Zong Hai-Yan, Liu Xiao, Liu Zhao-Sheng, Huang Yan-Ping
Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics (Theranostics), School of Pharmacy, Tianjin Medical University, Tianjin, China.
Electrophoresis. 2015 Mar;36(5):818-24. doi: 10.1002/elps.201400382. Epub 2015 Feb 4.
Molecular crowding is a new approach to stabilizing binding sites and improving molecular recognition. In this work, the concept was applied to the preparation of imprinted monolithic columns for CEC. The imprinted monolithic column was synthesized using a mixture of d-zopiclone (d-ZOP)(template), methacrylic acid, ethylene glycol dimethacrylate, and poly(methyl methacrylate) (PMMA) (molecular crowding agent). The resulting PMMA-based imprinted capillary was able to separate ZOP enantiomers in CEC mode. The resolution of enantiomer separation achieved on the d-ZOP-imprinted monolithic column was up to 2.09. Some polymerization factors, such as template-monomer molar ratio, functional monomer-cross-linker molar ratio and the composition of the porogen, on the imprinting effect of resulting molecularly imprinted polymer (MIP) monolithic column were systematically investigated. Chromatographic parameters, including pH values, the content of acetonitrile and the salt concentration on chiral separation were also studied. The results indicated the addition of PMMA resulted in MIPs with superior retention properties and excellent selectivity for d-ZOP, as compared to the MIPs prepared without addition of the crowding-inducing agent. The results revealed that molecular crowding is an effective method for the preparation of a highly efficient MIP stationary phase for chiral separation in CEC.
分子拥挤是一种稳定结合位点和改善分子识别的新方法。在本工作中，该概念被应用于制备用于毛细管电色谱（CEC）的印迹整体柱。使用右佐匹克隆（d-ZOP）（模板）、甲基丙烯酸、乙二醇二甲基丙烯酸酯和聚甲基丙烯酸甲酯（PMMA）（分子拥挤剂）的混合物合成了印迹整体柱。所得基于PMMA的印迹毛细管能够在CEC模式下分离佐匹克隆对映体。在d-ZOP印迹整体柱上实现的对映体分离分辨率高达2.09。系统研究了一些聚合因素，如模板-单体摩尔比、功能单体-交联剂摩尔比和成孔剂组成对所得分子印迹聚合物（MIP）整体柱印迹效果的影响。还研究了色谱参数，包括pH值、乙腈含量和盐浓度对手性分离的影响。结果表明，与未添加拥挤诱导剂制备的MIP相比，添加PMMA导致MIP对d-ZOP具有优异的保留性能和出色的选择性。结果表明，分子拥挤是制备用于CEC手性分离的高效MIP固定相的有效方法。
