HIGH PERFORMANCE METAL CHELATE INTERACTION CHROMATOGRAPHY

研制了一种能络合过渡金属离子的二乙烯三胺功能固定相，并对其在高效液相色谱分离中的应用进行了评价。 合成涉及从醋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 °下衍生化C和0.55 ℃。 在100埃、550平方米/克二氧化硅上获得3.0摩尔/平方米的可再现表面覆盖率。 分析柱加载Cu（II），Ni（II）和Zn（II）的前沿洗脱过程;突破体积对应以及通过原子吸收分光光度法测定的金属吸收。 采用缓冲水-有机移动的流动相分离磺胺类抗菌剂，包括磺胺嘧啶、磺胺噻唑、磺胺美拉嗪和磺胺吡啶。 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级金属-配体络合，以及c）相对疏水性溶质在移动的相中的增溶。 保留率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成正比。pH 7.3磷酸盐缓冲液和50%甲醇的洗脱液有效地使静电相互作用最小化，同时允许基于金属-配体相互作用的保留。 这项工作是一个博士的主题。论文，题为“磺胺类药物的静电和金属相互作用色谱法”，于1991年6月答辩并被接受。

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.