化学学报 ›› 2011, Vol. 69 ›› Issue (24): 3019-3027.DOI: 10.6023/A1106192 上一篇    下一篇

研究论文

采用新型分子表面印迹技术构建手性空穴实现对手性药物对映体的分子识别与高效拆分

李丁, 高保娇*, 许文梅   

  1. (中北大学化学工程系 太原 030051)
  • 收稿日期:2011-06-19 修回日期:2011-08-27 出版日期:2011-12-28 发布日期:2011-09-06
  • 通讯作者: 高保娇 E-mail:gaobaojiao@126.com

Realizing molecular recognition and high efficient Preparation for enantiomers of Chiral Drugs by constituting Chiral caves with Novel Surface-Molecular Imprinting Technique

LI Ding, GAO Bao-Jiao, XU Wen-Mei   

  1. (Department of Chemical Engineering, North University of China, Taiyuan 030051)
  • Received:2011-06-19 Revised:2011-08-27 Online:2011-12-28 Published:2011-09-06
  • Contact: Bao-jiao GAO E-mail:gaobaojiao@126.com

通过偶联剂γ-氨丙基三甲氧基硅烷(AMPS)的媒介, 通过表面引发接枝, 将功能单体甲基丙烯酸(MAA)接枝聚合在微米级硅胶微粒表面, 制得功能接枝微粒PMAA/SiO2|采用本课题组建立的新型分子表面印迹技术, 以四咪唑(TM)为模型手性药物, 用其左旋对映体L-TM为模板分子, 乙二醇二缩水甘油醚(EGDE)为交联剂, 对接枝在硅胶表面的PMAA大分子链进行了分子印迹, 制备了对映体L-TM分子表面印迹材料MIP-PMAA/SiO2. 探索了该印迹材料对外消旋体D,L-TM中两种对映体的拆分性能, 采用静态与动态两种方法考察了MIP-PMAA/SiO2对模板分子L-TM的分子识别特性与结合性能. 实验结果表明, 印迹材料MIP-PMAA/SiO2L-TM分子具有特异的分子识别选择性与优良的结合亲和性, 相对于右旋对映体D-TM, 识别选择性系数为4.03, MIP-PMAA/SiO2对外消旋体D,L-TM中的两种对映体表现出优良的拆分性能. 此外, 印迹材料MIP-PMAA/SiO2也具有良好的解吸性能, 以稀NaOH水溶液为洗脱液, 20个床体积内解吸率即达到99.08%.

关键词: 聚甲基丙烯酸, 硅胶, 表面分子印迹, 分子识别, 四咪唑, 手性拆分

Via the coupling effect of γ-aminopropyltrimethoxysilane, methacrylic acid was graft-polymerized onto the surface of silica gel particles, obtaining the grafted particles PMAA/SiO2. Then, the molecular imprinting towards the grafted PMAA was performed with one enantiomer of tetramisole (TM), L-TM, as template molecule and ethylene glycol diglycidyl ether (EGDE) as crosslinking agent by using the novel surface-molecular imprinting technique established by our research group, and the L-TM molecule-imprinted material MIP-PMAA/SiO2 was prepared. With another enantiomer, D-TM, as a contrast compound, both static and dynamic methods were adopted to study the chiral recognition character and binding property of MIP-PMAA/SiO2 for L-TM and to examine its ability to separate the two enantiomers in racemate. The experiment results show that MIP-PMAA/SiO2 have specific recognition selectivity and excellent binding affinity for L-TM, and its selectivity coefficient for L-TM with respect to D-TM reaches 4.03, displaying fine ability to separate the two enantiomers. Besides, MIP-PMAA/SiO2 has excellent elution property, and with a diluted aqueous solution of NaOH as the eluent, the desorption ratio of L-TM reaches 99.08% in 20 BV.

Key words: polymethacrylic acid, silica Gel, surface-molecular imprinting, molecule recognition, tetramisole, chiral separation

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