Oxo- and oxoperoxo-molybdenum(VI) complexes with aryl hydroxamates: synthesis, structure, and catalytic uses in highly efficient, selective, and ecologically benign peroxidic epoxidation of olefins

A solution obtained by dissolving MoO3 in H2O2 reacts separately with secondary hydroxamic acids (viz., N-benzoyl N-phenyl hydroxamic acid (BPHAH), N-benzoyl N-ortho-, -meta-, -para-tolyl hydroxamic acids, (BOTHAH, BMTHAH, and BPTHAH, respectively), and N-cinnamoyl N-phenyl hydroxamic acid (CPHAH) affording [MoO(O2)(BPHA)2] (1), [MoO(O2)(BOTHA)2] (2), [MoO(O2)(BMTHA)2] (3), [MoO(O2)(BPTHA)2] (4), and [Mo(O)2(CPHA)2](5), respectively. The O and O2 are situated cis to each other in 2-4, but in each case, they are disordered and distributed over four sites. This disorder does not exist in the 6-coordinate cis dioxo complex 5, to which crude MoO(O2)(CPHA)2 (5') was converted during recrystallization. An aqueous molybdate solution readily reacts with all those hydroxamic acids producing [Mo(O)2(hydroxamate)2] (6). While 2, 3, and 4 possess a very distorted pentagonal bipyramidal structure, 5 has a distorted octahedral geometry. In the solid state, as well as in solution, 5 exists as two apparently enantiomerically related molecules differing in the orientation of the pendant phenyl rings. To emphasize that the formation and structural uniqueness of 5 compared to 1-4 is caused by the influence of the cinnamoyl residue, one compound of the 6 series, namely, [Mo(O)2(BPHA)2] (6A), was structurally characterized to prove directly that the special stereochemical properties of 5 rely on the special electronic structure of CPHA- ligand. Complexes 1-5, as well as 6, show high potential and selectivity as catalysts in the epoxidation of olefins at room temperature in the presence of NaHCO3 as a promoter and H2O2 as a terminal oxidant. A comparative epoxidation study has been performed to determine the relative efficiency of the catalysts. To make the epoxidation method cost effective, a study to optimize the use of H2O2 has also been performed. To obtain evidence in favor of our suggested mechanism to this homogeneous olefin --> epoxide conversion, it was necessary to synthesize a peroxo-rich compound, namely, [MoO(O2)2BMTHA]- (7), but the attempted synthesis culminated in the isolation of [MoO(O2)2(C6H5COO)]- (8), obviously, via the hydrolysis of coordinated BMTHA.     

Kadomtsev-Petviashvili (KP) Burgers Equation in Dusty Negative Ion Plasmas: Evolution of Dust-Ion Acoustic Shocks

We study the nonlinear propagation of dust-ion acoustic (DIA) shock waves in an un-magnetized dusty plasma which consists of electrons, both positive and negative ions and negatively charged immobile dust grains. Starting from a set of hydrodynamic equations with the ion thermal pressures and ion kinematic viscosities included, and using a standard reductive perturbation method, the Kadomtsev-Petviashivili-Burgers (K-P-Burgers) equation is derived, which governs the evolution of DIA shocks. A stationary solution of the K-P-Burgers equation is obtained and its properties are analysed with different plasma number densities, ion temperatures and masses. It is shown that a transition from shocks with negative potential to positive one occurs depending on the negative ion concentration in the plasma and the obliqueness of propagation of DIA waves.     

Control of coexisting attractors via temporal feedback

We propose a method for controlling coexisting attractors in multistable dynamical systems. In this method, the feedback for an initial duration of time can drive the system to the desired state. We have illustrated this method by considering temporal feedback in autonomous as well as non-autonomous dynamical systems. The experimental realisation of the proposed method is also presented.     

Lower order three-dimensional Burgers equation having non-Maxwellian ions in dusty plasmas

The dust acoustic(DA) shock wave with dust charge fluctuations, non-Maxwellian ions, and non-isothermal electrons is studied theoretically. The perturbation technique is employed to derive the lower order three-dimensional(3D) Burgers equation, and shock wave solution is explored by the tan-hyperbolic method. The effects of flat trapped and trapped electron distributions in the presence of Maxwellian and non-Maxwellian ions on characteristics shock waves are observed. The temperature ratio of non-Maxwellian ion temperature and non-isothermal electron temperature is found to play an important role in forming the shock-like structure.     

Molecular Dynamics Simulation of MBE Growth of CdTe/ZnTe/Si

We simulate in three dimensions molecular beam epitaxial (MBE) growth of CdTe/ZnTe/Si using classical molecular dynamics. Atomic interactions are simulated with Stillinger–Weber potentials, whose parameters are obtained by fitting to experimental data or density function theory-calculated distortion energies of the component crystals. The effects of substrate temperature and atomic species flux ratios on epilayer morphology are investigated. The agreement between simulations and experiments suggests that this model has reasonable ability to predict the microstructures of CdTe/ZnTe/Si grown by MBE.     

Ion irradiation induced evolution of nanostructure in a graded multi-trilayer system

Nanostructural modifications in a double-graded Pt/Ni/C multi-trilayer, due to irradiation by an energetic ion-beam, have been analyzed using X-ray reflectivity (XRR), X-ray standing wave (XSW) and cross-sectional transmission electron microscopy (X-TEM) techniques. 2 MeV Au²⁺ ions were rastered on Pt/Ni/C multi-trilayer samples producing a uniformly irradiated area at ion-fluences ranging from 1 × 10¹⁴ ions/cm² to 2 × 10¹⁵ ions/cm². Ion irradiation induced modifications of microstructural parameters, e.g., layer thicknesses and electron densities of individual layers and interface roughnesses have been obtained from XRR analysis. Pt- and Ni-fluorescence yield from the as-deposited sample under the XSW condition show the distinct existence of Pt and Ni layers. The almost indistinguishable Pt- and Ni-fluorescence data over the first order Bragg peak from the sample irradiated at the highest ion-fluence, suggest complete mixing of Pt and Ni. Strong mixing between Pt and Ni in the ion irradiated samples is also corroborated by XRR results. X-TEM studies reveal the individual layer structure in the as-deposited sample. This layer structure is lost in the sample irradiated at the highest ion fluence indicating a complete mixing between Pt and Ni layers and nanoscale grain growth of Pt-Ni alloys. Additionally, formation of Pt-Ni alloy nano-clusters in the C-layers is observed. The results are understood in the light of the positive heat of mixing between Pt and C, and Ni and C and the negative heat of mixing between Pt and Ni. The effect of heat of mixing becomes dominant at high fluence irradiation.     

Dielectric relaxation in a new double perovskite oxide Ho2MgZrO6

A new double perovskite oxide holmium magnesium zirconate Ho₂MgZrO₆ (HMZ) was prepared by solid state reaction technique. The crystal structure has been determined by powder X-ray diffraction which shows monoclinic phase at room temperature with cell parameters a = 9.3028 ± 0.0030 Å, b = 5.2293 ± 0.0008 Å, c = 4.4009 ± 0.0009 Å, β = 103.3746 ± 0.0166°. An analysis of complex permittivity with frequency was carried out assuming a distribution of relaxation times. The frequency dependent electrical data are analyzed in the framework of conductivity and electric modulus formalisms. At the high temperature range, conductivity data satisfy the variable range hopping (VRH) model. In this regime, the conductivity of sample obeys Mott’s T^1/4 law, characteristic of VRH. High temperature data indicates the formation of thermally activated small polarons. The scaling behaviour of imaginary part of electric modulus suggests that the relaxation describes the same mechanism at various temperatures.     

Application of INAA for phyto-accumulation study of selenium by chickpea plant

The phyto-accumulation efficacy of selenium (Se) from soil by chickpea plant is reported. Chickpea plants were grown in soil having different concentrations (1–4 mg kg^?1) of Se. Samples of soil and different parts of chickpea plants in Se rich soil were analyzed for determination of Se concentrations by instrumental neutron activation analysis (INAA). Samples were irradiated in self-serve facility of CIRUS reactor, BARC, Mumbai at a neutron flux of the order of 10¹³ cm^?2 s^?1. The gamma activity at 264.7 keV of ⁷⁵Se (119.8 d) was measured using a 45% relative efficiency HPGe detector coupled to MCA. Dependence of Se distribution in soil and plants on its spiking concentration was evaluated in this work. The Se concentrations determined in plant parts grown in control soil and in soil spiked with Se (4 mg kg^?1) are in the range of 0.6–0.8 and 65–68 mg kg^?1 respectively.     

4H-SiC RF power MOSFETs

A 4H silicon carbide lateral RF MOSFET has been fabricated and characterized for the first time. The improved performance of this device was facilitated by a two-metal-layer process, which optimizes the conflicting requirements of acceptable inversion-layer mobility and low contact resistance. The cut-off frequency of the device with 1-μm gate length was in excess of 7 GHz