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化学学报
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化学学报 ›› 2012, Vol. 70 ›› Issue (12): 1355-1361.DOI: 10.6023/A1202023 上一篇    下一篇

研究论文

基于原子转移自由基聚合和“Click”化学方法制备手性色谱固定相

王怀松a,b, 彭江涛b,c, 魏纪平b, 姜安b,c   

  1. a 南京大学化学化工学院 南京 210093;
    b 江苏省质量安全工程研究院 南京 210046;
    c 南京财经大学管理科学与工程学院 南京 210046
  • 投稿日期:2012-02-23 修回日期:2012-04-23 发布日期:2012-04-20
  • 通讯作者: 姜安 E-mail:wanghuaiso@yahoo.com.cn

Synthesis of Novel Chiral Stationary Phase Based on Atom Transfer Radical Polymerization and Click Chemistry

Wang Huaisonga,b, Peng Jiangtaob,c, Wei Jipingb, Jiang Anb,c   

  1. a School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093;
    b Jiangsu Province Institute of Quality & Safety Engineering, Nanjing 210046;
    c School of Management Science & Industrial Engineering, Nanjing University of Finance & Economics, Nanjing 210046
  • Received:2012-02-23 Revised:2012-04-23 Published:2012-04-20

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应用原子转移自由基聚合(ATRP)法和“Click”化学方法, 以含叠氮基的烯类化合物为单体, 在硅胶表面引发聚合, 制备了“梳状”手性固定相. 该固定相的合成采用“接出”方法接枝聚合物链, 使接枝层更为均匀, 并且避免了传统合成方法(如物理吸附等)稳定性差的缺点. 所得到的“梳状”手性固定相实现了对一些手性药物的分离; 并考察了该固定相中聚合物链的密度和长度对其手性分离能力的影响.

关键词: 手性固定相, 原子转移自由基聚合, β-CD, “Click”化学

A novel chiral stationary phase was synthesized via the combination of atom transfer radical polymerization (ATRP) and click chemistry. In the synthesis, the silane coupling agent 3-(2-bromoisobutyryl)- propyl triethoxysilane (BPE) was chosen as the ATRP initiator and immobized on the porous silica gel. The polymer chains of poly(2-methyl-3-butyn-2-ol methacrylate) (pMBMA) were grafted on the silica substrates by surface-initiated ATRP. This “grafting-from” technique was used to synthesize polymers with controllable molecular weight and narrow molecular weight distributions. For immobilizing the chiral selector, azide-modified β-cyclodextrin (β-CD) was synthesized and bounded on the pMBMA by click chemistry, which can avoid the side-reactions in the preparation. The materials with different pMBMA chain density and length on the silica gel surface were prepared. Several pharmaceuticals were used to evaluate the enantioseparation ability of the materials under reversed-phase high performance liquid chromatography. The results demonstrate that ATRP can well design the polymer structure, and click chemistry can provide an effective route in the β-CD immobilization for chiral discrimination. It was found that the retention and separation factors of chiral compounds could be improved by adjusting the pMBMA chain density and length on the surface of silica gel.

Key words: chiral stationary phase, atom transfer radical polymerization (ATRP), β-cyclodextrin (β-CD), click chemistry