High-Performance Separation Systems Based on Kinetic Molecular Recognition

1.合成了纤维素和直链淀粉的环己基氨基甲酸酯类手性固定相，并考察了它们对手性固定相的拆分能力。CSPs具有较高的拆分能力，也可用于薄层色谱。这些衍生物可溶于氯仿，在~1H核磁共振波谱和HPLC.2中对某些手性化合物表现出手性识别。甲壳素是一种与纤维素和直链淀粉一样容易获得的1，4-糖苷键的多糖。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用CSPs。我们找到了一种制备甲壳素氨基甲酸酯的合适方法，如3，5-二甲基、4-氯和4-三氟甲基苯基氨基甲酸酯，具有较高的手性识别能力。甲壳素3，5-二甲基和3，5-二氯苯基氨基甲酸酯的CSPs在洗脱液中的溶解性较差，可以在氯仿存在的情况下作为洗脱液的组分使用。合成了一种新的含乙烯基团的纤维素苯氨基甲酸酯衍生物，并通过与苯乙烯的自由基共聚合将其固定在硅胶上。所得CSPs可在氯仿洗脱液的层析条件下稳定使用。提出了一种用CD激子手性方法确定单功能化合物绝对构型的新策略。设计了一些带有两个萘生色团的非手性CD辅助剂，利用这一新策略可以确定手性一元醇和手性单胺的绝对构型。成功地构建了第一个光驱动的手性分子马达，它只在一个方向上光化学旋转，反映了马达分子的手性。电机的旋转由手性和螺旋状的烯烃组成，其旋转受光照射和分子手性的控制。

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.