Thermal stability of aDesulfovibrio gigas periplasmic hydrogenase in reverse micelles

The thermal and operational stabilities ofDesulfovibrio gigas periplasmic hydrogenase were studied at 30 and 50°C in aqueous and micellar media. At the lower temperature the hydrogenase was more stable in reverse micelles of a cationic surfactant. No inactivation was detected over almost 16 d of incubation of the hydrogenase in the reverse micellar solution, during which the enzyme lost around 50% of the initial enzymatic activity in the aqueous solution. At 50°C the hydrogenase was more stable in aqueous medium, because of the changes that occur with the temperature in the organic phase—precipitation of surfactant and solvent evaporation. It was found that only micellar solutions of this enzyme can be repeatedly used, since the hydrogenase is inactivated after the first cycle of oxireduction in aqueous medium. The effect of glycerol and the electron carrier methylviologen as stabilizers of hydrogenase activity was also investigated. The results are interpreted on the grounds of hydrogenase and surfactant electrostatic properties.     

Synthesis and characterization of high cis-polybutadiene: influence of monomer concentration and reaction temperature

This paper reports the study of the dependence of reaction conversion, catalyst activity, polymer microstructure, molecular weight, molecular weight distribution curves and Mooney viscosity on reaction temperature and monomer concentration in the reaction medium used in the synthesis of high cis-polybutadiene. A ternary catalyst system composed by neodymium versatate, trans-butyl chloride and diisobutylaluminum hydride was used in its synthesis. The highest molecular weights were obtained at polymerization temperatures in the range from 70 to 80 °C. The highest content of cis-1,4 repeating units (about 99%) was observed when the polymerization was carried out at the lowest initial monomer concentration (0.56 mol/l).     

Simultaneous determination of zinc,copper, lead,and cadmium in fuel ethanol by anodic stripping voltammetry using a glassy carbon–mercury-film electrode

A new, versatile, and simple method for quantitative analysis of zinc, copper, lead, and cadmium in fuel ethanol by anodic stripping voltammetry is described. These metals can be quantified by direct dissolution of fuel ethanol in water and subsequent voltammetric measurement after the accumulation step. A maximum limit of 20% (v/v) ethanol in water solution was obtained for voltammetric measurements without loss of sensitivity for metal species. Chemical and operational optimum conditions were analyzed in this study; the values obtained were pH 2.9, a 4.7-m thickness mercury film, a 1,000-rpm rotation frequency of the working electrode, and a 600-s pre-concentration time. Voltammetric measurements were obtained using linear scan (LSV), differential pulse (DPV), and square wave (SWV) modes and detection limits were in the range 10^–9–10^–8 mol L^–1 for these metal species. The proposed method was compared with a traditional analytical technique, flame atomic absorption spectrometry (FAAS), for quantification of these metal species in commercial fuel ethanol samples.     

Interpolation of relative retentions as a tool for identification of perhalogenated compounds

Summary Separation of perhalogenated compounds resulting from thermolysis, photolysis or radiolysis of mixtures of halogens in carbon tetrachloride was carried out by programmed temperature gas chromatography. Plots of relative retentions (to CBr₄) vs the number of bromine atoms present for known compounds of the general formula C_xBr_yCl_z (x=1 and 2; y+z=4 or 6) gave three linear correlations (all with r>0.99). These correlations permitted projections of the identities of reaction products for which no standards were available. These projections were later confirmed by CG-MS. *** DIRECT SUPPORT *** A0732166 00010     

Thermodynamics of micellization of cationic surfactants in aqueous solutions: consequences of the presence of the 2-acylaminoethyl moiety in the surfactant head group

The enthalpies of micellization of the following surfactant series have been determined by calorimetry: benzyl (2-acylaminoethyl)dimethylammonium chlorides, RABzMe₂Cl, and alkyldimethylbenzylammonium chlorides, RBzMe₂Cl, where A, Bz and Me refer to amide, benzyl, and methyl groups, respectively and the acyl (for RABzMe₂Cl) and/or the alkyl (for RBzMe₂Cl) groups C₁₀, C₁₂, C₁₄, and C₁₆, respectively. For both series, the shapes of the calorimetric titration curves (enthalpograms) depend on the following micellar parameters: critical micelle concentration, aggregation number, and degree of counterion binding. The calorimetric-based critical micelle concentrations are in excellent agreement with those determined by conductivity. The Gibbs free energy, the enthalpy and the entropy of micellization were calculated, and divided into contributions from the CH₂ groups of the hydrophobic tail, and the terminal CH₃ plus head group of the surfactant. For both surfactant series, all thermodynamic parameters per CH₂ group were found to be similar, since their transfer (from bulk solution to the micelle) is independent of the surfactant head-group structure. The Gibbs free energy, the enthalpy, and the entropy of transfer of the head group of RABzMe₂Cl are more favorable than their counterparts for RBzMe₂Cl, because of direct and/or water mediated hygrogen bonding of the amide groups in the micelle.     

Catalytic oxidation of phenol in aqueous media over CuZSM-12 zeolite?

Summary The catalytic oxidation of phenol over CuZSM-12 (SAR = 200) has been studied using a semi-batch slurry reactor at temperatures of 110; 120 and 130^oC, and acidic neutral and basic pH. At 130^oC, the phenol undergoes total conversion to carbon dioxide and water in 1.5 h. The kinetic parameters were evaluated using a modified homogeneous-heterogeneous model for the experimental data. Using this modified model, the activation energy for the catalytic oxidation process was ca. 90 kJ mol^-1.     

Elastic scattering and total reaction cross section for the He + Al system

The elastic scattering of the radioactive halo nucleus ⁶He on ²⁷Al target was measured at four energies close to the Coulomb barrier using the RIBRAS (Radioactive Ion Beams in Brazil) facility. The São Paulo Potential (SPP) was used and its diffuseness and imaginary strength were adjusted to fit the elastic scattering angular distributions. Reaction cross-sections were extracted from the optical model fits. The reduced reaction cross-sections of ⁶He on ²⁷Al are similar to those for stable, weakly bound projectiles as ^6,7Li, ⁹Be and larger than stable, tightly bound projectile as ¹⁶O on ²⁷Al.     

A dynamic study of the quasi-one-dimensional hydrogen-bonded ferroelectric crystal CsH2PO4

The dynamics of the strong-anisotropic Ising model in a transverse field is used with the purpose to explain the dielectric critical slowing down observed experimentally in the quasi-one-dimensional hydrogen-bonded ferroelectric crystal CsH₂PO₄. A good agreement with the experimental data of the temperature dependence of the dielectric constant and the relaxation time is obtained.