碱性药物在硫醚嵌入苯磺酸硅胶固定相上的色谱行为

doi:10.3724/SP.J.1123.2018.04005

摘要/Abstract

摘要：

混合模式色谱（MMC）在复杂样品的分离分析方面具有独到的优势，相比于单一模式色谱，MMC受到多种作用控制，保留机理更为复杂。利用巯基-烯点击化学方法分别制备了单配体和双配体两种硫醚嵌入苯磺酸硅胶固定相，通过改变pH、离子强度和有机溶剂强度等流动相条件，以4种碱性药物为模型，对其保留机理进行了探讨。结果表明，两种固定相都具有反相和离子交换的混合保留机理。通过改变流动相中盐浓度、考察溶质保留因子与盐浓度倒数的关系，证明了反相、单纯离子交换和反相协同离子交换三种作用形式的保留模型更为合理。定量研究表明，在两个固定相上，由单纯离子交换和反相协同离子交换构成的总离子交换作用占主导，各作用占比与溶质、流动相组成、固定相配体的类型及其比例等密切相关，并且协同作用对溶质的保留和分离选择性影响很大。混合模式色谱保留机理的研究对于新型固定相设计和复杂体系的分离优化具有重要理论指导意义。

关键词: 保留机理, 反相, 混合模式色谱, 碱性药物, 巯基-烯点击化学, 阳离子交换

Abstract:

Mixed-mode chromatography (MMC) has pronounced advantages in the separation and analysis of complex samples. Compared with single-mode chromatography, the solute retention in MMC is controlled by multiple interactions, and the retention mechanism is more complicated. In this work, two thioether-embedded benzenesulfonate silica single-ligand and mixed-ligand stationary phases were prepared by thiol-ene click chemistry. The retention mechanisms of four basic drugs were investigated under various mobile phase compositions (pH, ionic and solvent strength). The results showed that both stationary phases have the mixed retention mechanism of the reverse phase and ion exchange. By changing the salt concentration of the mobile phase, the relationship between the retention factors of basic drugs and the reciprocal of ionic strength were investigated. The results indicate that a three-interaction-form model, containing reversed-phase, pure ion-exchange, and hydrophobically assisted ion-exchange interaction, is more suitable for the mechanism study of MMC. The quantitative results demonstrate that ion-exchange interaction composed of pure ion-exchange and hydrophobically assisted ion-exchange interaction is dominated on two phases. The relative contribution of each mechanism was varied with the solute, mobile phase composition, and ligand type and ratio. In addition, the hydrophobically assisted ion-exchange interaction had a significant impact on the solute retention and separation selectivity. These fundamental studies on the MMC retention mechanism are of great theoretical significance for the novel stationary phase design and the optimization of complex sample separation.

Key words: basic drugs, cation-exchange, mixed-mode chromatography (MMC), retention mechanism, reversed-phase, thiol-ene click chemistry

中图分类号:

O658

王晓欢, 陈磊. 碱性药物在硫醚嵌入苯磺酸硅胶固定相上的色谱行为[J]. 色谱, 2018, 36(9): 850-857.

WANG Xiaohuan, CHEN Lei. Chromatographic behavior of basic drugs on thioether-embedded benzenesulfonate silica stationary phases[J]. Chinese Journal of Chromatography, 2018, 36(9): 850-857.

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