色谱

色谱 ›› 2016, Vol. 34 ›› Issue (1): 50-56.DOI: 10.3724/SP.J.1123.2015.10015

• 研究论文 • 上一篇    下一篇

新型直链淀粉类手性固定相的制备与手性拆分性能

沈军1, 李庚1, 李平1, 杨超1, 刘双燕1, 冈本佳男1,2   

  1. 1. 哈尔滨工程大学材料科学与化学工程学院, 超轻材料和表面技术教育部重点实验室, 高分子材料研究中心, 黑龙江 哈尔滨 150001;
    2. 日本名古屋大学, 日本 名古屋 464-8603
  • 收稿日期:2015-10-12 出版日期:2016-01-08 发布日期:2012-08-01
  • 通讯作者: 沈军
  • 基金资助:

    国家自然科学基金项目(21474024,51073046);黑龙江省自然科学基金项目(B2015022);中央高校基本科研业务费专项资金(HEUCFT1009).

Preparation and enantioseparation property of novel amylose-based chiral stationary phases for high performance liquid chromatography

SHEN Jun1, LI Geng1, LI Ping1, YANG Chao1, LIU Shuangyan1, OKAMOTO Yoshio1,2   

  1. 1. Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology of Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China;
    2. Nagoya University, Nagoya 464-8603, Japan
  • Received:2015-10-12 Online:2016-01-08 Published:2012-08-01
  • Supported by:

    National Natural Science Foundation of China (21474024, 51073046); Natural Science Foundation of Heilongjiang Province (B2015022); Fundamental Research Fund for the Central Universities (HEUCFT1009).

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被引次数

2

摘要：

通过对糖单元2-位进行选择性酯化以及6-位保护与去保护,运用区域选择性方法合成了5种新型直链淀粉类衍生物,分别为直链淀粉-2-苯甲酸酯-3-(4-氯苯基氨基甲酸酯)-6-(3,5-二甲基苯基氨基甲酸酯)、直链淀粉-2-苯甲酸酯-3-(4-氯苯基氨基甲酸酯)-6-(3,5-二氯苯基氨基甲酸酯)、直链淀粉-2-苯甲酸酯-3,6-二(4-氯苯基氨基甲酸酯)、直链淀粉-2-(4-氯苯甲酸酯)-3,6-二(3,5-二氯苯基氨基甲酸酯)和直链淀粉-2-(4-氯苯甲酸酯)-3,6-二(环己基氨基甲酸酯),并将其涂覆在氨丙基硅胶表面制备了HPLC手性固定相。利用核磁共振-氢谱(1H-NMR)和傅里叶变换红外光谱(FT-IR)技术对所合成衍生物的结构进行了表征和分析,并用HPLC法评价所合成衍生物的手性识别能力。与具有单一取代基直链淀粉类手性固定相的对比分析表明,所合成的新型直链淀粉类手性固定相对于某些对映体具有更为优异的拆分结果。进一步分析表明,2-、3-和6-位取代基的性能和引入位置对直链淀粉衍生物的手性识别能力均有较大的影响。

关键词: 苯基氨基甲酸酯, 苯甲酸酯, 对映体拆分, 高效液相色谱, 手性固定相, 手性识别, 直链淀粉

Abstract:

Five new amylose derivatives, namely amylose 2-benzoate-3-(4-chlorophenylcarbamate)-6-(3,5-dimethylphenylcarbamate), amylose 2-benzoate-3-(4-chlorophenylcarbamate)-6-(3,5-dichlorophenylcarbamate), amylose 2-benzoate-3,6-bis(4-chlorophenylcarbamate), amylose 2-(4-chlorobenzoate)-3,6-bis(4-chlorophenylcarbamate) and amylose 2-(4-chlorobenzoate)-3,6-biscyclohexylcarbamate, were synthesized by a series of regioselective process. These derivatives were then coated on the surface of aminopropyl silica gels, and used as chiral stationary phases (CSPs) for high performance liquid chromatography (HPLC). These derivatives were characterized by 1H-nuclear magnetic resonance (1H-NMR) and Fourier transform infrared (FT-IR) spectroscopies, and their chiral recognition abilities were evaluated using nine racemates by HPLC. Compared with other amylose derivatives, some racemates were better resolved on the new CSPs. The obtained results indicate that the property and position of substituents at 2-, 3- and 6-positions of glucose unit have great influence on the chiral recognition abilities of the amylose derivatives.

Key words: amylose, benzoates, chiral recognition, chiral stationary phases (CSPs), enantioseparation, high performance liquid chromatography (HPLC), phenylcarbamates

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