Transition metal complexes enslaved in the supercages of zeolite-Y: DFT investigation and catalytic significance

A series of zeolite-Y encapsulated hybrid catalysts, [M(STCH)·xH₂O]-Y have been prepared by encapsulating Schiff base complexes [where M?=?Mn(II), Fe(II), Co(II), Ni(II); (x?=?3) and Cu(II); (x?=?1); H₂STCH?=?salicylaldehyde thiophene-2-carboxylic hydrazone] in zeolite-Y matrix by flexible ligand method. These hybrid materials have been characterized by various physico-chemical techniques such as ICP-OES, elemental analyses, (FT-IR and electronic) spectral studies, BET, scanning electron micrographs, thermal analysis and X-ray powder diffraction patterns. X-ray powder diffraction analysis reveals that the structural integrity of the mother zeolite in the hybrid material remained intact upon immobilization of the complex. Density functional theory is employed to calculate the relaxed structure, bond angle, bond distance, dihedral angle, difference of highest occupied molecular orbital and lowest unoccupied molecular orbital energies gap and electronic density of states of ligand and their neat transition metal complexes. The hybrid materials are active catalysts for the hydroxylation of phenol using hydrogen peroxide (30% H₂O₂) as an oxidant in order to selectively synthesize catechol or hydroquinone, amongst them [Cu(STCH)·H₂O]-Y shown the highest % of selectivity towards catechol (81.3%).     

Fracto-mechanoluminescence and mechanics of fracture of solids

The present paper explores the correlation between fracto-mechanoluminescence and fracture of solids and thereby provides a clear understanding of the physics of fracto-mechanoluminescence. When a fluorescent or non-photoluminescent crystal is fractured impulsively by dropping a load on it, then initially the mechanoluminescence (ML) intensity increases linearly with time, attains a maximum value I_m at a particular time t_m and later on it decreases exponentially with time. However, when a phosphorescent crystal is fractured impulsively by dropping a load on it, then initially the ML intensity increases linearly with time, attains a maximum value I_m at a particular time t_m and later on it decreases initially at a fast rate and then at a slow rate. For low impact velocity the value of t_m is constant, however, for higher impact velocity t_m decreases logarithmally with the increasing impact velocity. Whereas the peak ML intensity I_m increases linearly with the impact velocity, the total ML intensity I_T, initially increases linearly with the impact velocity and then it tends to attain a saturation value for higher values of the impact velocity. The value of t_m increases logarithmally with the thickness of crystals, I_m increases linearly with the area of cross-section of crystals and I_T increases linearly with the volume of crystals. Generally, the ML of non-irradiated crystals decreases with increasing temperature of crystals. Depending on the prevailing conditions the ML spectra consist of either gas discharge spectra or solid state luminescence spectra or combination of the both. On the basis of the rate of generation of cracks and the rate of creation of new surface area of crystals, expressions are derived for the ML intensity and they are found to explain satisfactorily the temporal, spectral, thermal, crystal-size, impact velocity, surface area, and other characteristics of ML. The present investigation may be useful in designing of damage sensors, fracture sensors, ML-based safety management monitoring system, fuse-system for army warheads, milling machine, etc. The present study may be helpful in understanding the processes involved in earthquakes, earthquake lights and mine-failure as they basically involve fracture of solids.     

Spatial distribution of radium in coastal marine waters of Tamil Nadu

An investigation on the distribution of radium activity levels in the entire south eastern coast of Tamil Nadu, India, from Chennai to Kanyakumari was carried out. Insitu preconcentration technique was adopted by passing 1,000?L of seawater through MnO₂ impregnated cartridge filters at all the locations. In the coastal waters, ²²⁶Ra and ²²⁸Ra concentration was observed to be in the range of 1 to 1.81 and 3.1 to 7.5?mBq/L, respectively with an average of 1.52 and 4.53?mBq/L. respectively, while the sediment samples showed ²²⁶Ra activity levels from 8.1 to 129.0?Bq/kg and ²²⁸Ra varied from 14.7 to 430.01?Bq/kg. The Kd values for ²²⁶Ra was observed to be from 5.3E03 to 3.5E05?L/kg and for ²²⁸Ra it was in the range of 2.3E03 to 5.9E04. It was observed that the concentration of ²²⁸Ra was more than ²²⁶Ra in all the locations. The spatial distribution of the activity with respect to location is discussed in the paper. The radioactive database obtained, represents reference values for coastal environment of Tamil Nadu.     

化学反应对竖直平板边界磁流体动力学微极流体滑流的影响

Heat and mass transfer effects on the unsteady flow of a micropolar fluid through a porous medium bounded by a semi-infinite vertical plate in a slip-flow regime are studied taking into account a homogeneous chemical reaction of the first order. A uniform magnetic field acts perpendicular to the porous surface absorb micropolar fluid with a suction velocity varying with time. The free stream velocity follows an exponentially increasing or decreasing small perturbation law. Using the approximate method, the expressions for the velocity microrotation, temperature, and concentration are obtained. Futher, the results of the skin friction coefficient, the couple stress coefficient, and the rate of heat and mass transfer at the wall are presented with various values of fluid properties and flow conditions.     

The translation planes admitting a nonsolvable doubly transitive line-sized orbit

The finite translation planes of ordern not in {3⁴,3⁶,11²,19²,29²,59² that admit a non-solvable doubly transitive line-sized orbit are completely classified.     

Two-transitive parabolic ovals

We investigate finite affine planes of even order possessing a parabolic oval and a collineation group G which leaves invariant and acts 2-transitively on its affine points. The main attention is devoted to translation planes. The odd order case has already been considered by Enea and Korchmaros in [5]. Our main result shows that if has even order and possesses two 2-transitive parabolic ovals which share at least two, but not all their affine points, then is Desarguesian. Received 20 July 1998.     

Graphene Oxide Supported Oxovanadium (IV) Complex for Catalytic Peroxidative Epoxidation of Styrene: An Eye-Catching Impact of Solvent

Graphene oxide (GO) supported transition metal complexes are apprised as sturdy and everlasting heterogeneous catalysts. GO surface was functionalized with 3-triethoxysilylpropylamine (TSPA) and this amino functionalized GO (A-f-GO) nanocomposite with vanadyl Schiff base complex (VO-f-GO) was prepared and to give credence of its potentiality, it was chosen for the selective epoxidation of styrene using environmentally benign 30% H₂O₂ to styrene oxide (SO). To evade the detrimental exposure of “inborn” water, a selective high boiling and potent hygroscopic solvent, ethylene glycol was chosen to make this transformation productively successful. With the assistance of theoretical studies, we have probed the effect of H₂O₂ on to structural properties, binding mechanism and electronic properties of the catalyst and substrate. Adsorption energy (E_ad), energy band gap (E_g) and HOMO-LUMO were also calculated. Based on DFT calculations, resonance Raman and UV/Vis studies, we confirmed the formation of metal-peroxo species and propose the plausible catalytic pathway. The influence of the diverse experimental parameters, like substrate to oxidant mole ratio, catalyst concentration, type of solvents, solvent amount, time, temperature and oxidant were tested. A clear relationship was found between different reaction parameters like solvent amount, oxidant, catalyst concentration and temperature etc. and product distribution. This heterogeneous catalyst yielded styrene oxide as nearly the sole product (selectivity = 98.7%) with a conversion value of 99.2% in the oxidation of styrene with hydrogen peroxide in ethylene glycol.     

Attenuation of Sommerfeld effect in an internally damped eccentric shaft-disk system via active magnetic bearings

Meccanica - Eccentric shaft-disk system with internal damping driven by a non-ideal power source exhibits Sommerfeld effect characterized by nonlinear jump phenomena of amplitude and rotor speed...     

On translation planes of orderq 2 that admit a group of orderq 2 (q−1); bartolone's theorem

This article is concerned with translation planesP of orderq ² and kernelK isomorphic toG F(q). IfP admits a collineation groupG in the linear translation. complement and the order ofG K/K isq ²(q?1) then it is shown thatP is either a semifield plane or is a Lüneburg-Tits, Walker or Betten plane. This generalizes earlier work of Bartolone.     

Electron impact single and double ionization of argon

Stable two-mode, and three-mode oscillations due to the spatial hole burning effect were observed experimentally with the increase of the pump power ratio in a laser-diode pumped sub-nanosecond microchip Cr,Yb:YAG self-Q-switched multimode laser. The stability of the output pulse trains was attributed to the mode coupling through antiphase dynamics between different modes. Modified multimode rate equations including the spatial hole-burning effect in the active medium and the non-linear absorption of the saturable absorber were proposed. Numerical simulations of the antiphase dynamics of such a laser were in good agreement with the experimental data, and the antiphase dynamics were explained by the evolution of the inversion population and the bleaching and recovery of the inversion population of the saturable absorber.