reaction convenient and eco-friendly. All the products were characterized by spectroscopic techniques and elemental analysis, and finally the structure of representative ;compound was also confirmed by X-ray crystallography. (C) 2012 Elsevier Ltd. All rights reserved.

On the Presumed Kinetic Consequences of Pre-equilibrium. Implications for the Michaelis-Menten Equation

The overall rate equation for a reaction sequence consisting of a pre-equilibrium and rate-determining steps should not be derived on the basis of the concentration of the intermediate product (X). This is apparently indicated by transition state theory (as the path followed to reach the highest energy transition state is irrelevant), but also proved by a straight-forward mathematical approach. The thesis is further supported by the equations of concurrent reactions as applied to the partitioning of X between the two competing routes (reversal of the pre-equilibrium and formation of product). The rate equation may only be derived rigorously on the basis of the law of mass action. It is proposed that the reactants acquire the overall activation energy prior to the pre-equilibrium, thus forming X in a high-energy state en route to the rate-determining transition state. (It is argued that conventional energy profile diagrams are misleading and need to be reinterpreted.) Also, these arguments invalidate the Michaelis-Menten equation of enzyme kinetics, and necessitate a fundamental revision of our present understanding of enzyme catalysis. (The observed ``saturation kinetics'' possibly arises from weak binding of a second molecule of substrate at the active site; analogous conclusions apply to reactions at surfaces).

Reactivity of Bispropargyl Sulfones under Basic Conditions: Interplay Between Garratt-Braverman and Schmittel/Myers-Saito Cyclization Pathway

The preference for GarrattBraverman (GB) over MyersSaito (MS) and Schmittel (SCM) cyclizations has recently been demonstrated in sulfones capable of undergoing all three of the processes. As the GB cyclization is a self-quenching process, there is a need to change the selectivity to the non-self-quenching MS or SCM pathway so as to enhance the DNA-cleaving efficiency that operates through the radical-mediated process. Herein we report a conformational constraint-based strategy developed by using computations (M06-2X/6-31+G*) to switch the selectivity from GB to MS/SCM pathway which also results in greater DNA-cleavage activity. The preference for GB could be brought back by easing the constraint with the help of spacers.

Relative effect of slope and equilibrium line altitude on the retreat of Himalayan glaciers

It has been observed that a majority of glaciers in the Himalayas have been retreating. In this paper, we show that there are two major factors which control the advance/retreat of the Himalayan glaciers. They are the slope of the glacier and changes in the equilibrium line altitude. While it is well known, that these factors are important, we propose a new way of combining them and use it to predict retreat. The functional form of this model has been derived from numerical simulations using an ice-flow code. The model has been successfully applied to the movement of eight Himalayan glaciers during the past 25 years. It explains why the Gangotri glacier is retreating while Zemu of nearly the same length is stationary, even if they are subject to similar environmental changes. The model has also been applied to a larger set of glaciers in the Parbati basin, for which retreat based on satellite data is available, though over a shorter time period.

Sensitivity of polyvinylidene fluoride films to mechanical vibration modes and impact after optimizing stretching conditions

The β-phase of polyvinylidene fluoride (PVDF) is well known for its piezoelectric properties. PVDF films have been developed using solvent cast method. The films thus produced are in α-phase. The α-phase is transformed to piezoelectric β-phase when the film is hot-stretched with various different stretching factors at various different temperatures. The films are then characterized in terms of their mechanical properties and surface morphological changes during the transformation from α- to β-phases by using X-ray diffraction, differential scanning calorimeter, Raman spectra, Infrared spectra, tensile testing, and scanning electron microscopy. The films showed increased crystallinity with stretching at temperature up to 80°C. The optimum conditions to achieve β-phase have been discussed in detail. The fabricated PVDF sensors have been tested for free vibration and impact on plate structure, and its response is compared with conventional piezoelectric wafer type sensor. The resonant and antiresonant peaks in the frequency response of PVDF sensor match well with that of lead zirconate titanate wafer sensors. Effective piezoelectric properties and the variations in the frequency response spectra due to free vibration and impact loading conditions are reported. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers.

Ultrahigh-temperature metamorphism from an unusual corundum plus orthopyroxene intergrowth bearing Al-Mg granulite from the Southern Marginal Zone, Limpopo Complex, South Africa

The Southern Marginal Zone of the Limpopo Complex is composed of granite-greenstone cratonic rocks reworked by a Neoarchean high-grade tectono-metamorphic event. Petrographic and mineral chemical characterization of an Al-Mg granulite from this zone is presented here. The granulite has a gneissic fabric with distinct Al-rich and Si-rich layers, with the former preserving the unusual lamellar (random and regular subparallel) intergrowths of corundum and symplectic intergrowth of spinel with orthopyroxene. The Al-rich layer preserves mineral assemblages such as rutile with orthopyroxene + sillimanite +/- A quartz, Al-rich orthopyroxene (similar to 11 wt%), spinel + quartz, and corundum in possible equilibrium with quartz, while the Si-rich layer preserves antiperthites and orthopyroxene + sillimanite +/- A quartz, all considered diagnostic of ultrahigh-temperature metamorphism. Application of Al-in-opx thermometry, ternary feldspar thermometry and construction of suitable pressure-temperature phase diagrams, compositional and model proportion isopleth results indicate P-T conditions as high as similar to 1,050-1,100 A degrees C, and similar to 10-12 kbars for the Al-Mg granulite. Our report of ultrahigh-temperature conditions is significant considering that the very high temperature was reached during decompression of an otherwise high-pressure granulite complex (clockwise P-T path), whereas most other ultrahigh-temperature granulites are linked to magma underplating at the base of the crust (counterclockwise P-T path).

Continuum theory of edge states of topological insulators: variational principle and boundary conditions

We develop a continuum theory to model low energy excitations of a generic four-band time reversal invariant electronic system with boundaries. We propose a variational energy functional for the wavefunctions which allows us to derive natural boundary conditions valid for such systems. Our formulation is particularly suited for developing a continuum theory of the protected edge/surface excitations of topological insulators both in two and three dimensions. By a detailed comparison of our analytical formulation with tight binding calculations of ribbons of topological insulators modelled by the Bernevig-Hughes-Zhang (BHZ) Hamiltonian, we show that the continuum theory with a natural boundary condition provides an appropriate description of the low energy physics.