Quinine and quinidine derivatives as chiral selectors .1. Brush type chiral stationary phases for high-performance liquid chromatography based on cinchonan carbamates and their application as chiral anion exchangers
Quinine and quinidine derivatives as chiral selectors .1. Brush type chiral stationary phases for high-performance liquid chromatography based on cinchonan carbamates and their application as chiral anion exchangers
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DOI：
10.1016/0021-9673(96)00137-9
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发表时间：
1996-08-09
影响因子：
4.1
通讯作者：
Lindner, W
中科院分区：
文献类型：
--
作者：
Lammerhofer, M;Lindner, W
利用两种不同类型的间隔基和/或接枝方式将奎宁和奎尼丁氨基甲酸酯分别固定在多孔硅胶上，得到了四种刷型手性固定相。这些CSP优先使用缓冲水相流动相来拆分酸性分析物的对映体，除了在修饰后的二氧化硅表面上的额外吸附之外，离子对机制是主要的结合和/或保留原理。成功拆分的外消旋体的光谱包括手性芳基、芳氧基和芳基硫代羧酸，以及N-衍生氨基酸(DNB-、B-、Ac-、F-、DNP-、DBD-、Fmoc-、Boc-、Z-、Dns-氨基酸等)。以及许多其他手性酸，包括磺酸、膦酸和磷酸。考察了流动相参数和分析物结构变化对保留和对映体选择性的影响。因此，提出了一个色谱学推导的DNB-氨基酸的初步手性识别模型，这些氨基酸被拆分成具有异常高的α值的对映体(例如，α值约为7的DNB-Leu)。
Quinine and quinidine carbamates, respectively, have been immobilized onto porous silica utilizing two different types of spacer and/or grafting modes, obtaining four brush type chiral stationary phases (CSPs). These CSPs have preferentially been operated with buffered aqueous mobile phases to resolve the enantiomers of acidic analytes involving ion pair mechanisms as the dominating binding and/or retention principle beside additional adsorption towards the modified silica surface. The spectrum of successfully resolved racemates contains chiral aryl-, aryloxy- and arylthiocarboxylic acids, as well as N-derivatized amino acids (DNB-, B-, Ac-, F-, DNP-, DBD-, Fmoc-, Boc-, Z-, DNS-amino acids, etc.) and many other chiral acids including also sulfonic, phosphonic and phosphoric acids. The influence of mobile phase parameters, as well as of structure variations of analytes on retention and enantioselectivity was evaluated. Thus, a chromatographically derived tentative chiral recognition model is proposed for DNB-amino acids which are resolved into enantiomers with exceptionally high alpha-values (e.g., DNB-Leu with an alpha-value of about 7).