A New Route to 1,3-Dienes: TMSI Elimination of 2-Ene-1,4-diols

Iodotrimethylsilane effects conversion of acyclic bis-secondary 2-ene-1,4-diols to 1,3-dienes in moderate yield. The reaction with 3-hexene-2,5-diol favors anti elimination but is largely nonstereospecific.     

New data on decomposition of nitric solutions of acetohydroxamic acid

Acetohydroxamic acid (AHA) is an important complexant/reductant for Pu(IV) in the UREX process. It decomposes in the presence of nitric acid. In literature, its decomposition kinetics in nitric acid is traditionally reported as pseudo-first order reaction. In this study, new experimental data were reported for kinetics experiments under wide consecration conditions. It was found that the decomposition reaction was first order with respect to both the components hence overall second order.     

Biodecolorization of Azo Dye Remazol Orange by Pseudomonas aeruginosa BCH and Toxicity (Oxidative Stress) Reduction in Allium cepa Root Cells

In this report a textile azo dye Remazol orange was degraded and detoxified by bacterium Pseudomonas aeruginosa BCH in plain distilled water. This bacterial decolorization performance was found to be pH and temperature dependent with maximum decolorization observed at pH 8 and temperature 30 °C. Bacterium tolerated higher dye concentrations up to 400 mg?l^?1. Effect of initial cell mass showed that higher cell mass concentration can accelerate decolorization process with maximum of 92 % decolorization observed at 2.5 g?l^?1 cell mass within 6.5 h. Effect of various metal ions showed Mn has inducing effect whereas Zn strongly inhibited the decolorization process at 5 mM concentration. Analysis of biodegradation products carried out with UV–vis spectroscopy, HPTLC and FTIR confirmed the decolorization and degradation of Remazol orange. Possible route for the degradation of dye was proposed based on GC-MS analysis. During toxicological scrutiny in Allium cepa root cells, induction in the activities of superoxide dismutase (SOD), guaiacol peroxidase (GPX) and inhibition of catalase (CAT) along with raised levels of lipid peroxidation and protein oxidation in dye treated samples were detected which conclusively indicated the generation of oxidative stress. Less toxic nature of the dye degraded products was observed after bacterial treatment.     

Emission characteristics of Dy3+ ions in lead antimony borate glasses

Glasses with the composition 30PbO–25Sb₂O₃–(45?x)B₂O₃–xDy₂O₃ for x=0 to 1 were prepared in steps of 0.2 by the melt-quenching method. Various physical parameters, viz., density, molar volume, and oxygen packing density, were evaluated. Optical absorption and luminescence spectra of all the glasses were recorded at room temperature. From the observed absorption edges optical band gap, the Urbach energies are calculated; the optical band gap is found to decrease with the concentration of Dy₂O₃. The Judd–Ofelt theory was applied to characterize the absorption and luminescence spectra of Dy³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties, like transition probability A, branching ratio β and the radiative life time τ for different emission levels of Dy³⁺ ions, have been evaluated. The radiative lifetime for the ⁴F_9/2 multiplet has also been evaluated from the recorded life time decay curves, and the quantum efficiencies were estimated for all the glasses. The quantum efficiency is found to increase with the concentration of Dy₂O₃.     

On the photomagnetism of nitronyl nitroxide, imino nitroxide, and verdazyl-substituted azobenzene

The cis- and trans-azobenzenes are known as photochromic isomers with the trans- converting into the cis-form and vice versa upon irradiation with specific wavelengths. We have quantum chemically investigated the cis- and trans-forms of substituted azobenzene diradicals, with two nitronyl nitroxides, imino nitoxides, or verdazyls at para positions and serving as monoradical centers, to determine whether they can exhibit a photoassisted magnetic crossover. Geometries of both substituted and unsubstituted molecules have been optimized by density functional (DF) method UB3LYP using the 6-311G(d,p) basis set. Optimization of the geometry of the cis isomers has required special care. Single point singlet, triplet, and broken symmetry calculations have been done using 6-311++G(3df, 3pd) basis set. The magnetic exchange coupling constants have been estimated from the broken symmetry calculations. Absorption wavelengths have been estimated for both substituted and unsubstituted species from time-dependent DF treatment using restricted spin-polarized methodology RB3LYP and 6-311++G(3df, 3pd) basis set. From the similarity in the calculated absorption wavelengths for the unsubstituted and substituted azobenzenes, and the increased oscillator strengths (f) for the substituted species, we predict that the diradical isomers would be strongly photochromic. From our triplet state and broken symmetry calculations, we predict that both the cis- and the trans-diradicals are antiferromagnetically coupled. This prediction is consistent with the spin alternation rule, and the possibility of a magnetic crossover is nonexistent for these species.     

Sequential catalytic isomerization and allylic substitution. Conversion of racemic branched allylic carbonates to enantioenriched allylic substitution products

A catalytic protocol for the conversion of readily accessible racemic, branched aromatic allylic esters to branched allylic amines, ethers, and alkyls has been developed. Palladium-catalyzed isomerization of branched allylic esters to terminal allylic esters, followed by sequential iridium-catalyzed allylic substitution, gave the branched allylic products in good yield with high regioisomeric and enantiomeric selectivity. Both electron-rich and electron-poor branched allylic esters gave products in >90% ee. High enantiomeric excesses were also observed for the products from the reactions of 2-thienyl acetates and dienyl carbonates.     

Photoacoustic and photoluminescence studies on ThO<Subscript>2</Subscript>:Sm<Superscript>3+</Superscript>

Nanocrystalline ThO₂:Sm³⁺ was synthesized using wet-chemical route and characterized using X-ray diffraction (XRD), photoacoustic (PA) and photoluminescence (PL) spectroscopy. PA absorptions of Sm³⁺ doped samples are found to be quite weak as compared to Nd³⁺, while PL of Sm³⁺ was intense. As the energy gap between lowest luminescent levels and highest non-luminescent level in samarium ion is around 7000 cm^?1; it is highly fluorescing compared to Nd³⁺ which has close by levels. Through photoacoustic data it was pointed out that large covalent character exists in ThO₂:Nd³⁺ compared to ThO₂:Sm³⁺.     

Experimental Determination of NH3 Solubility in Toluene at Pressures up to 340 kPa at 398 K

Journal of Solution Chemistry - The solubility of ammonia in toluene has been measured at 398&nbsp;K and at pressures up to 340&nbsp;kPa using a static, synthetic and isochoric technique....     

Silica nanowires: Growth,integration, and sensing applications

This review (with 129 refs.) gives an overview on how the integration of silica nanowires (NWs) into micro-scale devices has resulted, in recent years, in simple yet robust nano-instrumentation with improved performance in targeted application areas such as sensing. This has been achieved by the use of appropriate techniques such as di-electrophoresis and direct vapor-liquid-growth phenomena, to restrict the growth of NWs to site-specific locations. This also has eliminated the need for post-growth processing and enables nanostructures to be placed on pre-patterned substrates. Various kinds of NWs have been investigated to determine how their physical and chemical properties can be tuned for integration into sensing structures. NWs integrated onto interdigitated micro-electrodes have been applied to the determination of gases and biomarkers. The technique of directly growing NWs eliminates the need for their physical transfer and thus preserves their structure and performance, and further reduces the costs of fabrication. The biocompatibility of NWs also has been studied with respect to possible biological applications. This review addresses the challenges in growth and integration of NWs to understand related mechanism on biological contact or gas exposure and sensing performance for personalized health and environmental monitoring.

Silica nanowires decorated micro-electrodes for sensing application

     

Sorption of trifluoromethane in activated carbon

Sorption isotherms for trifluoromethane (R-23) in activated carbon have been measured at ca. 298 and 323 K using a gravimetric microbalance. High-resolution TEM images of the activated carbon show a very uniform microstructure with no evidence of any contaminants. The adsorption in the activated carbon reaches about 22.8 mol kg^?1 at 2.0 MPa and 298 K or 17.6 mol kg^?1 at 2.0 MPa and 323 K. Three different adsorption models (Langmuir, multi-site Langmuir, and BET equations) have been used to analyze the activated carbon sorption data, with a particular interest in the heat of adsorption (?ΔH). The heat of adsorption for R-23 in the activated carbon was about 29.78 ± 0.04 kJ mol^?1 based on the multi-site Langmuir model and is within the range of typical physical adsorption. According to the IUPAC classification, the activated carbon exhibits Type I adsorption behavior and was completely reversible. Compared with our previous work for the sorption of R-23 in zeolites (5A (Ca,Na-A), 13X (Na-X), Na,K-LSX, Na-Y, K,H-Y, Rb,Na-Y) and ionic liquids ([omim][TFES] and [emim][Tf₂N]) the activated carbon had the highest adsorption capacity. The adsorption process in the activated carbon also took less time than in the zeolites or the ionic liquids to reach thermodynamic equilibrium.