异丙醇-硫酸铵-水体系浮选硫氰酸亚铜法间接测定硫普罗宁

研究表明:控制溶液pH4.0,在SCN-存在下,Cu(Ⅱ)被硫普罗宁分子中的巯基(SH)还原生成的Cu(Ⅰ)与SCN-形成CuSCN白色乳状沉淀。该沉淀能被浮选在异丙醇/水两相界面之间。通过测定溶液中剩余Cu(Ⅱ)的量,从而间接测定硫普罗宁的量。硫普罗宁测量的线性范围0.30～12.0mg/L;检出限为0.20mg/L。本方法可直接用于片剂、血清、尿样中硫普罗宁含量的测定,结果满意。     

Quantitative determination of tiopronin in human plasma by LC-MS/MS without derivatization

Tiopronin (TP) is a synthetic thiol compound without chromophore. By optimizing the chromatographic conditions and sample preparation processes, an improved LC‐MS/MS analytical method without derivatization has been developed and validated to determine TP concentrations in human plasma. After reduction with 1,4‐dithiothreitol, plasma samples were deproteinized with 10% perchloric acid. The post‐treatment samples were analyzed on a C₈ column interfaced with a triple quadrupole tandem mass spectrometer in negative electrospray ionization mode. Methanol–5 mmol/L ammonium acetate (20:80, v/v) was used as the isocratic mobile phase. The assay was linear over the concentration range of 40.0–5000 ng/mL. The intra‐ and inter‐day precisions were within 12.9% in terms of relative standard deviation and the accuracy within 5.6% in terms of relative error. This simple and sensitive LC‐MS/MS method with short analytical time (3.5 min each sample) was successfully applied to the pharmacokinetic study of TP in healthy Chinese male volunteers after an oral dose of 300 mg TP. Copyright © 2011 John Wiley & Sons, Ltd.     

不同环境因子作用下水溶性CdTe量子点的生长动力学研究

以硫普罗宁为稳定剂,水热法制备了水溶性CdTe量子点,系统研究了回流时间、反应物配比、pH值、反应温度和电解质种类等环境因子对量子点生长动力学及光物理性质的影响。结果表明,溶液的pH值及反应物配比对CdTe量子点的光物理性质均有重要影响。优化条件后,回流5 h可得到发射峰位于550 nm的CdTe量子点,其荧光量子效率高达52%;在氯化钠作用下,量子点生长加快,即高浓度氯化钠会减弱溶液中粒子间静电排斥,促进离子扩散,有利于量子点的生长;添加苯磺酸钠会抑制量子点的生长,有利于制备高荧光量子效率的小尺寸CdTe量子点。     

硫普罗宁与牛血清白蛋白相互作用的研究

采用荧光技术研究了硫普罗宁与牛血清白蛋白(BSA)之间的结合作用,结果显示硫普罗宁对BSA的荧光猝灭为静态猝灭和动态猝灭共同作用的结果.经研究得到了反应的结合常数、结合热力学性质和结合位点等参数,确定了该药物与BSA之间的作用力类型为疏水作用.探究了金属离子和甘草次酸的共存对硫普罗宁与BSA结合的影响.     

Determination of D-penicillamine and tiopronin in human urine and serum by HPLC-FLD and CE-LIF with 1,3,5,7-tetramethyl-8-bromomethyl-difluoroboradiaza-s-indacene

Two rapid and sensitive analytical methods are developed for the determination of D-penicillamine (D-PEN) and tiopronin (TP) through high-performance liquid chromatography with fluorescence detection (HPLC-FLD) and capillary electrophoresis with laser-induced fluorescence detection (CE-LIF). A boron-dipyrrolemethene (BODIPY) fluorescence labeling reagent, 1,3,5,7-tetramethyl-8-bromomethyl-difluoroboradiaza-s-indacene (TMMB-Br) was successfully applied to derivatize these two thiol drugs. Fluorescein was used as the internal standard (IS) for the quantification of D-PEN and TP in CE-LIF. The derivatization and separation conditions were optimized carefully. Under the optimum conditions, the HPLC and CE separation of D-PEN and TP could be achieved within 12?min. The limits of detection were as low as 2.0 nmol/L for HPLC-FLD and 0.47 nmol/L for CE-LIF. The drugs in human urine and serum samples were determined successfully, and the recoveries were 95.0–06.7% and 95.2–104.3%, respectively.     

不同环境因素对水热法合成碲化镉量子点的影响

对比了不同巯基稳定剂和前体浓度对水热环境CdTe量子点的生长过程和光物理性质的影响。结果表明,巯基丙酸与镉前体的结合能力较强,一定程度上减小了前体溶液中镉的浓度,故CdTe量子点生长速率较慢;空间位阻较大的硫普罗宁与镉前体的结合相对较弱,因此导致CdTe量子点生长较快。巯基丙酸有利于制备发光波长较短的高荧光强度CdTe 量子点,而硫普罗宁有利于制备发光波长较长的高荧光强度CdTe量子点。前体浓度对CdTe量子点的生长速率和光物理性质的影响不明显。在上述实验结果基础上,考察了水溶性乙酸钠和聚丙烯酸钠电解质对水热环境中CdTe量子点的生长过程和光物理性质的影响。结果表明,添加乙酸钠后可提高CdTe量子点的生长速率,进而导致CdTe量子点的表面重构和钝化能力下降,使荧光强度降低;聚丙烯酸钠对镉单体独特的固定作用导致CdTe量子点生长缓慢,尺寸集中化受限,钝化能力降低,使荧光强度下降更加明显。     

Sensitive LC‐MS‐MS method for the determination of tiopronin in human plasma

A highly selective and sensitive LC‐MS‐MS method was developed and validated to quantify tiopronin in human plasma, using fudosteine as the internal standard (IS). L ‐Cysteine and 1,4‐dithiothreitol (DTT) were used as the reducer and the stabilizer to release and stabilify tiopronin from a dimmer and mix forms with endogenous thiols in the treatment of plasma samples. After a simple liquid–liquid extraction with ethyl acetate in acidic condition, the post‐treatment samples were analyzed on a C₁₈ column interfaced with a triple‐quadruple tandem mass spectrometer using negative electrospray ionization. Methanol and water (40:60, v/v) were used as the isocratic mobile phase, with 0.2% formic acid and 1.0 mM tris (hydroxymethyl) aminomethane (Tris) in water. The method was validated to demonstrate the specificity, lower limit of quantification, accuracy and precision of measurements. The assay was linear over the concentration range 0.078–10 μg/mL. The correlation coefficients for the calibration curves ranged from 0.9980 to 0.9990. The intra‐ and inter‐day precisions, calculated from quality control samples, were not more than 10.49%. The method was employed in a pharmacokinetic study after oral administration of 200 mg tiopronin tablets to 24 healthy volunteers. Copyright © 2009 John Wiley & Sons, Ltd     

Analytical Determination of N-(2-Mercapto Propionyl)Glycine (Tiopronin) by Voltammetric Methods

Abstract

The anodic processes which occur at the mercury electrode in N-(2-mercaptopropinyl)glycine (tiopronin) solutions are studied by polarographic techniques (d.c., d.p. and a.c₁.), controlled potential coulometry and cathodic stripping voltammetry. According to the observed electrochemical behaviour the overall electrode process is the formation of a mercury(II)-mercaptide. Adsorption on the electrode of both the mercaptide and the free thiol is present. The d.p.p. peak at -0.58 V or the voltammetric stripping peak at -0.56 V are used for the analytical determination of N-(2-mercaptopropionyl)glycine within the concentration ranges 7.0 10^?5 - 6.8 10^?6 mol 1^?1 or 3.0 10^?7 - 1.0 10^?9 mol I^?1, respectively. Calibration functions are reported in both cases. The interference of several organic compounds is described.     

生物相容的高荧光CdTe量子点的合成和表征

用硫普罗宁(tiopronin,TP)作为稳定剂,在水相中合成了荧光发射波长可调的高荧光CdTe量子点。本文详细地研究了稳定剂与Cd之比和pH值等实验条件对CdTe纳米粒子体系的荧光量子产率的影响。在pH=11.3回流2 h,纳米粒子体系在537 nm波长处的荧光量子产率达到了66%。通过控制实验条件,合成了各种尺寸的CdTe量子点,荧光发射光谱在504~602 nm范围连续可调。分别用X射线光电子能谱(XPS)、透射电子显微镜(TEM)、X射线衍射(XRD)、红外吸收光谱(FTIR)表征了CdTe粒子的分散性、形貌和晶型。溶血实验显示,这些由硫普罗宁稳定的CdTe量子点几乎不发生溶血作用(溶血率低于5%),具有良好的生物相容性。     

碳点-二氧化锰纳米复合材料的制备及硫普罗宁的荧光传感

以聚烯丙胺盐酸盐为反应底物,通过一步水热法制备了荧光碳点(CDs)并在其中引入高锰酸钾,通过原位的氧化还原反应制备了CDs-MnO2纳米复合材料.通过透射电子显微镜、X射线光电子能谱、纳米粒度分析、紫外-可见吸收光谱、荧光光谱、荧光寿命对其进行了形貌、结构、成分、发光性能的表征.结果 表明,MnO2通过静态猝灭效应(S...