Co-immobilization of polymeric luminol,iron(II) tris(5-aminophenanthroline) and glucose oxidase at an electrode surface,and its application as a glucose optrode

The anodic polymerization of 3-aminophthalhydrazide (luminol) and iron(II) tris 5-aminophenanthroline (Fe(phen-NH2)3(2+)) has been reported in this paper. A bilayer electrode was developed based on these polymers and the ITO conductive glass (denoted ITO[Fe(phen-NH2)3(2+)]luminol electrode). This electrode emitted light (lambdaem: 430 nm) as it was brought into contact with H2O2. At pH 10, the resulting electrochemiluminescence (ECL) showed a linear relationship with the concentration of H2O2 in the range of 10 microM(-1) mM. This bilayer electrode also showed an application potential for the detection of glucose after being further modified with glucose oxidase (denoted ITO[Fe(phen-NH2)3(2+)]luminol]GOx electrode). Although the resulting ECL decayed more rapidly in concentrated glucose solutions (e.g., I M) because of the consumption of luminol during use, the decay became less severe in diluted glucose solutions (e.g., 10 mM). According to the flow injection analysis, a linear relationship existed between the ECL and the concentration of glucose from 10(-5)-10(-3) M at pH 9. The detection limit could reach a level of 5 x 10(-5) M at this pH.     

源内裂解液相色谱-质谱鉴别人参皂甙Rf和拟人参皂甙F11

研究了利用源内碰撞诱导解离(in-source collision-induced d issoc iation)的高效液相色谱-大气压化学电离质谱(HPLC-APC I/MS)获取人参和西洋参的化学标志物———人参皂甙R f和拟人参皂甙F11的特征结构信息及鉴别人参和西洋参的方法。在乙腈-水梯度洗脱反相液相色谱及源内碰撞诱导解离条件下,能获得人参皂甙R f和拟人参皂甙F11的母核离子及去糖基离子的源内碰撞诱导解离谱,从其差别能清楚区分这对同分异构体。本方法对人参皂甙R f和拟人参皂甙F11的检出限能达到10-7g柱上样量,简单、快速,单次质谱实验就能鉴别人参和西洋参。     

In-channel indirect amperometric detection of nonelectroactive anions for electrophoresis on a poly(dimethylsiloxane) microchip

In the present paper, we describe a microfluidics-based sensing system for nonelectroactive anions under negative separation electric field by mounting a single carbon fiber disk working electrode (WE) in the end part of a poly(dimethylsiloxane) microchannel. In contrast to work in a positive separation electric field described in our previous paper (Anal. Chem. 2004, 76, 6902-6907), here the electrochemical reduction reaction at the WE is not coupled with the separation high-voltage (HV) system, whereas the electrochemical oxidation reaction at the WE is coupled with the separation HV system. The electroactive indicator is the carbon fiber WE itself but not dissolved oxygen. This provides a convenient and sensitive means for the determination of nonelectroactive anions by amperometry. The influences of separation voltage, detection potential, and the distance between the WE and the separation channel outlet on the response of the detector have been investigated. The present detection mode is successfully used to electrochemically detect F-, Cl-, SO4(2-), CH3COO-, H2PO4-. Based on the preliminary results, a detection limit of 2 microM and a dynamic range up to three orders of magnitude for Cl- could be achieved.     

TEM investigation of formation mechanism of monocrystal-thick b-oriented pure silica zeolite MFI film

The first direct transmission electron microscopic (TEM) observation has been carried out on the continuous monocrystal-thick b-oriented pure silica zeolite MFI films produced by in situ crystallization. The self-supporting film samples for TEM study were fabricated by dissolving the steel substrate with acid. This TEM study is free of those artifacts that are typically associated with TEM sample preparations, and allows us to investigate the "true" structure and texture of a very large area of the film and at the same time to focus at will on each individual zeolite crystal in the film. Abundant TEM information including crystallographic orientation relationships among crystals in the film (both out-of-plane and in-plane), grain boundaries, and each crystal grain was obtained. This TEM investigation provides direct unambiguous new evidence to support the homogeneous nucleation mechanism, by which the films form through homogeneous nucleation and crystal growth in the bulk to form equal-sized disk-shape crystals, followed by self-assembly of these crystals onto the substrate to produce a two-dimensional close-packed structure. The last stage of the film formation involves simultaneous space-limited growth and rotation of the individual crystals to realize the in-plane crystallographic control within the film.     

THERMODYNAMIC STUDY ON ADSORPTION OF AROMATIC SULFONIC ACIDS ONTO MACROPOROUS WEAK BASE ANION EXCHANGER FROM AQUEOUS SOLUTIONS

 The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy,and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.     

氧化铬着色的随角异色颜料的制备与性能研究

采用具有干涉色的云母钛作为基质材料,以氧化铬膜着色,制备了随角异色功能颜料。用XRD、X-RiteMA86Ⅱ5角度分光光度计对产物进行测试分析,研究了不同的基质材料对颜料随角异色效果的影响,分析比较了黑白两种不同背底对颜料的明度和变化效果的影响。结果表明,改变基质材料的干涉色可以制得不同变色效果的随角异色颜料,颜料在黑色背底上的明度值变化范围较大,颜料的变色效果比较明显。     

表面热电离质谱的进展

本文评述了表面热电离质谱（ＴＩＭＳ），特别是负离子质谱（ＮＴＩ－ＭＳ）对非金属和具有高电离电位的金属元素的同位素测定的进展，引用文献３４篇。     

［Mo_3（μ_3－O）（μ－Cl）_3（μ－O_2CR）_3Cl_3］~－系列三核钼的电化学及热化学性质的研究

用循环伏安法研究了［Ｍｏ_３ＯＣｌ_６（Ｏ_２ＣＲ）_３］－（其中Ｒ＝ＣＨ_３，Ｈ，ＣＨ_２Ｃｌ）系列三核钼簇合物在ＣＨ_３ＣＮ和ＤＭＦ溶剂中的电化学行为，并用差热－热重手段研究了它们的热稳定性和热分解过程的可能机理。结果表明在不同溶剂中它们有相似的二对氧化还原峰，而且在同一溶剂中随着Ｒ基团吸电子能力的增强，相应的第一氧化还原电位值向正向移动。当Ｒ＝ＣＨ_３，Ｈ时，它们的起始分解温度分别为２６５℃和２１０℃，即同样随着Ｒ基团吸电子能力的增强，起始分解温度降低。     

The first total synthesis of (-)-tamandarin A

[formula: see text] Tamandarin A (1), a newly isolated natural product similar in structure to didemnin B (2), was shown to be somewhat more active in vitro than 2 against pancreatic carcinoma with an ED50 value 1.5 to 2 ng/mL. We report here the first total synthesis of 1. The key steps include a practical stereoselective synthesis of the Hiv-isostatine unit, high-yielding linear precursor formation, a successful macrocyclization, and coupling of the macrocycle with the side chain to afford tamandarin A (1).