Spectroscopic and chemical reactivity analysis of D-Myo-Inositol using quantum chemical approach and its experimental verification

Glow discharge conditioning (GDC) has long been accepted as one of the basic wall conditioning techniques for achieving ultrahigh vacuum in an unbaked chamber. As a part of this fundamental experimental study, a test chamber has been fabricated from stainless steel 304 L with its inner surface electropolished on which a detailed investigation has been carried out. Both helium and hydrogen gases have been employed as discharge cleaning medium. The discharge cleaning was carried out at 0.1 A /m ² current density with working pressure maintained at 1.0 × 10 ^-2 mbar. It was experimentally observed that the pump-down time to attain the base pressure ~10 ^-8 mbar was reduced by 62% compared to the unbaked chamber being pumped to this ultimate vacuum. The results were similar irrespective of whether the discharge cleaning medium is either hydrogen or helium. It was also experimentally established that a better ultimate vacuum could be achieved as compared to theoretically calculated ultimate vacuum with the help of discharge cleaning.     

Probing surface plasmons by bare V-shaped tips: modeling by geometrical optics and rigorous diffraction theory

Optical Review - We consider probing inhomogeneous waves in the near fields of metallic nanostructures with the aid of a dielectric V-shaped wedge connected to a waveguide. A geometrical model...     

Quantum interference in the Raman scattering from the silicon nanostructures

We report here microscopic process involved in the photo-excited Fano interaction due to nonlinear process in the silicon nanostructures. Photo-excited Raman line-shapes are investigated to reveal the presence of nonlinear Fano interaction in the silicon nanostructures for three different sizes. The Fano interaction is found to be more prominent due to the phase matching between electronic and phonon Raman scatterings for smaller sized nanostructures. Phase matching is achieved by nonlinear process of two-wave mixing in the silicon nanostructures followed by the formation of electron-phonon bound state.     

Effect of overlapping Debye spheres on structures of 2D dusty plasmas

In dusty plasmas, overlapping Debye spheres around dust grains could produce an attractive force between them. Its effects on static structures of two-dimensional (2D) dusty plasmas are studied here by using molecular dynamics simulations. Results, in terms of the equilibrium radial distribution function, are compared with those deduced from purely repulsive Debye-Hückel or Yukawa potential for different Coulomb-coupling and screening parameters. The effect of the attractive force is found quite noticeable for usual experimental conditions, and becomes more pronounced for larger screening parameter κ. In particular, it is observed that for large κ the attractive force is dominant, and dust grains tend to aggregate and form patterns with scattering voids.     

Mordenite-incorporated PVA–PSSA membranes as electrolytes for DMFCs

Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm² is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm² with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.     

A mechanistic study of Protein A chromatography resin lifetime

A mechanistic study into Protein A chromatographic resin lifetime limitations is presented. Binding and mass transport properties of two widely used agarose-based Protein A resins were studied to distinguish between the roles of resin fouling due to product/impurity build-up and ligand degradation as contributory factors towards the decline in binding capacity with use. Cycling studies were conducted with and without product loading on the columns to separate out the influence of resin fouling. Ligand degradation under the mildly alkaline conditions used for column regeneration was determined to be the primary cause for Protein A resin capacity decline with usage. The use of lower concentrations of caustic and the use of stabilizing excipients to protect the Protein A ligand during cleaning and sanitization were found to be useful techniques in maintaining column performance. The results presented in this paper provide a clearer understanding of the causative factors that limit Protein A chromatographic resin lifetime. It is anticipated that these findings will assist in the development of more robust and economical downstream manufacturing processes for monoclonal antibody and Fc fusion protein purification.     

Cigarette smoke extract induced protein phosphorylation changes in human microvascular endothelial cells in vitro

Phosphorylation is the most widely studied posttranslational modification (PTM) and is an important regulatory mechanism used during cellular responses to external stimuli. The kinases and phosphatases that regulate protein phosphorylation are known to be affected in many human diseases. Cigarette smoking causes cardiovascular disease (CVD). Endothelial cells play a pivotal role in CVD initiation and development; however, there have been limited investigations of the specific signaling cascades and protein phosphorylations activated by cigarette smoke in endothelial cells. The purpose of this research was to better understand the differential protein phosphorylation in endothelial cells stimulated with extracts of cigarette smoke total particulate matter (CS-TPM) in vitro. Human microvascular endothelial cells were exposed in vitro to CS-TPM at concentrations that were shown to cause endothelial cell dysfunction. The phosphorylated proteins were isolated using phosphoprotein-specific chromatography, followed by enzymatic digestion and nano-flow capillary liquid chromatography (ncap-LC) coupled to high resolution mass spectrometry. This study putatively identified 94 proteins in human microvascular endothelial cells that were differentially bound to a phosphoprotein-specific chromatography column following exposure to CS-TPM suggesting differential phosphorylation. Pathway analysis has also been conducted and confirmations of several observations have been made using immunoaffinity-based techniques (e.g., Western blotting). Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Effect of proton irradiation on electrical properties of a-As2S3

This paper reports the effect of proton irradiation on the electrical properties of a-As₂S₃ in the temperature range of 323–418 K and frequency range 0.1–100 kHz. The variation of transport property is studied with proton irradiation dose (1 × 10¹³ ions/cm² and 1 × 10¹⁵ ions/cm²). It has been observed that proton irradiation changes the dc conductivity (σ_dc), dc activation energy (ΔE_dc) and ac conductivity (σ_ac(ω)). The σ_dc and σ_ac(ω) increases with dose of proton irradiation. The value of frequency exponent (s) decreases with the temperature and irradiation dose. These results are explained in terms of change in density of defect states in these glasses.     

Modeling the survival of a resource-dependent population: Effects of toxicants (pollutants) emitted from external sources as well as formed by its precursors

In this paper, a nonlinear mathematical model is proposed and analyzed to study the survival of a resource-dependent population. It is assumed that this population and its resource are affected simultaneously by a toxicant (pollutant) emitted into the environment from external sources as well as formed by precursors of this population. It is shown that as the cumulative rates of emission and formation of the toxicant into the environment increase, the densities of population and its resource settle down to lower equilibria than their initial carrying capacities, and their magnitudes decrease as rates of emission and formation of the toxicant increase. On comparing different cases, it is noted that when population is not affected directly by the toxicant but only its resource is affected, the possibility of its survival is greater than the case when both are affected simultaneously. But for large emission rate of toxicant, the affected resource may be driven to extinction under certain conditions and the population which wholly depends on it may not survive for long even if it is not affected directly by the toxicant.     

Quantification of clopidogrel in human plasma by sensitive liquid chromatography/tandem mass spectrometry

A simple, sensitive and rapid high-performance liquid chromatography/positive electrospray ionization tandem mass spectrometry method was developed and validated for the assay of clopidogrel in human plasma. Following liquid-liquid extraction, the analytes were separated using an isocratic mobile phase on a reversed-phase column and analyzed by mass spectrometry in the multiple reaction monitoring mode using the respective [M+H](+) ions, m/z 322/212 for clopidogrel and m/z 264/154 for the internal standard. The assay exhibited a linear dynamic range of 5-6000 pg/mL for clopidogrel in human plasma. The lower limit of quantification was 5 pg/mL with a relative standard deviation of less than 8%. Acceptable precision and accuracy were obtained for concentrations over the standard curve range. A run time of 2.5 min for each sample made it possible to analyze more than 400 human plasma samples per day. The validated method has been successfully used to analyze human plasma samples for application in pharmacokinetic, bioavailability or bioequivalence studies.