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.

多糖（例如纤维素和双糖）的苯基钙氨酸衍生物显示出高性质固定相（CSP）的高性识别能力，用于高性能液相色谱（HPLC），并且可以解决广泛的映体。在这项研究中，主要研究了苯基氨基酯衍生物的手性识别机制。1。我们发现，聚合程度低的链淀粉Tris（3，5-二甲基苯基碳酸盐）（ADMPC）可溶于氯仿。这使我们能够通过NMR光谱研究ADMPC的手性识别机制。 ADMPC在NMR和HPLC中表现出了许多对映异构体的手性歧视。当使用氯仿作为常见溶剂时，就HPLC和NMR研究的结果观察到了良好的一致性。此外，通过NMR使用2D Noesy技术与计算机建模和左手4.3的螺旋结构一起研究了ADMPC在溶液中的结构，作为ADMPC.2的最可能的螺旋结构。通过各种方法进行了纤维素三（3,5-二甲基苯基氨基甲酸酯）和一些种族群之间的相互作用能量（3,5-二甲基苯基氨基甲酸酯）和一些种族酸盐的计算。计算的结果与色谱分辨率的结果非常一致。3。水溶性链淀粉和一些二糖在毛细管电泳中用作手性选择器，它们可以解决一些包括多种手性药物在内的种族群体。

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。

Y.Okamoto: "Polysaccharide Derivatives for Chromatographic Separation of Enantiomes" Angew.Chem.Int.Ed.37. 1020-1043 (1998)

Y.Okamoto：“用于对映体色谱分离的多糖衍生物”Angew.Chem.Int.Ed.37。