Transition metal catalyzed carboannulation of diazabicyclic alkenes with ambiphilic bifunctional reagents: a facile route towards functionalized indanones and indanols

Functionalized indanones are readily prepared in good to excellent yields by the Pd/Rh catalyzed carboannulation of bicyclic and tricyclic hydrazines with 2-iodobenzonitrile, 2-cyanophenylboronic acid and 2-formylphenylboronic acid. The reaction with 2-formylphenylboronic acid afforded 3,4-disubstituted cyclopentenes as minor product along with indanones under Rh catalyzed conditions, whereas indanols were obtained as the major product under Pd catalyzed conditions. The products obtained can be synthetically manipulated easily to pharmaceutically important molecules.     

Synthesis of polyethylene glycol (PEG) assisted tungsten oxide (WO3) nanoparticles for L-dopa bio-sensing applications

Nanocrystalline tungsten oxides (WO_3−δ) are currently receiving a lot of attention because of their interesting electrical, magnetic, optical and mechanical properties. In this report, we present the synthesis of PEG assisted tungsten oxide (WO₃) nanoparticles by simple household microwave irradiation (2.45 GHz) method. The samples were characterized using powder X-ray diffraction (XRD), thermal analysis (TG/DTA), transmission electron microscopy (TEM), UV-visible diffusion reflectance spectroscopy (UV-VIS-DRS), cyclic voltammetry and electrochemical impedance spectroscopy. Powder XRD results revealed that both the samples prepared with and without surfactant crystallize in the orthorhombic structure corresponding to WO₃·H₂O phase. Subsequent annealing under identical conditions (600 °C/air/6 h) led to significantly different products i.e. monoclinic W₁₇O₄₇ from surfactant free sample and orthorhombic WO₃ from PEG assisted sample. Blue emission was observed through UV-VIS-DRS with blue shift and the band gap energy was estimated as 2.7 and 3.28 eV for PEG assisted as prepared (WO₃·H₂O) and annealed samples (WO₃) respectively. Electrochemical measurements have been performed on all the samples deposited on the surface of glassy carbon (GC) electrode which showed high sensitivity and good selectivity for PEG assisted sample (WO₃·H₂O) for the direct detection of l-dopa.     

Shape- and size-controlled synthesis in hard templates: sophisticated chemical reduction for mesoporous monocrystalline platinum nanoparticles

Here we report a novel hard-templating strategy for the synthesis of mesoporous monocrystalline Pt nanoparticles (NPs) with uniform shapes and sizes. Mesoporous Pt NPs were successfully prepared through controlled chemical reduction using ascorbic acid by employing 3D bicontinuous mesoporous silica (KIT-6) and 2D mesoporous silica (SBA-15) as a hard template. The particle size could be controlled by changing the reduction time. Interestingly, the Pt replicas prepared from KIT-6 showed polyhedral morphology. The single crystallinity of the Pt fcc structure coherently extended over the whole particle.     

Determination of perfluorooctanoate and perfluorooctanesulfonate in water matrices by inline matrix elimination liquid chromatography with reversed phase separation and suppressed conductivity detection

This work describes a new method for the determination of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) in water matrices by suppressed conductivity detection. Separation was achieved by isocratic elution on a reversed-phase column thermostated at 45°C using an aqueous mobile phase containing boric acid and acetonitrile. The PFOA and PFOS content in the water matrix were quantified by a pre-concentration technique. For the concentration range of 1 to 15 ng/mL and 2 to 30 ng/mL, the linear calibration curve for PFOA and PFOS yielded coefficients of determination (R(2)) of 0.9995 and 0.9985, respectively. The relative standard deviations were smaller than 1.5% for PFOA and PFOS. The retention-time precision of four consecutive 12 h injections was smaller than 0.641% and 0.818%, respectively. The presence of common divalent cations, such as calcium, magnesium, and iron in water matrices impairs PFOS recovery. This drawback was overcome by applying inline matrix elimination method. The optimized method was successfully applied for drinking water, ground water, and seawater samples.     

Computational studies on tetrazole derivatives as potential high energy materials

The tetrazole is an important functionality of the most of energetic materials due to 80% nitrogen content, stability, and high enthalpy of formation. The present structure–property relationship study focuses on the optimized geometries of tetrazole derivatives obtained from density functional theory (DFT) calculations at B3LYP/6-31G* levels. The heat of formation (HOF) of tetrazole derivatives have been calculated by designing the appropriate isodesmic reactions. The increase in nitro groups on azole rings shows the remarkable increase in HOF. Density has been predicted by using CVFF force field. Increase in the nitro group increases the density. Detonation properties of the designed compounds were evaluated by using the Kamlet–Jacobs equation based on predicted densities and HOFs. Designed tetrazole derivatives show detonation velocity (D) over 8 km/s and detonation pressure (P) of about 32 GPa. Thermal stability was evaluated via bond dissociation energies (BDE) of the weakest C–NO₂ bond at B3LYP/6-31G* level. Charge on the nitro group has been used to assess the sensitivity correlation. Overall, the study implies that designed compounds of this series are found to be stable and expected to be the novel candidates of high energy materials (HEMs).     

Synthesis, characterization and structures of 2-(3,5-dimethylpyrazol-1-yl)ethylseleno derivatives and their probable glutathione peroxidase (GPx) like activity

A series of 2-(3,5-dimethylpyrazol-1-yl)ethylseleno derivatives has been synthesized. The glutathione peroxidase like catalytic activity of these compounds has been studied in a model system, in which reduction of hydrogen peroxide with dithiothreitol (DTT(red)), in the presence of an organoselenium compound was investigated by (1)H NMR spectroscopy. All these compounds exhibit GPx like catalytic activities and the catalytic reaction proceeds through a selenoxide intermediate, identified by (77)Se{(1)H} NMR spectroscopy.     

Generalized Langevin dynamics of a nanoparticle using a finite element approach: thermostating with correlated noise

A direct numerical simulation (DNS) procedure is employed to study the thermal motion of a nanoparticle in an incompressible Newtonian stationary fluid medium with the generalized Langevin approach. We consider both the Markovian (white noise) and non-Markovian (Ornstein-Uhlenbeck noise and Mittag-Leffler noise) processes. Initial locations of the particle are at various distances from the bounding wall to delineate wall effects. At thermal equilibrium, the numerical results are validated by comparing the calculated translational and rotational temperatures of the particle with those obtained from the equipartition theorem. The nature of the hydrodynamic interactions is verified by comparing the velocity autocorrelation functions and mean square displacements with analytical results. Numerical predictions of wall interactions with the particle in terms of mean square displacements are compared with analytical results. In the non-Markovian Langevin approach, an appropriate choice of colored noise is required to satisfy the power-law decay in the velocity autocorrelation function at long times. The results obtained by using non-Markovian Mittag-Leffler noise simultaneously satisfy the equipartition theorem and the long-time behavior of the hydrodynamic correlations for a range of memory correlation times. The Ornstein-Uhlenbeck process does not provide the appropriate hydrodynamic correlations. Comparing our DNS results to the solution of an one-dimensional generalized Langevin equation, it is observed that where the thermostat adheres to the equipartition theorem, the characteristic memory time in the noise is consistent with the inherent time scale of the memory kernel. The performance of the thermostat with respect to equilibrium and dynamic properties for various noise schemes is discussed.     

Fourier Transform 13C NMR Analysis of Some Methaqualone Metabolites

The natural abundance carbon-13 nuclear magnetic resonance spectra of some methaqualone metabolites were recorded using the pulse fourier transform technique. The chemical shift of various carbon resonances have been assigned on the basis of the chemical shift theory, multiplicities observed in SFORD spectrum and comparison with the chemical shifts of the corresponding carbons of methaqualone.     

Bianchi type I inflationary universe in general relativity

In this paper, we have investigated Bianchi type I inflationary universe in the presence of massless scalar field with a flat potential. To get an inflationary solution, we have considered a flat region in which potential V is constant. The inflationary scenario of the model is discussed in detail.     

Studies on photoinduced effects in pulse-electrodeposited Ag/Hg-1212/CdSe hetero-nanostructures

Metal/superconductor/semiconductor (Ag/Hg-1212/CdSe) hetero-nanostructures have been fabricated using pulse-electrodeposition technique and are characterized by X-ray diffraction (XRD), full-width at half-maximum (FWHM) and scanning electron microscopy (SEM) studies. The junction capacitance of Ag/Hg-1212, Hg-1212/CdSe and Ag/Hg-1212/CdSe heterojunctions is measured in dark and under laser irradiation at room temperature. The nature of the junction formed and built-in-junction potentials were determined. The increase in carrier concentration across the junction due to photo-irradiation has been observed.