High-Performance Separation Systems Based on Kinetic Molecular Recognition

基于动力学分子识别的高性能分离系统

基本信息

批准号：
10208103
负责人：
OKAMOTO Yoshio
金额：
$ 1.41万
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

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10208103/
关键词：
Polysaccharide Chiral Discrimination HPLC Chiral Stationary Phase TLC Immobilization CD Exciton Chirality Method Molecular Motor シクロアルキルカルバメート HPLC CD励起子法 CDスペクトル TLC トランス-シス異性化アルキルカルバメートキチン不斉識別

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 of eluents owing to their poor solubilities in the eluent.3. A new cellulose phenylcarbamate derivative having a vinyl group was synthesized and immobilized onto silica gel via radical copolymerization with styrene. The resulting CSPs could be stably used under chromatographic conditions with a chloroform as an eluent.4. A new strategy for determining the absolute configuration of mono-functional compounds by the CD exciton chirality method was proposed. Some achiral CD auxiliaries with two naphthalene chromophores were designed, and the absolute configurations of chiral mono-alcohols and chiral mono-amines could be determined by this new strategy.5. The first light-powered chiral molecular motor, which photochemically rotates only in one-direction reflecting the chirality of the motor molecule was successfully constructed. The motor rotation was composed of a chiral and helical olefin, and its rotation was controlled by the irradiation of light and molecular chirality.

1。制备纤维素和双链淀粉的环己基核酸酯，并将其对映异构体的分辨能力评估为高性能液相色谱（HPLC）的手性静止相（CSP）。 CSP具有高分辨率的能力，也可以用于薄层色谱法（TLC）。这些衍生物可溶于氯仿，并在1H NMR光谱以及HPLC.2中表现出手性歧视对某些手性化合物的表现。几丁质是一种容易获得的多糖，具有1,4-糖苷键以及纤维素和淀粉酶。但是，直到最近，这种多糖还没有成功用于为HPLC制备CSP。我们找到了一种适合制备甲壳质载体的方法，例如3,5-二甲基，4-氯和4-三氟甲基苯基钙甲甲酸酯，具有相对较高的手性识别能力。几丁质3,5-二甲基的CSP和3,5-二氯苯基氨基甲酸酯可以在氯仿存在下用作洗脱液中的溶解度的组成部分。3。合成了乙烯基的新型纤维素苯卡氨酸衍生物，并通过与苯乙烯自由共聚合成并将其固定在硅胶上。所得的CSP可以在带有氯仿的色谱条件下稳定使用。4。提出了一种新的策略，用于通过CD激子手性方法确定单功能化合物的绝对构型。设计了一些具有两个萘式发色团的Achiral CD辅助机，并且可以通过这种新策略来确定手性单酒精和手性单胺的绝对构型。5。成功构建了第一个轻度手性分子电动机，仅在反映运动分子的手学的一方向上旋转。运动旋转由手性和螺旋烯烃组成，其旋转受光和分子手性的照射控制。