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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. 制备了纤维素和直链淀粉的环己基氨基甲酸酯，并将其作为手性固定相（CSPs）用于高效液相色谱（HPLC）。csp具有较高的分辨能力，也可用于薄层色谱（TLC）。这些衍生物在氯仿中可溶，在1H NMR和hplc中对一些手性化合物表现出手性识别。甲壳素是一种容易获得的多糖，具有1,4-糖苷键，以及纤维素和直链淀粉。然而，直到最近，这种多糖还没有成功地用于制备高效液相色谱的csp。我们找到了一种合适的方法来制备具有较高手性识别能力的氨基甲酸甲酯类化合物，如3,5-二甲基、4-氯和4-三氟甲基苯基氨基甲酸甲酯。由于甲壳素3,5-二甲基和3,5-二氯苯氨基甲酸酯的csp在洗脱液中的溶解度较差，可以在氯仿存在下作为洗脱液的组分使用。合成了一种新的含乙烯基的苯基氨基甲酸酯纤维素衍生物，并与苯乙烯通过自由基共聚将其固定在硅胶上。所得CSPs在氯仿为洗脱液的色谱条件下稳定使用。提出了一种利用CD激子手性法测定单官能团化合物绝对构型的新方法。设计了一些具有两个萘发色团的非手性CD助剂，并利用这种新策略确定了手性单醇和手性单胺的绝对构型。成功构建了首个光动力手性分子马达，该马达仅沿一个方向光化学旋转，反映了马达分子的手性。马达旋转由手性烯烃和螺旋烯烃组成，其旋转由光照射和分子手性控制。