Geometries and properties of bimetallic phosphido-bridged complex Cp(CO)2W(μ-PPh2)W(CO)5 and Cp(CO)3W(μ-PPh2)W(CO)5

Complete geometry optimizations were carried out by HF and DFT methods to study the molecular structure of binuclear transition-metal compounds (Cp(CO)₃W(μ-PPh₂)W(CO)₅) (I) and (Cp(CO)₂W(μ-PPh₂)W(CO)₅) (II). A comparison of the experimental data and calculated structural parameters demonstrates that the most accurate geometry parameters are predicted by the MPW1PW91/LANL2DZ among the three DFT methods. Topological properties of molecular charge distributions were analyzed with the theory of atoms in molecules. (3, −1) critical points, namely bond critical point, were found between the two tungsten atoms, and between W1 and C10 in complex II, which confirms the existence of the metal–metal bond and a semi-bridging CO between the two tungsten atoms. The result provided a theoretical guidance of detailed study on the binuclear phosphido-bridged complex containing transition metal–metal bond, which could be useful in the further study of the heterobimetallic phosphido-bridged complexes.     

锑化镓的光助微刻蚀及其表面氧化物的研究

用电化学和光电化学方法研究锑化镓表面的腐蚀以及锑化镓表面氧化膜的生成和溶解，锑化镓电极在一定电势下生成的氧化膜，用俄歇能谱证明，其主要成分为难溶的氧化锑，此氧化膜的存在抑制了锑化镓的进一步腐蚀，同时亦使锑化镓的半导体光电化学性能大为减弱，通过激光微刻蚀及电子显微镜的观察，在刻蚀剂中添加酒石酸，柠檬酸和氢氟酸等试剂，可使刻蚀形得改善，实验研究了锑化镓的平带电势的测定。     

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of > 80% was achieved when applied to the analysis of curcumin in extracts of tumeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 kV, injection for 6 s at 9 kV and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 x 10(-8) mol/l (S/N = 3), high efficiency of 1.0 x 10(5) N, linear range of 7 x 10(-4) -3 x 10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.     

Theoretical analysis and computer simulation of fluorescence lifetime measurements. I. Kinetic regimes and experimental time scales

The configuration-controlled regime and the diffusion-controlled regime of conformation-modulated fluorescence emission are systematically studied for Markovian and non-Markovian dynamics of the reaction coordinate. A path integral simulation is used to model fluorescence quenching processes on a semiflexible chain. First-order inhomogeneous cumulant expansion in the configuration-controlled regime defines a lower bound for the survival probability, while the Wilemski-Fixman approximation in the diffusion-controlled regime defines an upper bound. Inclusion of the experimental time window of the fluorescence measurement adds another dimension to the two kinetic regimes and provides a unified perspective for theoretical analysis and experimental investigation. We derive a rigorous generalization of the Wilemski-Fixman approximation [G. Wilemski and M. Fixman, J. Chem. Phys. 60, 866 (1974)] and recover the 1/D expansion of the average lifetime derived by Weiss [G. H. Weiss, J. Chem. Phys. 80, 2880 (1984)].     

肉桂酸类分子非线性光学效应的理论研究

计算了一系列肉桂酸（苯基丙烯酸）类化合物的二阶非线性光学系数，系统地研究了取代基的电子性质和取代位置对其非线性光学性质的影响，并且探讨了该类化合物的饱和取代效应．研究表明，该类化合物的非线性光学性质与其分子结构有着密切的关系．     

Solid-state nanopores for ion and small molecule analysis

Solid-state nanopore in analytical chemistry has developed rapidly in the 1990s and it is proved to be a versatile new tool for bioanalytical chemistry. This review focuses on the analysis of ions and small molecules with nanopores including nanopipettes, polymer film nanopores, Si₃N₄ nanopores, graphene nanopores, MoS₂ nanopores and MOFs.     

离子液体萃取阿魏酸和咖啡酸的性能研究

以1-甲基-3-丁基咪唑六氟磷酸盐([C4mim][PF6])和1-甲基-3-己基咪唑六氟磷酸盐([C6mim][PF6])离子液体为萃取剂,采用紫外分光光度法研究了溶液pH值、温度、相比率及盐的种类和浓度对其萃取阿魏酸和咖啡酸效率的影响,考察了被萃取物的回收及离子液体的循环使用,探讨了两种离子液体替代传统有机溶剂阿魏酸和咖啡酸的可能性。实验结果表明:萃取温度和无机盐的种类及浓度对FA和CA萃取效率的影响较小;水相pH值对萃取效率有较大的影响,萃取FA适宜pH应小于3.67,萃取CA适宜pH应小于3.71;被萃取物浓度增大,萃取效率降低,而相体积比增大其萃取效率升高;两种离子液体对FA和CA的萃取效率[C4mim][PF6]大于[C6mim][PF6],同种离子液体对FA的萃取效率大于CA;在萃取相中的FA和CA可定量回收,且被萃取物中离子液体的残留[C6mim][PF6]小于[C4mim][PF6],离子液体可循环使用。     

锌,锰对K—Fe／ZSM—48CO加氢催化反应性能的影响

锌、锰对ＫＦｅ／ＺＳＭ４８ＣＯ加氢催化反应性能的影响范彬彬马静红樊卫斌李瑞丰曹景慧（太原工业大学精细化工研究所，太原０３００２４）关键词ＣＯ加氢，ＺＳＭ４８，助剂效应ＫＦｅ／ＺＳＭ４８在一氧化碳加氢合成低碳烯烃的反应中表现出良好的性能。沸石载体不仅...     

Analysis of flavonoids in <Emphasis Type="Italic">Ginkgo biloba</Emphasis> L. and its phytopharmaceuticals by capillary electrophoresis with electrochemical detection

A high-performance capillary electrophoretic (CE) method with electrochemical detection (ED) has been developed for determination of the pharmacologically active flavonoids in Ginkgo biloba L. and phytopharmaceuticals containing its extract. Epicatechin, catechin, rutin, apigenin, luteolin, and quercetin are important flavonoids in this plant. Operated in a wall-jet configuration, a 300 micro m diameter carbon-disk electrode was used as working electrode with good response to the six analytes at +1000 mV (relative to the SCE). Under the optimum conditions, the analytes were separated within 22 min in a borax buffer (pH 9.0). Excellent linearity was obtained over two orders of magnitude and detection limits (S/N=3) ranged from 1.4 x 10(-7) to 5.0 x 10(-7) g mL(-1) for all six analytes. The method was successfully used for assay of Ginkgo biloba L. and its phytopharmaceuticals after a relatively simple extraction procedure; the results obtained were satisfactory.     

Potentiometric immunosensor based on antiserum of Japanese B encephalitis immobilized in nano-Au/polymerized o-phenylenediamine film

A novel potentiometric immunosensor for detection of Japanese B encephalitis vaccine was developed by immobilizing antiserum of Japanese B encephalitis on nano-Au/polymerized o-phenylenediamine (o-PDA) film on the platinum (Pt) electrode. The performance and factors influencing the performance of the resulting immunosensor were studied. The immunosensor showed a specific response to Japanese B encephalitis vaccine in the range 1.1 × 10⁻⁸ to 2.0 × 10⁻⁶ lgpfu/ml (plaque forming unit) with a detection limit of 6 × 10⁻⁹ lgpfu/ml. The correlation coefficient is 0.9986. The incubation time, incubation temperature, pH, reproducibility and stability of the immunosensor were also studied. The present work supplied a promising test method for biological products.