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.     

Effects of polymer architecture and composition on the adhesion of poly(tetrafluoroethylene).

Poly(glycidyl methacrylate), PGMA, chains in linear and arborescent structures were incorporated onto surfaces of poly(tetrafluoroethylene), PTFE, films by hydrogen plasma and ozone treatment and atom transfer radical polymerization. The epoxide groups of the PGMA chains were further reacted with acetic acid (AAc), oxalic acid (XAc), allyl amine (AA), and ethylenediamine (EDN) to introduce hydroxyl and amine groups to the surfaces of the PTFE films. Surface characterizations performed by Fourier Transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the surface modification and the chemical structure. The PGMA chains in arborescent structures show a high effectiveness for the enhancement of the adhesion of PTFE films. The adhesion of PTFE films was also significantly enhanced by ring-opening reactions of the PGMA epoxide groups with acetic acid and amine compounds. A high value of 9.5 N cm(-1) in the optimum 180 degrees peel strength test was observed with PTFE/copper assemblies.     

Designed nanostructured pt film for electrocatalytic activities by underpotential deposition combined chemical replacement techniques

Multiple-deposited Pt overlayer modified Pt nanoparticle (MD-Pt overlayer/PtNPs) films were deliberately constructed on glassy carbon electrodes through alternately multiple underpotential deposition (UPD) of Ag followed redox replacement reaction by Pt (II) cations. The linear and regular growth of the films characterized by cyclic voltammetry was observed. Atomic force spectroscopy (AFM) provides the surface morphology of the nanostructured Pt films. Rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry demonstrate that the MD-Pt overlayer/PtNPs films can catalyze an almost four-electron reduction of O(2) to H(2)O in air-saturated 0.1 M H(2)SO(4). Thus-prepared Pt films behave as novel nanostructured electrocatalysts for dioxygen reduction and hydrogen evolution reaction (HER) with enhanced electrocatalytic activities, in terms of both reduction peak potential and peak current, when compared to that of the bulk polycrystalline Pt electrode. Additionally, it is noted that after multiple replacement cycles, the electrocatalytic activities improved remarkably, although the increased amount of Pt is very low in comparison to that of pre-modified PtNPs due to the intrinsic feature of the UPD-redox replacement technique. In other words, the electrocatalytic activities could be improved markedly without using very much Pt by the technique of tailoring the catalytic surface. These features may provide an interesting way to produce Pt catalysts with a reliable catalytic performance as well as a reduction in cost.     

关于静电作用对酶活性部位残基pKa影响的定量计算

随着基因技术的发展,人们几乎已经可以任意替换蛋白质序列中的特定残基。由于理论上对蛋白质性能的预测工作还远远跟不上实验的发展,只能花费大量的人力、物力利用实验方法筛选突变体。这就迫切需要建立一套能够正确预测蛋白质性质的方法。静电作用在酶促反应中起到了重要作用。基于表面带电残基对酶活性部位残基pK_α的影响,可利用替换表面残基的方法改变酶促反应随pH的变化趋势,是蛋白质工程研究中的一种有效方法。由于表面极性残基处于高介电常数的溶剂(水)与低介电常数的蛋白质的界面上,对此问题尚未有圆满的理论方法进行解决。我们利用Kirkwood理论定量地表述了表面荷电残基的替换对酶活性部位残基pK_α的影响,为研究酶突变体的性质,如突变体的电化学性质、酶催化反应随pH变化趋势的改变,酶专一性的改变等提供了一种简便的方法。     

少量人发中硫的测定

建立了测定一根长2～3cm人发中硫的间接分光光度法,表观吸光系数为5.1×10~4,络合物组成Ba:CPA-mA为1:2,比耳定律范围为0～20μg硫。硫的检测限为0.025μg/mL,变动系数为2.7%,回收率为91.2～97.2%,且不用掩蔽即可直接进行测定,测定211例人发的结果表明,含硫量范围为(28.5±3.2)×10~3μg/g。     

Excess partial molar enthalpies,entropies, Gibbs energies,and volumes in aqueous dimethylsulfoxide

The excess partial molar enthalpies, the vapor pressures, and the densities of dimethylsulfoxide (DMSO)–H₂O mixtures were measured and the excess partial molar Gibbs energies and the partial molar volumes were calculated for DMSO and for H₂O. The values of the excess partial molar Gibbs energies for both DMSO and H₂O are negative over the entire composition range. The results for the water-rich region indicated that the presence of DMSO enhances the hydrogen bond network of H₂O. Unlike monohydric alcohols, however, the solute-solute interaction is repulsive in terms of the Gibbs energy. This was a result of the fact that the repulsion among solutes in terms of enthalpy surpassed the attraction in terms of entropy. The data in the DMSO-rich region suggest that DMSO molecules form clusters which protect H₂O molecules from exposure to the nonpolar alkyl groups of DMSO.     

The synthesis and fluxional behavior of the first [2.1.2.1] metacyclophane

8,15,23,30-Tetramethyl[2.1.2.1]metacyclophane,4, is synthesised. Variable temperature ¹Hmr and ¹³Cmr spectra indicate that 4e is the most likely conformation and that at temperatures above 50°C the molecule is fluxional (ΔG^≠₃₂₃ = 15.4 kcal/mole).