Additive-free vapour-phase hydrogenation of benzonitrile over MgO-supported Ni catalysts

Research on Chemical Intermediates - MgO-supported Ni catalysts were selectively catalysed by the hydrogenation of benzonitrile to benzylamine in continuous flow at atmospheric pressure without any...     

Ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of saquinavir in rat serum: application to pharmacokinetics

An ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of the most commonly prescribed protease inhibitor, saquinavir, in rat plasma was developed and validated. The effects of different ionic liquids, dispersive solvents, extractant/disperser ratio and salt concentration on sample recovery and enrichment were studied. Among the ionic liquids investigated, 1‐butyl‐3‐methylimidazolium hexafluorophosphate was found to be most effective for extraction of saquinavir from rat serum. The recovery was found to be 95% at an extractant/disperser ratio of 0.43 using 1‐butyl‐3‐methylimidazolium hexafluorophosphate and methanol as extraction and dispersive solvents. The recovery was further enhanced to 99.5% by addition of 5.0% NaCl. A threefold enhancement in detection and quantification limits was achieved, at 0.01 and 0.03 µg/mL, compared with the conventional protein precipitation method. A linear relationship was observed in the range of 0.035–10.0 µg/mL with a correlation coefficient (r²) of 0.9996. The method was validated and applied to study pharmacokinetics of saquinavir in rat serum. Copyright © 2014 John Wiley & Sons, Ltd.     

Two fluid flow and heat transfer in an inclined channel containing porous and fluid layer

Convective flow and heat transfer in an inclined channel bounded by two rigid plates held at constant different temperatures with one region filled with porous matrix saturated with a viscous fluid and another region with a clear viscous fluid different from the fluid in first region is studied analytically. The coupled nonlinear governing equations are solved using regular perturbation method. It is found that the presence of porous matrix in one of the region reduces the velocity and temperature. Results have been presented for a wide range of governing parameters such as Grashof number, porous parameter, angle of inclination, ratio of heights of the two layers and also the ratio of viscosities.     

Preparation and characterization of transparent conducting ZnS:Al films

Al-doped ZnS films were deposited using close-spaced evaporation of the powders synthesized by chemical precipitation method. The films were prepared for different Al concentrations in the range 0–10 at.% on glass substrates kept at 300 °C. The effect of Al-doping on ZnS composition, microstructure and optoelectronic properties of as-grown ZnS layers was determined using appropriate techniques. The films were polycrystalline and showed (111) preferred orientation for all the doping concentrations in spite of an additional phase of Al₂S₃ observed at higher dopant levels. The surface morphological studies indicated that the Al incorporation had a considerable effect on the surface roughness of the films. The optical measurements indicated that the optical energy band gap decreased slightly with the increase of dopant concentration without affecting the optical transmittance characteristics significantly. The electrical analysis indicated that the resistivity of the layers changed significantly with the doping concentration in the layers. The change of photoluminescence behaviour of the as-grown ZnS:Al films with dopant concentration was also studied.     

Cytoprotective Potential of Aged Garlic Extract (AGE) and Its Active Constituent,S-allyl-l-cysteine,in Presence of Carvedilol during Isoproterenol-Induced Myocardial Disturbance and Metabolic Derangements in Rats

This study was conducted to determine the potential interaction of aged garlic extract (AGE) with carvedilol (CAR), as well as to investigate the role of S-allyl-l-cysteine (SAC), an active constituent of AGE, in rats with isoproterenol (ISO)-induced myocardial dysfunction. At the end of three weeks of treatment with AGE (2 and 5 mL/kg) or SAC (13.1 and 32.76 mg/kg), either alone or along with CAR (10 mg/kg) in the respective groups of animals, ISO was administered subcutaneously to induce myocardial damage. Myocardial infarction (MI) diagnostic predictor enzymes, lactate dehydrogenase (LDH) and creatinine kinase (CK-MB), were measured in both serum and heart tissue homogenates (HTH). Superoxide dismutase (SOD), catalase, and thiobarbituric acid reactive species (TBARS) were estimated in HTH. When compared with other groups, the combined therapy of high doses of AGE and SAC given alone or together with CAR caused a significant decrease in serum LDH and CK-MB activities. Further, significant rise in the LDH and CK-MB activities in HTH was noticed in the combined groups of AGE and SAC with CAR. It was also observed that both doses of AGE and SAC significantly increased endogenous antioxidants in HTH. Furthermore, histopathological observations corroborated the biochemical findings. The cytoprotective potential of SAC and AGE were dose-dependent, and SAC was more potent than AGE. The protection offered by aged garlic may be attributed to SAC. Overall, the results indicated that a high dose of AGE and its constituent SAC, when combined with carvedilol, has a synergistic effect in preventing morphological and physiological changes in the myocardium during ISO-induced myocardial damage.     

State preparation and excited electronic and vibrational behavior in hemes

The temporally overlapping, ultrafast electronic and vibrational dynamics of a model five-coordinate, high-spin heme in a nominally isotropic solvent environment has been studied for the first time with three complementary ultrafast techniques: transient absorption, time-resolved resonance Raman Stokes, and time-resolved resonance Raman anti-Stokes spectroscopies. Vibrational dynamics associated with an evolving ground-state species dominate the observations. Excitation into the blue side of the Soret band led to very rapid S2 --> S1 decay (sub-100 fs), followed by somewhat slower (800 fs) S1 --> S0 nonradiative decay. The initial vibrationally excited, non-Boltzmann S0 state was modeled as shifted to lower energy by 300 cm(-1) and broadened by 20%. On a approximately 10 ps time scale, the S0 state evolved into its room-temperature, thermal distribution S0 profile largely through VER. Anti-Stokes signals disappear very rapidly, indicating that the vibrational energy redistributes internally in about 1-3 ps from the initial accepting modes associated with S1 --> S0 internal conversion to the rest of the macrocycle. Comparisons of anti-Stokes mode intensities and lifetimes from TRARRS studies in which the initial excited state was prepared by ligand photolysis [Mizutani, T.; Kitagawa, T. Science 1997, 278, 443, and Chem. Rec. 2001, 1, 258] suggest that, while transient absorption studies appear to be relatively insensitive to initial preparation of the electronic excited state, the subsequent vibrational dynamics are not. Direct, time-resolved evaluation of vibrational lifetimes provides insight into fast internal conversion in hemes and the pathways of subsequent vibrational energy flow in the ground state. The overall similarity of the model heme electronic dynamics to those of biological systems may be a sign that the protein's influence upon the dynamics of the heme active site is rather subtle.     

Near-infrared spectrophotometric determination of compositions of fullerene samples

A novel method has been developed for the sensitive and accurate determination of compositions of fullerene samples. The method is based on the synergistic use of spectrophotometric measurements and partial least square method. The method is not only simple, inexpensive and fast but also is non-destructive. Compositions of various fullerene samples including fullerite which is the precursor to C(60) and C(70), can be directly and non-destructively determined by this method without any time-consuming separation step as in the HPLC method or destruction as in the MS method.     

Magnetic switch of permeability for polyelectrolyte microcapsules embedded with Co@Au nanoparticles

We explored using a magnetic field to modulate the permeability of polyelectrolyte microcapsules prepared by layer-by-layer self-assembly. Ferromagnetic gold-coated cobalt (Co@Au) nanoparticles (3 nm diameter) were embedded inside the capsule walls. The final 5 mum diameter microcapsules had wall structures consisting of 4 bilayers of poly(sodium styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH), 1 layer of Co@Au, and 5 bilayers of PSS/PAH. External alternating magnetic fields of 100-300 Hz and 1200 Oe were applied to rotate the embedded Co@Au nanoparticles, which subsequently disturbed and distorted the capsule wall and drastically increased its permeability to macromolecules like FITC-labeled dextran. The capsule permeability change was estimated by taking the capsule interior and exterior fluorescent intensity ratio using confocal laser scanning microscopy. Capsules with 1 layer of Co@Au nanoparticles and 10 polyelectrolyte bilayers are optimal for magnetically controlling permeability. A theoretical explanation was proposed for the permeability control mechanisms. "Switching on" of these microcapsules using a magnetic field makes this method a good candidate for controlled drug delivery in biomedical applications.     

Photonic control of surface anchoring on solid colloids dispersed in liquid crystals

The anchoring of liquid-crystal (LC) mesogens to the surfaces of colloids is an important factor in determining intercolloidal interactions and the symmetry of the ensuing colloidal assembly in nematic colloids. The dynamic control of surface anchoring could therefore provide a handle to tune the colloidal organization and resulting properties in these systems. In this article, we report our results on the study of thermotropic nematic LC (E7) dispersions of silica and glass microcolloids bearing photosensitive surface azobenzene groups. By the photoinduced modulation of the colloidal-LC interfacial properties, due to the trans-cis isomerization of azobenzene units, we tune the anchoring on silica colloids from homeotropic (trans-azobenzene) to homogeneous planar (cis-azobenzene) reversibly. In tune with the change in surface anchoring, the interparticle interactions were also dictated by dipolar and quadrupolar symmetries for homeotropic and homogeneous planar anchoring, respectively. In our experiments, we find that, in addition to the isomerization state of the surface-bound azobenzene units, the nature of the colloid plays a crucial role in determining the anchoring state obtained on applying photostimuli. We also study the LC anchoring on colloids as a function of the azobenzene surface density and find that beyond a threshold value the anchoring properties remain invariant.