Laboratory of Bioanalytical Chemistry, Department of Chemistry, University of Torino, 10125 Torino, Italy.
J Mol Recognit. 2012 Jun;25(6):377-82. doi: 10.1002/jmr.2186.
Molecularly imprinted polymers have been successfully used as selective stationary phases in capillary electrophoresis. Notwithstanding, this technique suffers from several drawbacks as the loss of molecular recognition properties in aqueous media and the lack of feasibility for imprinted systems directed towards highly polar templates soluble in aqueous environments only. Thus, the preparation of imprinted polymers for highly polar, water-soluble analytes, represents a challenge. In this work, we present an innovative approach to overcome these drawbacks. It is based on a surface molecular imprinting technique that uses preformed macromonomers as both functional recognition elements and cross-linking agents. A poly-2-hydroxyethyl-co-methacrylic acid linear polymer was grafted from the surface of silica capillaries. The grafted polymer was exhaustively esterified with methacrylic anhydride to obtain polyethylendimethacrylate-co-methacrylic acid linear chains. Then, as a proof of concept, an adequate amount of a very polar template like penicillin V was added in a hydro-organic mixture, and a thin layer of imprinted polymer was obtained by cross-linking the polymer linear chains. The binding behaviour of the imprinted and non-imprinted capillaries was evaluated in different separation conditions in order to assess the presence of template selectivity and molecular recognition effects. The experimental results clearly show that this innovative kind of imprinted material can be easily obtained in very polar polymerization environments and that it is characterized by enhanced molecular recognition properties in aqueous buffers and good selectivity towards the template and strictly related molecules.
分子印迹聚合物已成功地用作毛细管电泳中的选择性固定相。尽管如此,该技术仍存在一些缺点,例如在水介质中丧失分子识别性能,以及对于仅在水环境中可溶的高极性模板的印迹系统缺乏可行性。因此,制备用于高极性、水溶性分析物的印迹聚合物是一个挑战。在这项工作中,我们提出了一种克服这些缺点的创新方法。它基于一种表面分子印迹技术,该技术使用预形成的大分子单体作为功能识别元件和交联剂。将聚-2-羟乙基-co-甲基丙烯酸线性聚合物从硅胶毛细管表面接枝。接枝聚合物与甲基丙烯酰酐进行了充分酯化反应,得到聚乙二甲基丙烯酸-co-甲基丙烯酸线性链。然后,作为概念验证,在水-有机混合物中加入适量的非常极性的模板(如青霉素 V),通过交联聚合物线性链,获得一层薄薄的印迹聚合物。在不同的分离条件下评估印迹和非印迹毛细管的结合行为,以评估模板选择性和分子识别效应的存在。实验结果清楚地表明,这种创新型印迹材料可以在非常极性的聚合环境中轻松获得,并且具有增强的在水缓冲液中的分子识别性能以及对模板和严格相关分子的良好选择性。