Kinetics and mechanism of the oxidation of some cyclic and acyclic ketones by dodecatungstocobaltate(III)—A comparative study

The kinetics of oxidation of cyclohexanone(chxn), 2-butanone(but), and 1,3-dihydroxy-2-propanone (dhp) have been investigated in aqueous acidic media. A first-order dependence in complex is obtained at high acid and low oxidant concentration for these ketones. However, a zero-order rate prevails at high oxidant and low acid concentration, and this rate has been shown to be the acid catalyzed enolization rate of the ketone. A general rate expression has been derived to explain these behaviors and plausible mechanism has been offered by assuming the enol as the reactive species.     

Design and synthesis of multidentate ligands via metal promoted C-N bond formation processes and their coordination chemistry

This presentation reports some novel examples of organic ring amination reactions via metal mediation. The organic transformations are highly regioselective and can be controlled by the proper selection of the mediator complex. The two isomeric organic ligands viz. HL¹ and HL² were isolated in their pure states by the removal of the metal ions. These were fully characterized. The ligand HL¹ has lowpKa, 8.5. Upon deprotonation, it behaves as a potentialbis chelating N,N,N-donors. The coordination chemistry of the HL¹ ligand involving some 3d-metal ions is described. Two unusual low-spin complexes of manganese(II) and iron(III) are reported. The ferric complex displayed a rhombic EPR while, the corresponding manganese compound showed a complex pattern due to hyperfine coupling. All the complexes displayed large number of redox responses. A brief mention about the future projection of this work is noted.     

On the determination and construction of optimal row-column designs having unequal row and column sizes

In this paper we consider experimental situations requiring usage of a row-column design where v treatments are to be applied to experimental units arranged in b ₁ rows and b ₂ columns where row i has size k _1i , i=1,..., b ₁ and column j has size k _2j , j=1,..., b ₂. Conditions analogous to those given in Kunert (1983, Ann. Statis., 11, 247–257) and Cheng (1978, Ann. Statist., 6, 1262–1272) are given which can often be used to establish the optimality of a given row-column design from the optimality of an associated block design. In addition, sufficient conditions are derived which guarantee the existence of an optimal row-column design which can be constructed by appropriately arranging treatments within blocks of an optimal block design.Visiting from the Indian Statistical Institute.     

Electrical spin injection and threshold reduction in a semiconductor laser

A spin-polarized vertical-cavity surface-emitting laser is demonstrated with electrical spin injection from an Fe/Al0.1Ga0.9As Schottky tunnel barrier. Laser operation with a spin-polarized current results in a maximum threshold current reduction of 11% and degree of circular polarization of 23% at 50 K. A cavity spin polarization of 16.8% is estimated from spin-dependent rate equation analysis of the observed threshold reduction.     

Extraordinary Changes in the Electronic Structure and Properties of CdS and ZnS by Anionic Substitution: Cosubstitution of P and Cl in Place of S

Unlike cation substitution, anion substitution in inorganic materials such as metal oxides and sulfides would be expected to bring about major changes in the electronic structure and properties. In order to explore this important aspect, we have carried out first‐principles DFT calculations to determine the effects of substitution of P and Cl on the properties of CdS and ZnS in hexagonal and cubic structures and show that a sub‐band of the trivalent phosphorus with strong bonding with the cation appears in the gap just above the valence band, causing a reduction in the gap and enhancement of dielectric properties. Experimentally, it has been possible to substitute P and Cl in hexagonal CdS and ZnS. The doping reduces the band gap significantly as predicted by theory. A similar decrease in the band gap is observed in N and F co‐substituted in cubic ZnS. Such anionic substitution helps to improve hydrogen evolution from CdS semiconductor structures and may give rise to other applications as well.     

Fe(iii) phytate metallogel as a prototype anhydrous,intermediate temperature proton conductor

A proton conducting metallogel [FNPA; ferric nitrate (FN)–phytic acid (PA)] is synthesized by immobilizing a protogenic ligand (phytic acid) using iron(iii) nitrate in DMF. The xerogel shows high proton conductivity of 2.4 × 10^–2 S cm^–1 at 120 °C, the best value known among all metal organic materials (MOMs). Marking the first such attempt in MOMs, an electrode made using the xerogel showed a power density of 0.94 mW cm^–2 at 0.6 V under dry fuel cell conditions.     

A new method for exact solutions of variant types of time‐fractional Korteweg‐de Vries equations in shallow water waves

The current article devoted on the new method for finding the exact solutions of some time‐fractional Korteweg–de Vries (KdV) type equations appearing in shallow water waves. We employ the new method here for time‐fractional equations viz. time‐fractional KdV‐Burgers and KdV‐mKdV equations for finding the exact solutions. We use here the fractional complex transform accompanied by properties of local fractional calculus for reduction of fractional partial differential equations to ordinary differential equations. The obtained results are demonstrated by graphs for the new solutions. Copyright © 2016 John Wiley & Sons, Ltd.     

The transport dynamics in complex systems governing by anomalous diffusion modelled with Riesz fractional partial differential equations

In this paper, numerical solutions of fractional Fokker–Planck equations with Riesz space fractional derivatives have been developed. Here, the fractional Fokker–Planck equations have been considered in a finite domain. In order to deal with the Riesz fractional derivative operator, shifted Grünwald approximation and fractional centred difference approaches have been used. The explicit finite difference method and Crank–Nicolson implicit method have been applied to obtain the numerical solutions of fractional diffusion equation and fractional Fokker–Planck equations, respectively. Numerical results are presented to demonstrate the accuracy and effectiveness of the proposed numerical solution techniques. Copyright © 2016 John Wiley & Sons, Ltd.