Development of Efficient Chiral Packing and Their Recognition Mechanism

纤维素和直链淀粉等多糖的苯氨基甲酸酯衍生物作为高效液相色谱（HPLC）的手性固定相（CSPs）具有很高的手性识别能力，可以分辨多种对映体。本研究主要研究了苯氨基甲酸酯类衍生物的手性识别机理。我们发现低聚合度的直链淀粉三（3,5 -二甲基苯基氨基甲酸酯）（ADMPC）可溶于氯仿。这使我们能够通过核磁共振光谱研究ADMPC的手性识别机制。在核磁共振和高效液相色谱中，ADMPC对许多对映体表现出手性识别。以氯仿为常用溶剂时，HPLC和NMR的研究结果吻合较好。此外，利用二维NOESY技术结合计算机模拟对ADMPC在溶液中的结构进行了核磁共振研究，得到了ADMPC.2最可能的左旋4.3螺旋结构。通过不同的方法计算了纤维素三（苯基氨基甲酸酯）或纤维素三（3,5-二甲基苯基氨基甲酸酯）与一些外消旋物的相互作用能，以深入了解纤维素对苯基氨基甲酸酯的手性识别机理。计算结果与色谱分辨率结果吻合较好。用水溶性直链糖和一些双糖作为毛细管电泳的手性选择剂，它们可以溶解一些外消旋物，包括一些手性药物。

Phenylcarbamate derivatives of polysaccharides such as cellulose and amylose show high chiral recognition abilities as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) and can resolve a broad range of enantiomers. In this study, the chiral recognition mechanism of the phenylcarbamate derivatives was mainly investigated.1. We found that amylose tris (3, 5-dimethylphenylcarbamate) (ADMPC) with low degree of polymerization is soluble in chloroform. This enabled us to study the chiral recognition mechanism of ADMPC by NMR spectroscopy. ADMPC exhibited chiral discrimination for many enantiomers in NMR as well as in HPLC.A good agreement was observed on the results of HPLC and NMR studies when chloroform was employed as a common solvent. Moreover, the structure of ADMPC in solution was investigated by NMR using 2D NOESY technique coupled with a computer modeling and left-handed 4.3 helical structure was obtained as the most probable one for ADMPC.2. The calculations of interaction energies between cellulose tris (phenylcarbamate) or cellulose tris (3,5-dimethylphenylcarbamate) and some racemates were performed by various methods to gain insight into the mechanism for the chiral recognition on phenylcarbamates of cellulose. The results of the calculations were good agreement with the results in the chromatographic resolution.3. Water-soluble amylose and some disaccharides were used as chiral selectors in capillary electrophoresis and they could resolve some racemates including several chiral drugs.