Development of Efficient Chiral Packing and Their Recognition Mechanism

高效手性堆积及其识别机制的研究进展

• 批准号: 08559008
• 负责人: OKAMOTO Yoshio
• 金额: $ 9.22万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08559008/
• 关键词: Polysaccharide; Chiral Discrimination; HPLC; Chiral Stationary Phase; Chiral Recognition; CE; Cellulose; Amylose; 酵素重合; セルロースフェニルカルバメート; アミロースフェニルカルバメート; キラル充填剤

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.

纤维素和直链淀粉等多糖的苯基氨基甲酸酯衍生物作为高效液相色谱手性固定相具有很高的手性识别能力，可以拆分多种对映体。本论文主要研究了苯基氨基甲酸酯衍生物的手性识别机理.研究发现，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。这使我们能够研究ADMPC的手性识别机制的NMR光谱。ADMPC在NMR和HPLC中对多种对映体均表现出手性识别作用，以氯仿为溶剂时，HPLC和NMR的结果一致性较好。此外，通过核磁共振研究了ADMPC在溶液中的结构，采用二维NOESY技术结合计算机模拟，得到ADMPC最可能的左旋4.3螺旋结构.采用多种方法计算了纤维素三（苯基氨基甲酸酯）和纤维素三（3，5-二甲基苯基氨基甲酸酯）与某些外消旋体的相互作用能，以探讨纤维素对苯基氨基甲酸酯的手性识别机理.计算结果与色谱分离度结果吻合较好.水溶性直链淀粉和某些双糖作为毛细管电泳手性选择剂，对包括多种手性药物在内的外消旋体具有较好的拆分效果。

项目成果

N.Enomoto: "Preparation of Silica Gel-Bonded Amylose through Enzyme-Catalyzed Polymerization and Chiral Recognition Ability of Its Phenylcabamate Derivatives in HPLC" Anal.Chem.68. 2798-2804 (1996)

N.Enomoto：“通过酶催化聚合制备硅胶键合直链淀粉及其 HPLC 中苯基氨基甲酸酯衍生物的手性识别能力”Anal.Chem.68。

B.Chankvetadze: "Dichloro-, Dimethyl-and Chloromethylphenylcarbamates Derivatives of Cyclodextrins as Chiral Stationary Phases for HPLC" Chirality. 8. 402-407 (1996)

B.Chankvetadze：“环糊精的二氯、二甲基和氯甲基苯基氨基甲酸酯衍生物作为 HPLC 手性固定相”手性。

C.Yamamoto: "Enantiomeric Resolution of Cycloenantiomeric Rotaxane, Topologically Chiral Catenane, and Pretzel-Shaped Molecules : Observation of Pronounced Circular Dichroism" J.Am.Chem.Soc.119. 10547-10548 (1997)

C.Yamamoto：“环对映体轮烷、拓扑手性链烷和椒盐卷形分子的对映体拆分：显着圆二色性的观察”J.Am.Chem.Soc.119。

K.Lorenz: "Enantiomeric Enrichment of Stereolabile Chiral Spiro Compounds by Dynamic HPLC on Chiral Stationary Phases" Angew.Chem.Int.Ed.37. 1922-1924 (1998)

K.Lorenz：“通过手性固定相动态 HPLC 富集立体手性螺环化合物”Angew.Chem.Int.Ed.37。

E.Yashima: "Chromatographic Enantioseparation and Chiral Discrimination in NMR by Trisphenylcarbamate Derivatives of Cellulose, Amylose, Oligosaccharides, and Cyclodextrins" Enantiomer. 2. 225-240 (1997)

E.Yashima：“纤维素、直链淀粉、低聚糖和环糊精的三苯基氨基甲酸酯衍生物在 NMR 中的色谱对映分离和手性辨别”对映体。