气动雾化进样微波等离子体炬（MPT）原子荧光光谱法测定锌的研究

本文将水溶液雾化进样与微波等离子体炬原子荧光光谱法联用,建立了HCL-MPT-AFS测定Zn的新方法。讨论了实验条件的选择问题以及溶液中共存离子对测定Zn的影响,本文所推荐的方法具有较高的灵敏度和精密度,并将其用于实际样品分析。     

高分辨电感耦合等离子体质谱仪测定中亚山地冰川雪冰中超痕量元素

在超净实验条件下,利用高分辨电感耦合等离子体质谱仪直接测定雪冰样品中浓度在1ng/L~100μg/L之间的多种超痕量元素Al、Fe、Mn、Co、Cu、Zn、Sr、Sb、Cd、CsBa、Tl、Pb和Bi的实验方法进展。在测定过程中灵敏度的变化可通过监测ArAr质谱峰的变化进行校正,并建立了数学校正公式。以1%HNO3为空白溶液获得了各元素的检出限(ng/L)分别为:Al40、Mn6、Fe40、Co2.74、Cu9.6、Zn20、Sr0.03、Sb0.15、Cs0.04、Ba0.4、Tl0.07、Pb0.8和Bi0.05。利用标准参考物质SLRS-4对测试方法的准确度进行了评价。研究了在硝酸含量分别为0.5%、1%、2%和4%时雪冰中超痕量元素质谱信号强度的变化特点。测定结果发现,对于污化层样品,当硝酸的含量为1%时痕量元素的质谱信号强度最大;对于非污化层样品,痕量元素的质谱信号强度在硝酸含量为0.5%时较大,但与硝酸含量为1%时的质谱信号强度相比变化率小于10%。结合中亚山地冰川雪冰中痕量元素浓度差别大的特点,确定硝酸在样品中的含量为1%为合适的酸度。并对卓奥友峰和珠穆朗玛峰雪坑样品进行了分析方法的重复性研究。     

川芎嗪的结构修饰及生物活性

介绍了川芎嗪的结构修饰及其衍生物的生物活性、川芎嗪衍生物合成及其在新药开发方面的发展前景。     

Investigation of photoinduced electron transfer in model system of vitamin E-duroquinone by time-dependent density functional theory

Photoinduced electron transfer of the model system composed of vitamin E and duroquinone has been investigated using time-dependent density functional theory. Calculations for the excited states tell that the photoexcitation of the model system can directly yield the charge transfer states in which the vitamin E moiety is positively charged but the duroquinone moiety is negatively charged. Our theoretical investigations indicate that the second charge transfer state of the model system can also be produced through the decay of higher locally excited state S(4). Since S(4) state in the model system corresponds to S(1) state of the isolated duroquinone used as a model for peroxyl radical, and S(2) state has the character of electron transfer from the tertiary amine group of the vitamin E moiety to the duroquinone moiety, the decay from S(4) to S(2) corresponds to the dynamic process following the photoexcitation of the duroquinone moiety of the model system, i.e., the initial stage of antioxidant reaction of vitamin E. Calculations of the kinetic parameters for the electron transfer have been carried out in the framework of the Marcus-Jortner-Levich formalism. Our calculations confirm that the electron transfer from S(4) to S(2) possesses the character of the inverted regime and the barrier is negligibly small.     

室温以上磁制冷材料La(Fe1-xCox)11.7Al1.3化合物的研究

通过X射线衍射分析和超导量子干涉磁强计（SQUID）磁性测量,研究了Co替代Fe含量对居里温度在室温以上的磁制冷材料La（Fe1-xCox）11.7Al1.3（x=0.072,0.081）磁结构和磁性能的影响。La（Fe1-xCox）11.7Al1.3材料的居里温度随Co的含量增加而增加,La（Fe0.919Co0.081）11.7Al1.3的居里温度为311 K。当外场变化为1.9 T时磁熵变达到3.6 J·kg^-1·K^-1,RCP值为168.6 J·kg^-1,虽然它的磁熵变小于具有巨磁熵变的磁制冷材料,但是它在磁场为1.9 T时的制冷能力与这些材料相当。     

Synthesis, crystal structure and equilibrium studies on the bidentate amine adducts of bis(S-methyl-β-N-(4-methyloxyphenyl) methylendithiocarbazide)nickel(II) complex

The crystal structure of the 1,10-phenanthroline bis(S-methyl-β-N-(4-methyloxyphenyl)methylendithiocarbazide)nickel(II) adduct, (Ni(SN)₂phen) [SN = S-methyl-β-N-(4-methyloxyphenyl)methylendithiocarbazide, PHEN = phenanthroline], has been determined by single crystal X-ray diffraction. The nickel atom is in an octahedral environment, surrounded by two chelating SN ligands and one chelating phen molecule. The nitrogen atoms from phen are in the cis configuration. The other chelating diamines adducts of the parent complex (Ni(SN)₂) were also studied, where the chelating diamnies are 5-nitro-1,10-phenanthroline(NO₂phen), 2,2′-bipyridine (bipy), 4,4′-methyl-2,2′-bipyridine (Mebipy). The equilibria were determined by UV-vis spectrometry in dichloromethane. The coordination ability of the added ligands were influenced by substitute groupings and steric factors. From the structure and addition equilibrium studies, the possible addition mechanisms are also discussed.     

HCl-NaCl-C3H8O3-H2O体系溶液热力学性质

在恒定丙三醇质量分数x=0．1的条件下，测定了无液接电池（A）和电池（B）的电动势根据电池（A）电动势确定了丙三醇和水混合溶剂中的Ag－AgCl电极的标准电极电势，讨论了HCl的迁移性质；由电池（B）测得的电动势计算了HCl在该体系中的活度系数γA，计算的结果表明，对于所讨论的体系，在溶液中总离子强度保持恒定，HCl的活度系数服从Harned规则．在溶液组成恒定时，IgγA是温度倒数1／T的线性函数，讨论了混合物中HCl的相对偏摩尔焓及介质效应．     

Determination of Tiopronin in Human Plasma by SPE then Reversed-Phase HPLC–UV

An accurate, simple and sensitive method based on reversed-phase high-performance liquid chromatography with UV detection has been developed for determination of tiopronin (TP) in human plasma. TP in plasma was reacted with p-bromophenacyl bromide (p-BPB) to give the TP-p-BPB adduct and this derivative was then extracted from the plasma on a silica gel cartridge. Potential interfering compounds were removed by washing with water, and the TP-p-BPB adduct was then eluted with acetonitrile. The organic phase obtained was evaporated to complete dryness under a stream of nitrogen. The residue was dissolved in acetonitrile and this solution was injected on to a reversed-phase ODS HPLC column. The mobile phase was usually the ternary mixture acetonitrile–water–trifluoroacetic acid, 40:59.88:0.12 (v/v). The retention times of TP-p-BPB and the internal standard adduct were 14.4 and 17.9 min, respectively. No interfering peaks were encountered in several blank plasma samples examined. The limit of detection for TP was 12 ng mL^?1. Extraction recovery exceeded 70%. The calibration plot for the TP derivative was linear in the range 40?4000 ng mL^?1, regression coefficient 0.9989, and the coefficient of the variation of the points of the calibration plot was below 10%. The method was validated appropriately and successfully applied to the determination of TP in human plasma.     

Amperometric glucose biosensor based on electrodeposition of platinum nanoparticles onto covalently immobilized carbon nanotube electrode

A new amperometric biosensor for glucose was developed based on adsorption of glucose oxidase (GOx) at the gold and platinum nanoparticles-modified carbon nanotube (CNT) electrode. CNTs were covalently immobilized on gold electrode via carbodiimide chemistry by forming amide linkages between carboxylic acid groups on the CNTs and amine residues of cysteamine self-assembled monolayer (SAM). The fabricated GOx/Au_nano/Pt_nano/CNT electrode was covered with a thin layer of Nafion to avoid the loss of GOx in determination and to improve the anti-interferent ability. The immobilization of CNTs on the gold electrode was characterized by quartz crystal microbalance technique. The morphologies of the CNT/gold and Pt_nano/CNT/gold electrodes have been investigated by scanning electron microscopy (SEM), and the electrochemical performance of the gold, CNT/gold, Pt_nano/gold and Pt_nano/CNT/gold electrodes has also been studied by amperometric method. In addition, effects of electrodeposition time of Pt nanoparticles, pH value, applied potential and electroactive interferents on the amperometric response of the sensor were discussed.

The enzyme electrode exhibited excellent electrocatalytic activity and rapid response for glucose in the absence of a mediator. The linear range was from 0.5 to 17.5 mM with correction coefficient of 0.996. The biosensor had good reproducibility and stability for the determination of glucose.     

固定化酶反应器及其在蛋白质组研究中的应用

综述了近年来国内外酶固定化载体的研究进展,侧重于无机材料和有机聚合物材料上的固定化酶方法;此外,也介绍了固定化胰蛋白酶反应器与分离系统联用在蛋白质样品分析中的应用,并展望了固定化酶反应器的研究方向及其在蛋白质组中的应用前景。