31P solid state NMR studies of metal selenophosphates containing [P2Se6]4-, [P4Se10]4-, [PSe4]3-, [P2Se7]4-, and [P2Se9]4- ligands

31P solid-state nuclear magnetic resonance (NMR) spectra of 12 metal-containing selenophosphates have been examined to distinguish between the [P(2)Se(6)](4-), [PSe(4)](3-), [P(4)Se(10)](4-), [P(2)Se(7)](4-), and [P(2)Se(9)](4-) anions. There is a general correlation between the chemical shifts (CSs) of anions and the presence of a P[bond]P. The [P(2)Se(6)](4-) and [P(4)Se(10)](4-) anions both contain a P[bond]P and resonate between 25 and 95 ppm whereas the [PSe(4)](3-), [P(2)Se(7)](4-), and [P(2)Se(9)](4-) anions do not contain a P[bond]P and resonate between -115 and -30 ppm. The chemical shift anisotropies (CSAs) of compounds containing [PSe(4)](3-) anions are less than 80 ppm, which is significantly smaller than the CSAs of any of the other anions (range: 135-275 ppm). The smaller CSAs of the [PSe(4)](3-) anion are likely due to the unique local tetrahedral symmetry of this anion. Spin-lattice relaxation times (T(1)) have been determined for the solid compounds and vary between 20 and 3000 s. Unlike the CS, T(1) does not appear to correlate with P-P bonding. (31)P NMR is also shown to be a good method for impurity detection and identification in the solid compounds. The results of this study suggest that (31)P NMR will be a useful tool for anion identification and quantitation in high-temperature melts.     

Lithiation and electrophilic substitution of 8-chlorodibenz[b,f][1,4]-oxazepine-10-tert-butylcarbamate: The preparation of novel fused heterocyclic derivatives of 8-chlorodibenzoxazepine

Lithiation of 8-chlorodibenz[b,f][1,4]oxazepine-10-tert-butylcarbamate ( 1 ) is described. Electrophilic substitution of the resulting N-Boc dibenzoxazepine α- lithioamine 2 with ketones, aldehydes, nitriles, iso-cyanates and imines, followed by an in-situ cyclization, gave fused carbamates 5–26 , fused 2H-imidazol-2-ones 27–29 , fused hydantoins 30–32 , and fused ureas 33–35 , respectively, in 11–66% yield.     

Microheterogeneity in aqueous-organic solutions: Heat capacities,volumes and expansibilities of some alcohols,aminoalcohol and tertiary amines in water

The heat capacities per unit volume and the densities of aqueous solutions of 2-propanol, neopentanol, tert-amylalcohol, 2-amino-2-methylpropanol, triethylamine and diethylmethylamine were measured, in many cases as a function of temperature, over the whole mole fraction or solubility range. Apparent and partial molal heat capacities, volumes and expansibilities were derived. The concentration dependence of these functions suggest the existence of transitions in some of these systems, in the water-rich region, qualitatively similar to micellization. The large relaxation contribution observed with some of the thermodynamic functions of hydrophobic alcohols and amines suggests a reinforcement of hydrophobic hydration due to strong hydrogen-bonding interactions of the polar groups with water.     

Ultraviolet photolysis of CH2I2 in methanol: O-H insertion and HI elimination reactions to form a dimethoxymethane product

Ultraviolet photolysis of low concentrations of CH2I2 in methanol solution found that CH2I2 is converted into dimethoxymethane and some H+ and I- products. Picosecond time-resolved resonance Raman (ps-TR3) experiments observed that the isodiiodomethane (CH2I-I) photoproduct decayed faster as the concentration of methanol increases, suggesting that isodiiodomethane is reacting with methanol. Ab initio calculations indicate isodiiodomethane is able to react with methanol via an O-H insertion/HI elimination to form an iodoether (ICH2-O-CH3) and HI products. The iodoether can then further react via another O-H insertion/HI elimination reaction to form the dimethoxymethane (CH3-O-CH2-O-CH3) observed in the photochemistry experiments. A reaction mechanism consistent with these experimental and theoretical observations is proposed.     

Comparison of the dehalogenation of dihalomethanes (CH2XI, where X = Cl, Br, I) following ultraviolet photolysis in aqueous and NaCl saltwater environments

The ultraviolet photolysis of low concentrations of CH(2)XI (X = Cl, Br, I) were investigated in water and saltwater solutions by photochemistry and picosecond time-resolved resonance Raman spectroscopy. Photolysis in both kinds of solutions formed mostly CH(2)(OH)(2) and HI and HX products. However, photolysis of the CH(2)XI molecules in saltwater resulted in production of some CH(2)XCl products not observed in aqueous solutions without salt present. The appearance of these new products in saltwater solutions is accompanied by a decrease in the amount of CH(2)(OH)(2), HI, and HX products compared to photolysis in aqueous solutions without salt present. The possible implications for photolysis of CH(2)XI and other polyhalomethanes in seawater and other salt aqueous environments compared to nonsaltwater solvated environments is briefly discussed.     

Dilute sulfuric acid pretreatment of corn stover at high solids concentrations

Applied Biochemistry and Biotechnology - The enzymatic digestibility of a pretreated substrate is enhanced by increasing the severity of the pretreatment conditions, apparently because a greater...     

Enzymatic polymerizations using surfactant microstructures and the preparation of polymer-ferrite composites

Applied Biochemistry and Biotechnology - Horseradish peroxidase has been used as a biocatalyst to synthesize a polymeric material from alkyl-substituted phenols. The synthesis is carried out in a...     

The search for a new model structure of β-Factor XIIa

We present the search for a new model of -factor XIIa, a blood coagulation enzyme, with an unknown experimental 3D-structure. We decided to build not one but three different models using different homologous proteins as well as different techniques and different modellers. Additional studies, including extensive molecular dynamics simulations on the solvated state, allowed us to draw several conclusions concerning homology modelling, in general, and -factor XIIa, in particular.     

A Three-Dimensional Two-Phase Model for Thermal Plasma Chemical Vapor Deposition with Liquid Feedstock Injection

In this paper, a comprehensive model for thermal plasma chemical vapor deposition (TPCVD) with liquid feedstock injection is documented. The gas flow is assumed to be steady, of a single temperature. Radiation and charged species contributions are excluded, but extensive homogeneous and heterogeneous chemistry is included. The liquid phase is traced by considering individual droplets. Discussion on the model's application to diamond production from acetone in a hydrogen–argon plasma is included. The major conclusions are: (1) Liquid injection possesses a capability to deliver the hydrocarbon precursor directly onto the deposition target. (2) For the case of complete evaporation of the droplet before reaching the substrate, the deposition rate is similar to that obtained with gaseous precursors. (3) The computational results compare well with experimental data. The modeling results can be used to optimize the injection parameters with regard to the deposition rate.