High-Performance Chiral Separation Systems Based on Polysaccharide Derivatives

基于多糖衍生物的高性能手性分离系统

• 批准号: 10208206
• 负责人: OKAMOTO Yoshio
• 金额: $ 27.78万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10208206/
• 关键词: Polysaccharide; Chiral Discrimination; HPLC; Chiral Stationary Phase; Crystalline Inclusion; Steroidal Bile Acid; Molecular Imprinting; Membrane; 分子インプリント法; 包接結晶化法; 胆汁酸ステロイド

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 … More of eluents owing to their poor solubilities in the eluent.3. We studied the molecular recognition in crystalline inclusion compounds of bile acids and their derivatives. The existence of many asymmetric carbons and multiple hydrogen bonding groups enabled us to check notable effects of any point mutations of their molecular structures on chiral recognition. Recrystallization of the derivatives from liquid organic compounds afforded inclusion crystals suitable for single-crystal X-ray analysis. The host assemblies mostly have bilayered structures which involve one-dimensional spaces with some pockets. This research led to the reasonable interpretation of molecular recognition in size, shape, polarity and chirality.4. We have found that a membrane which contains an oligopeptide residue from an L-amino acid and is imprinted by a L-amino acid derivative recognizes the L-isomer in preference to the corresponding D-isomer, and vice versa. Enantioselective electrodialysis was attained with the membranes reflecting their adsorption selectivity. Less

1.合成了纤维素和直链淀粉的环己基氨基甲酸酯，并评价了它们作为高效液相色谱手性固定相的拆分能力。所制备的CSPs具有良好的分离能力，可用于薄层色谱分析。这些衍生物可溶于氯仿，并在^1H NMR光谱和HPLC中对某些手性化合物表现出手性区分。2。甲壳素是一种容易获得的多糖，具有1，4-糖苷键以及纤维素和直链淀粉。然而，直到最近，这种多糖还没有成功地用于制备用于HPLC的CSP。我们找到了一种合适的方法来制备具有较高手性识别能力的甲壳素氨基甲酸酯，如3，5-二甲基、4-氯和4-三氟甲基苯基氨基甲酸酯。甲壳素3，5-二甲基和3，5-二氯苯氨基甲酸酯的CSP可以在氯仿存在下作为组分使用 ...更多信息 由于洗脱剂在洗脱剂中的溶解性差，洗脱剂的溶解性差。研究了胆汁酸及其衍生物结晶包合物的分子识别作用。许多不对称碳和多个氢键基团的存在，使我们能够检查显着的影响，任何点突变的分子结构上的手性识别。从液体有机化合物的衍生物的重结晶提供适合于单晶X-射线分析的包合晶体。主体组件大多具有双层结构，其涉及具有一些口袋的一维空间。该研究对分子识别在大小、形状、极性和手性等方面给出了合理的解释.我们已经发现，含有来自L-氨基酸的寡肽残基并被L-氨基酸衍生物印迹的膜优先识别L-异构体而不是相应的D-异构体，反之亦然。利用反映其吸附选择性的膜实现了对映选择性电透析。少

项目成果

M.Yoshikawa: "Chiral Recognition of N-α-acetyltryptophans with Molecularly Imprinted Polymeric Membranes Containing DVNE Derivatives" Sen-i Gakkaishi. 54. 77-84 (1998)

M. Yoshikawa：“含有 DVNE 衍生物的分子印迹聚合物膜对 N-α-乙酰色氨酸的手性识别”Sen-i Gakkaishi 54. 77-84 (1998)。

Y.Kondo: "Molecularly imprinted polyamide membranes for chiral recognition"Polym.Bull.. 44. 517-524 (2000)

Y.Kondo：“用于手性识别的分子印迹聚酰胺膜”Polym.Bull.. 44. 517-524 (2000)

C.Yamamoto: "Computational Studies on Chiral Discrimination Mechanism of Phenylcarbamate Derivatives of Cellulose"Bull.Chem.Soc.Jpn.. 72. 1815-1825 (1999)

C.Yamamoto：“纤维素苯基氨基甲酸酯衍生物的手性判别机制的计算研究”Bull.Chem.Soc.Jpn.. 72. 1815-1825 (1999)

M. Chikada: "Intercalation and Polymerization in Chenodeoxycholic Acid Channels with Retention of a Crystalline State"Polym. J.. 31. 1061-1064 (1999)

M. Chikada：“鹅去氧胆酸通道中的嵌入和聚合并保留晶态”聚合物。

K.Sada: "Controlled Expansion of a Molecular Cavity in a Steroid Host Compound"J.Am.Chem.Soc.. (in press).

K.Sada：“类固醇主体化合物中分子腔的受控扩张”J.Am.Chem.Soc.（正在出版）。