Torres-Lapasió J R, Ruiz-Angel M J, García-Alvarez-Coque M C, Abraham M H
Department of Analytical Chemistry, University of Valencia, 46100 Burjassot, Valencia, Spain.
J Chromatogr A. 2008 Feb 29;1182(2):176-96. doi: 10.1016/j.chroma.2008.01.010. Epub 2008 Jan 8.
The performance of the solvation parameter model is examined for micellar liquid chromatography. The results are compared with those offered with hydro-organic eluents, intending to reveal the properties that influence the retention and distinguish the particular behaviour of micellar systems. The retention data of several series of non-ionisable and ionisable compounds (mainly steroids, polyaromatic hydrocarbons, phenols, sulfonamides, beta-blockers, phenethylamines, antihistamines, and diuretics) were used as probe compounds. The micellar mobile phases contained an anionic (sodium dodecyl sulphate), non-ionic (Brij-35), or cationic (cetyltrimethylamonium bromide) surfactant, with or without the addition of an organic solvent (either propanol, butanol, pentanol or acetonitrile). In some instances (steroids, sulfonamides, beta-blockers and diuretics), the processed data were obtained in both micellar and hydro-organic chromatographic modes using the same column. Accuracy in predictions is critically examined and a correction term that takes into account contributions not considered in the original Abraham model, such as electrostatic or steric ones, is suggested to improve the correlations. The proposed correction takes into account differences between the descriptors of ionic and neutral species. The case of compounds showing different degrees of ionisation is discussed. Three solvation parameter approaches that allow the prediction of retention at varying mobile phase composition are proposed, which also revealed differences between the micellar and hydro-organic modes.
考察了溶剂化参数模型在胶束液相色谱中的性能。将结果与使用水-有机洗脱剂得到的结果进行比较，旨在揭示影响保留的性质并区分胶束体系的特殊行为。使用了几类非离子化和离子化化合物（主要是甾体、多环芳烃、酚类、磺胺类、β-受体阻滞剂、苯乙胺类、抗组胺药和利尿剂）的保留数据作为探针化合物。胶束流动相含有阴离子型（十二烷基硫酸钠）、非离子型（Brij-35）或阳离子型（十六烷基三甲基溴化铵）表面活性剂，添加或不添加有机溶剂（丙醇、丁醇、戊醇或乙腈）。在某些情况下（甾体、磺胺类、β-受体阻滞剂和利尿剂），使用同一根色谱柱在胶束和水-有机色谱模式下获得处理后的数据。严格检验预测的准确性，并提出一个校正项，该校正项考虑了原始亚伯拉罕模型中未考虑的贡献，如静电或空间贡献，以改善相关性。所提出的校正考虑了离子和中性物种描述符之间的差异。讨论了显示不同电离程度的化合物的情况。提出了三种溶剂化参数方法，可预测不同流动相组成下的保留情况，这也揭示了胶束模式和水-有机模式之间的差异。
