Anion control of isomerism, crystal packing and binding properties in a mononuclear zinc complex

The coordination chemistry of the tetradentate pyridyl N-donor ligand cis-3,5-bis-[2-pyridinyleneamin]-trans-hydroxycyclohexane (DDOP) has been investigated with zinc(II) nitrate and triflate. The resulting complexes, [Zn(DDOP)(H₂O)(NO₃)](NO₃) (1), and [Zn(DDOP)(H₂O)(OTf)](OTf) (2) differ not only in their counterions, but also the arrangement of the axial ligands and their solid state hydrogen bonded networks. Isothermal titration calorimetry was used to assess the difference in binding properties exhibited by the two zinc complexes at physiological pH in an aqueous environment. A series of coordinating amino acids were found to preferentially bind to the mononuclear zinc triflate (1) complex over the corresponding nitrate (2) assembly, with histidine exhibiting a two centre binding mode.     

Investigation of the luminescent properties of terbium-anthranilate complexes and application to the determination of anthranilic acid derivatives in aqueous solutions

The luminescent properties of terbium complexes with furosemide (FR), flufenamic (FF) acid, tolfenamic (TF) acid and mefenamic (MF) acid have been investigated in aqueous solutions. For all four compounds, complexation occurs when the carboxylic acid of the aminobenzoic group is dissociated and is greatly favoured in the presence of trioctylphosphine oxide as co-ligand and Triton X-100 as surfactant. Under optimum conditions, luminescence of the lanthanide ion is efficiently sensitised and the lifetime of the resonance level of terbium in the complex is ranging between 1 and 1.9 ms, against 0.4 ms for the aqua ion. The sensitivity of the method for the determination of anthranilic acid derivatives is improved by one to two orders of magnitude with respect to that achieved using native fluorescence or terbium-sensitised luminescence in methanol. The limits of detection are 2×10⁻¹⁰, 5×10⁻¹⁰ and 2×10⁻⁹ mol l⁻¹ for flufenamic acid, furosemide and tolfenamic acid, and mefenamic acid, respectively, with within-run RSD values of less than 1%. The method has been applied to the determination of flufenamic acid in spiked calf sera with and without sample pretreatment. Depending on the method and the analyte concentration, the recovery was ranging between 83 and 113% and the lowest concentration attainable in serum samples was close to 1×10⁻⁷ mol l⁻¹.     

无烟煤氧化制苯多羧酸

对阳泉无烟煤进行了碱－氧气氧化研究。发现反应温度、碱的用量、反应时间以及氧初压是影响和控制水溶酸产率和反应速度的重要因素。最佳氧化条件为：温度２６０℃，碱煤比３．２８：１，反应时间２ｈ，氧初压５．５ＭＰａ。在最佳氧化条件下水溶酸的产率高达６６．０％，其中６７．４％为苯多羧酸。并采用红外光谱和气相色谱对反应产物进行了定性和定量分析。     

A High Sensitivity Fluorescent Chemo-sensory System Based on β-Cyclodextrin Dimer Modified with Dansyl Moieties

-Cyclodextrin dimer linked with ethylenediamine at the upper rim of the cyclodextrin has been synthesized and then modified with two dansyl moieties inthe presence of N,N'-dicyclohexylcarbodiimide. The sensing ability and bindingproperty of the title compound were investigated for steroids and terpenoids. Thefluorescence intensity of this dimer was decreased when a host–guest complex was formed. The value I/I⁰, where I⁰ and I are fluorescence intensitiesin the absence and presence of a guest and I is I⁰- I, was used as a parameter of sensitivity. This host exhibited a much higher sensitivity and selective molecular recognition ability for bile acids such as ursodeoxycholic acid andchenodeoxycholic acid and terpenoids such as (-)-borneol than the dansyl-modifiedcyclodextrins reported previously including -cyclodextrin dimer. The behaviors of the appended moieties of the host during the formation of host–guest complexes were studied using induced circular dichroism (ICD) and fluorescence spectra. The ICD intensityof this dimer was decreased on accommodation of a guest and this spectral pattern of the title dimer was opposite to that of bis dansyl-modified -cyclodextrin monomer. Theguest-induced variations in the fluorescence and ICD intensities suggest that this dimer formed a 1 : 1 host–guest complex and the appended moieties act as a hydrophobic cap.     

硫酸喹啉荧光猝灭法测定脱氧核糖核酸

基于DNA在pH2～4的范围内对硫酸喹啉的荧光具有较强的猝灭作用，建立了一种测定DNA的新方法。当DNA的浓度为10～700μg／L时，荧光猝灭程度与DNA浓度呈线性关系，其线性回归方程为：△IF=1．52118 0．11038G(μg／L)；相关系数r=0．9985；检出限为5．9μg／L。本方法用于大肠杆菌提取的质粒DNA的测定，获得满意结果。     

草酸电还原制取乙醛酸的研究

研究了由草酸电解还原制备乙醛酸时，温度、草酸纯度、电解时间、电极状态和电解产物对电流效率和产率的影响。实验发现，除温度和原料纯度是重要的影响因素外，电极表面的有机物吸附和电解产物－乙醛酸的浓度具有更大的影响。     

水溶液中降冰片二烯衍生物敏化学异构化反应

研究了水溶液中双环［２，２，１］－２，５庚二烯－２，３－二羧酸在吖和吖啶橙的敏化作用下的光诱导价键异构化反应。量子效率分别为０，３３（ＡＹ）和０，３１（ＡＯ）。     

Anion-exchange behaviour of a number of metal ions on DEAE-cellulose in hydrobromic and hydriodic acid media

Summary The adsorption behaviour of 48 metal ions on DEAE-cellulose layers has been investigated in aqueous hydrobromic and hydriodic acid media. R_F values are given as a function of the hydrobromic and hydriodic acid concentration over the ranges 0.01–6 mol dm^–3 and 0.01–3 mol dm^–3, respectively, and are compared with those obtained with Avicel SF. R_F spectra are comparatively simple in both media, reflecting the strong affinity of the bromide and iodide ions to the DEAE-cellulose phase. Pd, Pt, Re, Au and Hg are distributed chromatographically in either system, while most other metal ions exhibit rather extreme R_F values of near unity or zero. Therefore, the selectivity of the systems is particularly high for Pd, Pt, Re, Au and Hg, providing the possibility of their excellent selective separations.     

Interaction of (1-phenylethyl)indole-2-carbonitrile with C-nucleophiles

Methods of obtaining ketones and enamino esters have been developed on the basis of reactions of 1-(1-phenylethyl)indole-2-carbonitrile with organomagnesium and organozinc compounds. Removal of a benzyl group from the indole nitrogen atom by the Grignard reagent has been discovered. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1179–1183, August, 2006.     

亚氨基二乙酸—硅胶键合相的合成及其在核苷酸分析中的应用

以大孔微球硅胶（３０ｎｍ，８μｍ）为基体，经γ－氨丙基三乙氧基硅烷活化与间隔臂氯代环氧丙烷反应后，再与螯合剂亚氨基二乙酸键合，后者与铜离子（Ⅱ）螯合后，构成定位金属离子亲和色谱固定相。用磷酸盐缓冲溶液（ｐＨ＝７．０）作流动相，经紫外吸收检测（２６０ｎｍ）对核苷酸混合物进行了高效液相色谱分析，取得较满意的结果。