Controlled sulfur oxygenation of the ruthenium dithiolate (4,7-bis-(2'-methyl-2'-mercaptopropyl)-1-thia-4,7-diazacyclononane)RuPPh(3) under limiting O(2) conditions yields thiolato/sulfinato, sulfenato/sulfinato, and bis-sulfinato derivatives

The ruthenium(II) dithiolate complex (bmmp-TASN)RuPPh(3) (1) reacts with O(2) under limiting conditions to yield isolable sulfur oxygenated derivatives as a function of reaction time. With this approach, a family of sulfur-oxygenates has been prepared and isolated without the need for O-atom transfer agents or column chromatography. Addition of 5 equiv of O(2) to 1 yields the thiolato/sulfinato complex (bmmp-O(2)-TASN)RuPPh(3) (2) in 70% yield within 5 min. Increasing the reaction time to 12 h yields the sulfenato/sulfinato derivative (bmmp-O(3)-TASN)RuPPh(3) (3) in 82% yield. Longer reaction times and/or additional O(2) exposure yield the bis-sulfinato complex (bmmp-O(4)-TASN)RuPPh(3) (4). All products remain in the Ru(II) oxidation state under the conditions employed. Stoichiometric hydrolysis of acetonitrile to acetamide by 2 and 3 is observed in mixed acetonitrile, methanol, PIPES buffer (pH = 7.0) mixtures. The Ru(III)/(II) reduction potential of -0.85 V (versus ferrocenium/ferrocene) for 1 shifts to -0.39 and -0.26 V for 2 and 3, respectively, because of the decreased donor ability of sulfur upon oxygenation. X-ray diffraction studies reveal a decrease in Ru-S bond distances upon oxygenation by 0.045(1) and 0.158(1) ? for the sulfenato and sulfinato donors, respectively. Conversely, sulfur-oxygenation increases the Ru-P bond distance by 0.061(1) ? from 1 to 2 and an additional 0.027(1) ? from 2 to 3. Density functional theory investigations using the BP86 and B3LYP functionals with a LANL2DZ basis set for Ru and the 6-31G(d) basis set for all other atoms reveal a direct correlation between the oxygenation level and the Ru-P distance with an increase of 0.031 ? per O-atom.     

Effect of sphere to rod transition on the probe microenvironment in sodium dodecyl sulphate micelles: A time resolved fluorescence anisotropy study

The effect of different hydrotropic salts on the microenvironment at the anionic head group region of sodium dodecyl sulphate (SDS) micelle has been studied through time-resolved fluorescence anisotropy measurements of a solubilized probe, coumarin-153 (C153). The organic cations of the hydrotropic salts used in this study, i.e. aniline hydrochloride (AHC) and o-, m- and p-toluidine hydrochlorides (OTHC, MTHC and PTHC, respectively), differ in their charge to size ratio and hydrophobicity. Present study utilizes the sensitivity of the fluorescence technique to understand the changes in the micropolarity and microviscosity experienced by the fluorescent probe, C153, solubilized in the micellar Stern layer, on addition of different hydrotropic salts. Significant changes are observed in the rotational relaxation dynamics of the probe with increasing concentration of the salts. The changes in the rotational relaxation dynamics clearly reflect the sphere to rod transition in the SDS micelles and correspond nicely with the reported results from dynamic light scattering measurements. The growth behavior of SDS micelles is found to be sensitive to the hydrophobicity of the organic cations. The charge to size ratio of the organic cations also indicated to play a role in inducing the sphere to rod transition in the SDS micelles. The interesting observation made from this study is that the sphere to rod transition of SDS micelles is largely facilitated by the presence of the hydrotropic salts and such a transition is successfully indicated by the simple fluorescence anisotropy measurements of a probe in the micelle carried out in the presence of different hydrotropic salts.     

Electrophoretically deposited polyaniline nanotubes based film for cholesterol detection

Polyaniline nanotube (PANI-NT) based films have been fabricated onto indium-tin-oxide (ITO) coated glass plates via electrophoretic technique. These PANI-NT/ITO electrodes have been utilized for covalent immobilization of cholesterol oxidase (ChOx) using glutaraldehyde (Glu) as cross-linker. Structural, morphological and electrochemical characterization of PANI-NT/ITO electrode and ChOx/Glu/PANI-NT/ITO bioelectrode have been done using FT-IR spectroscopy, SEM, electrochemical impedance spectroscopy and cyclic voltammetry techniques. Response studies of the ChOx/Glu/PANI-NT/ITO bioelectrode have been carried out using both linear sweep voltammetry and UV-Visible spectrophotometry. The results of the biosensing studies reveal that this bioelectrode can be used to detect cholesterol in wide detection range of 25-500 mg/dL with high sensitivity of 3.36 mA mg(-1) dL and fast response time of 30 s at pH 7.4. This bioelectrode exhibits very low value of Michaelis-Menten constant of 1.18 mM indicating enhanced interactions between cholesterol and ChOx immobilized onto this nanostructured PANI matrix.     

Diode laser-based sensor for high precision measurements of ambient CO<Subscript>2</Subscript> in network applications

The increasing need for better spatial and temporal measurements of greenhouse gases, especially CO₂, to support global climate change modeling is driving the expansion of monitoring networks. Currently, networks making ambient CO₂ measurements use environmentally stabilized sensors based on non-dispersive infrared absorption spectroscopy. To expand both measurement capability and coverage, much work is underway to develop highly accurate, reliable yet economical sensors for the greenhouse gases. The US Department of Energy has created specifications for a new sensor that has high performance but at a cost that permits widespread deployment. We report on a sensor designed to meet this need. We have demonstrated a compact, automated, high precision sensor for ambient CO₂ that offers good performance in an economical package. The sensor is a near-IR diode laser-based absorption spectrometer operating near 2 μm and using Integrated Cavity Output Spectroscopy (ICOS). Field demonstrations were carried out at both the UNH/AirMap Thompson Farm Observatory and the NOAA Boulder Atmospheric Observatory. The sensor has a demonstrated precision of between 0.090 and 0.125 ppmv for a 30 sec acquisition, or 1 part in 3000 to 4000.     

Solutions of a system of forced burgers equation in terms of generalized laguerre polynomials

In this article, we obtain explicit solutions of a linear PDE subject to a class of radial square integrable functions with a monotonically increasing weight function |x|ⁿ⁻¹eβ|x|²/2,${\left|x\right|}^{n-1}{e}^{\beta {\left|x\right|}^2}/2,$, β≥0, x ∈?n$\beta \ge 0,\hspace{0.17em}x\hspace{0.17em}\in {?}^n$. This linear PDE is obtained from a system of forced Burgers equation via the Cole-Hopf transformation. For any spatial dimension n > 1, the solution is expressed in terms of a family of weighted generalized Laguerre polynomials. We also discuss the large time behaviour of the solution of the system of forced Burgers equation.     

Holonomy group scheme of an integral curve

Let Y be a projective variety over a field k (of arbitrary characteristic). Assume that the normalization X of Y is such that is normal, being the algebraic closure of k. We define a notion of strong semistability for vector bundles on Y. We show that a vector bundle on Y is strongly semistable if and only if its pull back to X is strongly semistable and hence it is a tensor category. In case , we show that strongly semistable vector bundles on Y form a neutral Tannakian category. We define the holonomy group scheme of Y to be the Tannakian group scheme for this category. For a strongly semistable principal G‐bundle , we construct a holonomy group scheme. We show that if Y is an integral complex nodal curve, then the holonomy group of a strongly semistable vector bundle on Y is the Zariski closure of the (topological) fundamental group of Y.     

Stability and bandwidth enhancement of difference frequencygeneration (DFG)-based wavelength conversion by pump detuning

The authors report on a method for enhancing the operating stability and signal bandwidth of difference-frequency-generation-based wavelength conversion by detuning the pump from the degenerate phase matching wavelength; both can be further enhanced by using nonuniform quasi-phase-matching structures     

Recent advances in the synthesis of C-5-substituted analogs of 3,4-dihydropyrimidin-2-ones: A review

3,4-Dihydropyrimidin-2-ones act as a versatile scaffold in organic synthesis, which serves as a significant template for the development of various therapeutic agents and shows a wide spectrum of activities. The attractive application of 3,4-dihydropyrimidin-2-ones in organic synthesis is undoubtedly owing to C-5 ester group, which is responsible for the change in its bioactivity. Introduction of various groups like electron-withdrawing and electron-donating groups at positions 1, 2, 3, 5, and 6 greatly increased biological activity. Significant efforts have been undertaken to exploit different synthetic routes to synthesize various derivatives of 3,4-dihydropyrimidin-2-ones. This review article gives a comprehensive account of the synthetic utility of C-5 substitution of 3,4-dihydropyrimidin-2-ones used in the design and synthesis of different types of compounds with greater emphasis on recent literature.     

Group theoretic method for analyzing interaction of a discontinuity wave with a strong shock in an ideal gas

A group theoretic method is used to obtain an exact particular solution to the system of partial differential equations, describing one-dimensional unsteady planar, cylindrically and spherically symmetric motions in an ideal gas, involving shock waves. It is interesting to remark that the exact solution obtained here is precisely the blast wave solution obtained earlier using a different method of approach. Further, the evolution of a discontinuity wave and its interaction with the strong shock are studied within the state characterized by the exact particular solution. The properties of reflected and transmitted waves and the jump in the shock acceleration are completely characterized, and certain observations are noted in respect to their contrasting behavior.     

Purification and Characterization of Enterocin LR/6, a Bacteriocin from <Emphasis Type="Italic">Enterococcus faecium</Emphasis> LR/6

Enterocin LR/6, a bacteriocin obtained from the culture filtrate of Enterococcus faecium strain LR/6, has been purified to homogeneity using ammonium sulfate precipitation, cation-exchange chromatography, gel-filtration, and checked on reverse-phase high-performance liquid chromatography. It is active at high temperatures (boiling as well as autoclaving) and over a wide range of pH (2.0–8.0). Also, it is sensitive to a number of proteolytic enzymes but is stable in the presence of surfactants and organic solvents. The protein could be stored at least up to 1 year at low temperatures (4 °C and −20 °C) without any loss of activity. The N-terminal sequence of enterocin LR/6 showed no homology with known enterocins or other bacteriocins present in the database, suggesting it to be a novel enterocin. Matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry and tricine sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis revealed its mass to be ∼6.1 kDa. It showed a bactericidal mode of action against indicator strain, Micrococcus luteus.