Development of Highly Sensitive Analytical Systems to Determine the Absolute Configuration of Chiral Compounds

为了开发高灵敏度的方法来确定手性分子的绝对构型，设计并制备了新型手性衍生化试剂(+)-TBMB和(+)-TBB羧酸。通过对L苯丙氨酸衍生物的X-射线分析，确定前者的绝对构型为(2S)。它们被设计成具有CD(圆二色)发色团、分离的Me基团和体内的荧光，可以有效地用于CD、核磁共振和高效液相分析，以确定手性分子的绝对构型和光学纯度。对其衍生化、纯化、分离和检测的分析条件进行了考察。建立了简便、灵敏的D，L-异构体分析方法。对于糖和氨基酸，有效地利用了核磁共振和高效液相色谱技术。对于甘油脂，基于激子手性的圆二色谱(CD)与高效液相系统相结合，建立了一个同时测定甘油脂绝对构型和光学纯度的系统。该体系用于脂肪酶催化甘油三酯的立体化学研究。

With aims to develop highly sensitive ways to determine the absolute configurations of chiral molecules, new type of chiral derivatizing agents, (+)-TBMB and (+)-TBB carboxylic acids were designed and prepared. The absolute configurations of the former was determined to be (2S) by X-ray analysis of the L-phenylalanie derivative. They were designed to have a CD (circular dichroism) chromophore, isolated Me groups and fluorescent in the bodies which can be effectively used in the CD, NMR and HPLC analyzes to determine the absolute configuration and the optical purity of chiral molecules.Targets for applying these two reagents were directed to three biomolecules, carbohydrates, amino acids and glycerolipids. The analytical conditions were investigated for the derivatization, purification, separations and detections for each. Consequently, simple and highly sensitive methods were established to analyze the D, L-isomers. For sugars and amino acids, NMR and HPLC were effectively employed in the system. For glycerolipids, circular dichroism (CD) based on exciton chirality way was coupled with HPLC system to build a simultaneous system to determine the absolute configuration and the optical purity. This system was employed in the study on the stereochemistries of lipase-catalyzed hydrolysis of glycerides.