High-Performance Chiral Separation Systems Based on Polysaccharide Derivatives

基于多糖衍生物的高性能手性分离系统

基本信息

批准号：
10208206
负责人：
OKAMOTO Yoshio
金额：
$ 27.78万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas (B)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

1. Cyclohexylcarbamates of cellulose and amylose were prepared and their resolving abilities for enantiomers were evaluated as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). The CSPs showed high resolving abilities, and could also be used for thin-layer chromatography (TLC). These derivatives were soluble in chloroform and exhibited chiral discrimination to some chiral compounds in ^1H NMR spectroscopy as well as in HPLC.2. Chitin is a readily available polysaccharide with 1,4-glycosidic linkage as well as cellulose and amylose. However, until recently this polysaccharide had not successfully been used for the preparation of CSPs for HPLC. We have found a suitable method for the preparation of chitin carbamates, such as 3,5-dimethyl, 4-chloro and 4-trifluoromethylphenylcarbamates, with relatively high chiral recognition abilities. The CSPs of chitin 3,5-dimethyl and 3,5-dichlorophenylcarbamates can be used in the presence of chloroform as a component … More of eluents owing to their poor solubilities in the eluent.3. We studied the molecular recognition in crystalline inclusion compounds of bile acids and their derivatives. The existence of many asymmetric carbons and multiple hydrogen bonding groups enabled us to check notable effects of any point mutations of their molecular structures on chiral recognition. Recrystallization of the derivatives from liquid organic compounds afforded inclusion crystals suitable for single-crystal X-ray analysis. The host assemblies mostly have bilayered structures which involve one-dimensional spaces with some pockets. This research led to the reasonable interpretation of molecular recognition in size, shape, polarity and chirality.4. We have found that a membrane which contains an oligopeptide residue from an L-amino acid and is imprinted by a L-amino acid derivative recognizes the L-isomer in preference to the corresponding D-isomer, and vice versa. Enantioselective electrodialysis was attained with the membranes reflecting their adsorption selectivity. Less

1.制备了纤维素和直链淀粉的环己基氨基甲酸酯，并作为高效液相色谱（HPLC）的手性固定相（CSP）评估了它们对对映体的分离能力。CSP表现出高分离能力，也可用于薄层色谱。这些衍生物可溶于氯仿，并在 1H NMR 光谱中表现出对某些手性化合物的手性辨别。 2. 甲壳素是一种容易获得的具有 1,4-糖苷键以及纤维素和直链淀粉的多糖，但是，直到最近，我们还没有成功地使用这种多糖来制备用于 HPLC 的 CSP。适用于制备具有较高手性识别能力的甲壳素氨基甲酸酯，例如3,5-二甲基、4-氯和4-三氟甲基苯基氨基甲酸酯甲壳素 3,5-二甲基和 3,5-二氯苯基氨基甲酸酯的 CSP 可在氯仿存在下用作洗脱液的组分，因为它们在洗脱液中的溶解度较差。3。胆汁酸及其衍生物的包合物中存在许多不对称碳和多个氢键基团，使我们能够检查其分子结构的任何点突变对手性识别的显着影响。液体有机化合物的衍生物的重结晶提供了适合单晶 X 射线分析的包合物晶体，其主体组件大多具有双层结构，其中涉及带有一些口袋的一维空间。这项研究导致了分子识别尺寸的合理解释。、形状、极性和手性。4.我们发现含有L-氨基酸寡肽残基并被L-氨基酸衍生物印记的膜可识别L-异构体。膜的吸附选择性较低，反之亦然。