Development of New Chiral Packing Material for HPLC Based on the Structure Control of Polysaccharide Derivatives and Their Immobilization onto Silica Gel

基于多糖衍生物结构控制及其硅胶固定化的新型高效液相色谱手性填料的研制

• 批准号: 13355033
• 负责人: OKAMOTO Yoshio
• 金额: $ 26.62万
• 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13355033/
• 关键词: Polysaccharide Derivatives; HPLC; Enantioseparation; Immobilization; Chiral Packing Material; Radical Polymerization; Chiral Recognition; Chiral Stationary Phase; ジメチルブタジエン; 共重合; スチレン

Phenylcarbamate derivatives of cellulose and amylose are known to show high chiral recognition as chiral stationary phases (CSPs) in HPLC. However, the solvents such as chloroform and tetrahydrofuran, which dissolve or swell the polysacoharide derivatives, cannot be used as main mobile phases for the CSPs. In order to overcome this defect, the cellulose 3,5-dimethylphenylcarbamate derivative having a regioselective vinyl group was immobilized to silica gel via the radical copolymerization with vinyl monomer under various immobilization conditions.・When the content of the vinyl monomer was low, the chiral recognition abilities of the obtained CSPs were similar to those of the coated CSP.・The immobilization was attained more effectively by using silica gel having a vinyl group.・Cellulose derivative having a random vinyl group at the 2-, 3-, and 6-positions were prepared by the one-pot process to avoid the complicated synthetic process. The obtained derivative was quantitatively immobilized on silica gel as well as the cellulose derivatives having the regioselective vinyl group.・When the cellulose derivative having a vinyl group was copolymerized with 2,3-dimethylbutadiene, the chiral recognition ability of the immobilized CSP was close to those of the coated CSP.This immobilization method was effective for other phenylcarbamate derivatives of cellulose and amylose, indicating that it must be valuable for the preparation of the polysaccharide-based packing materials for the next generation.

纤维素和直链淀粉的苯氨基甲酸酯衍生物作为手性固定相（CSPs）在HPLC中具有较高的手性识别。然而，溶剂如氯仿和四氢呋喃，溶解或膨胀的多糖衍生物，不能作为csp的主要流动相。为了克服这一缺陷，在不同的固定条件下，通过与乙烯基单体的自由基共聚，将具有区域选择性乙烯基的纤维素- 3,5-二甲基苯基氨基甲酸酯衍生物固定在硅胶上。·当乙烯基单体含量较低时，所得CSP的手性识别能力与包覆CSP相似。使用具有乙烯基的硅胶可以更有效地实现固定化。·为避免复杂的合成过程，采用一锅法制备了2-、3-和6-位随机乙烯基的纤维素衍生物。将得到的衍生物定量固定在硅胶和具有区域选择性乙烯基的纤维素衍生物上。当含有乙烯基的纤维素衍生物与2,3-二甲基丁二烯共聚时，固定化CSP的手性识别能力与包覆CSP接近。该固定化方法对其他苯氨基甲酸酯类纤维素和直链淀粉衍生物的固定化效果良好，对下一代多糖基包装材料的制备具有一定的应用价值。

项目成果

Tsuchida, T.Hasegawa, K.Kobayashi, C.Yamamoto, Y.Okamoto: "Resolution of Enantiomers Using Sugar-Carrying Polyisocyanides as Chiral Stationary Phases for HPLC"Bull.Chem.Soc.Jpn.. 75. 2681-2685 (2002)

Tsuchida、T.Hasekawa、K.Kobayashi、C.Yamamoto、Y.Okamoto：“使用携带糖的多异氰化物作为 HPLC 手性固定相来解析对映体”Bull.Chem.Soc.Jpn.. 75. 2681-2685 (2002

Yamamoto, Y.Okamoto: "Optically Active Polymers for Chiral Separation"Bull.Chem.Soc.Jpn.. 77. 227-257 (2004)

Yamamoto, Y.Okamoto：“用于手性分离的光学活性聚合物”Bull.Chem.Soc.Jpn.. 77. 227-257 (2004)

T.Kubota: "Phenylcarbamate Derivatives of Cellulose and Amylose Immobilized onto Silica Gel as Chiral Stationary Phases for High-Performance Liquid Chromatography"J.Polym.Sci., Part A. 42(印刷中). (2004)

T.Kubota：“纤维素和直链淀粉的苯基氨基甲酸酯衍生物作为高效液相色谱的手性固定相固定在硅胶上”，J.Polym.Sci.，A. 42 部分（出版中）。

C.Yamamoto: "Optically Active Polymers for Chiral Separation"Bull.Chem.Soc.Jpn. 77・2. 227-257 (2004)

C.Yamamoto：“用于手性分离的光学活性聚合物”Bull.Chem.Soc.Jpn. 77・2 (2004)。

C.Yamamoto: "Structural Analysis of Amylose Tris(3,5-Dimethylphenylcarbamate) by NMR Relevant to Its Chiral Recognition Mechanism in HPLC"J.Am.Chem.Soc.. 124・42. 12583-12589 (2002)

C. Yamamoto：“通过NMR对直链淀粉三(3,5-二甲基苯基氨基甲酸酯)进行与其手性识别机制在HPLC中的结构分析” J.Am.Chem.Soc.. 124・42 (2002)。