HIGH PERFORMANCE METAL CHELATE INTERACTION CHROMATOGRAPHY

高效金属螯合物相互作用色谱

• 批准号: 6293818
• 负责人: ALFRED DEL GROSSO
• 金额: --
• 依托单位国家: 美国
• 资助国家: 美国
• 起止时间: 至
• 项目状态: 未结题
• 来源: https://reporter.nih.gov/project-details/6293818
• 关键词: acidity /alkalinity; analytical method; atomic absorption spectrometry; chelating agents; high performance liquid chromatography; ionic bond; metal complex; method development; pyridine; solubility; sulfanilamides; thiazoles

A diethylenetriamine functional stationary phase, capable of complexing transition metal ions, was developed and evaluated for use in HPLC separations. Synthesis involved evaporation of the trimethoxysilylpropyl-monomer from acetate buffered aqueous solution and derivatization at 200?C and 0.55 torr. Reproducible surface coverages of 3.0 moles/m-squared were obtained on 100-angstrom, 550 m-squared/g silica. Analytical columns were loaded with Cu(II), Ni(II) and Zn(II) by frontal elution process; breakthrough volumes corresponded well with metal uptake determined by atomic absorption spectrophotometry. Buffered aqueous-organic mobile phases were used for separations of sulfonamide antimicrobials that included sulfa- diazine, sulfa-thiazole, sulfa-merazine and sulfa-pyridine. An empirical retention expression was developed that related chromatographic retention to: a) electrostatic interaction of the acidic sulfonamide function with the cationic stationary phase, b) secondary metal-ligand complexations involving the heterocyclic aromatic substituents of the solutes and c) solubilization of the relatively hydrophobic solutes in the mobile phase. Retentions were inversely proportional to concentrations of organic modifier and buffer and were generally directly proportional to eluent pH. An eluent of pH 7.3 phosphate buffer and 50% methanol was effective in minimizing electrostatic interactions while allowing retention based on metal-ligand interactions. This work was the topic of a Ph.D. dissertation, entitled "Electrostatic and Metal Interaction Chromatography of Sulfonamides" that was defended and accepted in June, 1991.

开发并评估了能够络合过渡金属离子的二乙烯三胺功能固定相，用于 HPLC 分离。 合成包括从乙酸盐缓冲水溶液中蒸发三甲氧基甲硅烷基丙基单体，并在 200°C 和 0.55 托下进行衍生化。 在 100 埃、550 平方米/克二氧化硅上获得了 3.0 摩尔/平方米的可重复表面覆盖率。 分析柱采用正面洗脱工艺装载 Cu(II)、Ni(II) 和 Zn(II)；突破体积与原子吸收分光光度法测定的金属吸收量完全一致。 缓冲水-有机流动相用于分离磺酰胺类抗菌剂，包括磺胺嘧啶、磺胺噻唑、磺胺米拉嗪和磺胺吡啶。 开发了一种经验保留表达式，将色谱保留与以下因素相关：a) 酸性磺酰胺官能团与阳离子固定相的静电相互作用，b) 涉及溶质的杂环芳族取​​代基的二次金属-配体络合，以及 c) 相对疏水性溶质在流动相中的溶解。 保留量与有机改性剂和缓冲液的浓度成反比，并且通常与洗脱液 pH 值成正比。 pH 7.3 磷酸盐缓冲液和 50% 甲醇的洗脱液可有效最大限度地减少静电相互作用，同时允许基于金属-配体相互作用的保留。 这项工作是博士学位的主题。论文题目为“磺酰胺的静电和金属相互作用色谱法”，于1991年6月答辩并被接受。