Initial study of two-phase laminar flow extraction chip for sample preparation for gas chromatography

A sample preparation method for gas chromatography using a two-phase, laminar flow extraction PDMS/glass chip has been developed. A stable two-phase laminar interface was obtained by surface modification, and the organic extraction phase and the aqueous sample phase were separated effectively when the two-phase laminar flows exit the chip. Experiments were conducted on the chip to extract ephedrine from aqueous solution. Good reproducibility was obtained over the entire range of ephedrine concentration using the extraction chips (CV range 2.7%-4.5%). Effects of salt and solvent on extraction efficiency were studied.     

Three-stage multilayer formation kinetics during adsorption of an anionic fluorinated surfactant onto germanium. 1. Concentration effect

The adsorption of tetraethylammonium perfluorooctylsulfonate (TEA-FOS) from aqueous solution onto hydroxylated germanium is studied using in situ polarized attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The adsorption is monitored at a series of bulk solution concentrations spanning from well below to above the critical micelle concentration (CMC; 1.0 mM). The kinetics of adsorption is followed by monitoring the intensity of the fluorocarbon bands. The orientation of the fluorocarbon director with respect to the germanium surface is determined by circular dichroism measurements of CF2 stretching bands. At bulk concentrations ranging from 10% of the CMC to at least 500% of the CMC, the adsorption occurs in an unusual sequence of three stages. Initially, rapid adsorption occurs within 200 min, leading to coverage of a monolayer or less. A long period of slow adsorption follows, during which we hypothesize that surfactant molecules form clusters, some of which serve as nuclei for multilayer growth. This stage concludes suddenly with an acceleration in the rate of adsorption, which eventually leads to multilayer formation. Because this is an anionic surfactant adsorbing onto a negatively charged surface at pH 6, the tetraethylammonium ions must mediate the interactions between the surfactant headgroups and the surface. The dichroism measurements show that TEA-FOS is initially oriented randomly or somewhat parallel to the surface, but over time adopts an orientation somewhat normal to the surface. This behavior is consistent with initial adsorption at isolated sites, followed by aggregation into isotropic admicelles, and finally growth into flattened admicelles. The sudden onset of accelerated adsorption can be explained either by autoaccelerating adsorption or nucleation and growth of a hydrophobic multilayer structure.     

Room-temperature ferromagnetism in CuO sol-gel powders and films

Both CuO nanopowders and thin films prepared by sol-gel method exhibit room-temperature ferromagnetism (FM), even though CuO bulk presents a paramagnetism (PM) at room temperature above its antiferromagnetic Néel temperature. For CuO nanopowders at room temperature, FM likely occurs at surfaces of nanograins, while PM may remain in the inner of grains. The vacuum annealing greatly enhances room-temperature FM, and the air reheating after vacuum annealing reduces FM again, indicating that the observed FM in CuO sol-gel powders and thin films are connected with oxygen vacancies. The room-temperature FM of CuO nanograins decreases with an increase of grain size, possibly due to the decrease of oxygen vacancy concentrations at surfaces of nanograins.     

Density functional theory studies on the B-containing lithium salts

Three B-containing lithium salts, lithium bis(oxalato)borate, lithium (malonatooxalato)borate, and lithium bis(malonato)borate, are studied by density functional theory. The relationships between the structure of lithium salts and their physical chemistry characteristics are investigated. A linear correlation is observed between the highest occupied molecular orbital energy of lithium salts and their oxidation potentials. The correlation between ionic conductivity and binding energy of lithium salt is also studied. The physical chemistry characteristics of a novel lithium salt, lithium oxalyldifluoroborate, are predicted according to the rules concluded from other B-containing lithium salts.     

GaH(X1Σ+)自由基的光谱常数与分子常数研究

采用内收缩多参考组态相互作用(MRCI)方法和系列相关一致基aug-cc-pVnZ对GaH (X1Σ+)自由基的光谱性质进行了研究. 通过与实验结果的比较, 发现在aug-cc-pV5Z基组、且考虑相对论修正时得到的De, Re和ωe与实验结果较为一致. 在这一基组下对GaH(X1Σ+)自由基的势能曲线进行了计算、并将计算结果拟合成了Murrell-Sorbie函数, 由此得到的光谱常数(ωeχe, αe和 Be)也与实验结果较为相符. 以得到的解析势能函数为基础, 通过求解双原子分子核运动的径向Schrödinger方程, 找到了J = 0时该自由基存在的全部27个振动态. 针对每一振动态, 还计算了它的振动能级、经典转折点、转动惯量和离心畸变常数, 文中的大部分分子常数均属首次报导.     

O(3P)+H2→OH+H反应的立体动力学研究

利用BMS1势能面[Brandao等,J.Chem.Phys.121,8861(2004)],选取碰撞能为34.6 kcal/mol,用准经典轨线方法研究了O(3P)+H2反应的立体动力学性质.计算并讨论了k与j'的夹角的分布关系P(θr)以及描述k-k'-j'三者关系的二面角分布P((ρ)r).(k)为反应物速度方向,k'为产物的速度方向,j'为产物的角动量方向)P(θr)的峰值在90°附近并且关于90°呈对称性分布,这表明产物角动量的方向与初速度的方向垂直.二面角分布P((ρ)r)关于散射平面呈反对称性分布,这一结果表明产物的角动量具有强烈的极化效应.另外,我们还研究了振动激发对产物角动量的影响,结果表明产物的矢量性质对反应物的初始振动态非常敏感.     

非球形烟尘粒子后向散射场的光谱分析

在利用后向散射法测量烟尘浓度和粒径的过程中,对烟尘粒子模型的后向散射光谱特性进了计算,确定影响后向散射光谱强度的主要因素并进行分析。对实际排放的烟尘进行显微观察表明,利用椭球、圆柱和广义切比雪夫3种非球模型可以较好地模拟烟尘粒子,其等效直径约1μm。通过"T矩阵法"对这3种非球形粒子模型后向散射场的光谱特性进行了分析,结果表明:非球形粒子的可见/红外波段后向散射现象较球形粒子明显,特别是广义切比雪夫粒子的后向散射光强最高可达到前向的3.5倍;对于吸收性非球形粒子(复折射率m=1.57-0.56i),后向散射光强远大于非吸收性非球形粒子(复折射率m=1.57-0.001i);随着粒子等效半径的增大,光源波长也应随之增加。这为在实际测量时光源及方位的选择提供了理论依据。     

Pump power dependence of the electron-hole plasma luminescence in Ga-doped ZnO film

Time resolved two-photon absorption induced electron-hole plasma (EHP) luminescence of Ga-doped ZnO thin film was measured by an ultrafast optical Kerr gate (OKG) in femtosecond time regime. Experimental results showed that the buildup time of the EHP luminescence was strongly dependent on the excitation fluence. The dependence of the buildup time of EHP on excitation fluence probably arose mainly from the relaxation of the hot carriers due to the carrier-carrier interaction, which increased with the increase of excitation fluence.     

Additive-free controllable fabrication of bismuth vanadates and their photocatalytic activity toward dye degradation

Bismuth vanadates (BiVO₄) with various crystal structures (tetragonal scheelite, monoclinic scheelite, and tetragonal zircon) and morphologies (sphere-, nanosheet-, dendrite-, and flower-like) were controllably fabricated by using a mild additive-free hydrothermal treatment process under the different preparation conditions. The crystal structures, morphologies, and photophysical properties of the products were well-characterized. Subsequently, their UV- as well as visible-light photocatalytic performance was evaluated via dyes rhodamine B (RB) and methylene blue (MB) degradation. Special attention was paid to evaluate the correlation of the reactivity with crystal structure, morphology, and electronic structure of as-prepared BiVO₄ samples.