Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics (Theranostics), School of Pharmacy, Tianjin Medical University, Tianjin, China.
J Chromatogr A. 2011 Dec 16;1218(50):9071-9. doi: 10.1016/j.chroma.2011.10.027. Epub 2011 Oct 19.
This report provided the first example of using pivot concept to prepare monolithic molecularly imprinted polymers (MIPs) with ketoprofen (KET) imprints, in which metal ions were employed as mediator between the functional monomer and the template to achieve higher fidelity of imprint. To solve metal ions in pre-polymerization system, a new ternary porogen of dimethyl sulfoxide-toluene-isooctane was developed for preparation of MIP monoliths with high porosity and good permeability. The effect of polymerization parameters such as the nature of metal ions, the ratio of template to metal ion and the degree of crosslinking, on the permeability, morphology and affinity of the metal ion mediated MIP monolith were studied. The experiments demonstrated that Ni(2+), Co(2+) and Zn(2+) can be applied as pivot to prepare KET-imprinted monolith. Relative to monolithic MIP without metal ions, all the ion-mediated macropore MIP monoliths showed enhanced permeability, capacity factor and selectivity factor. High permeability (1.06×10(-7)mm(2)) was obtained on the Co(2+)-mediated MIP monolith and great selectivity factor (3.84) was achieved on the Ni(2+)-mediated one. The stoichiometric displacement model was constructed to investigate the recognition mechanism of metal-ion mediated MIP. The results indicate that metal ion as pivot not only improves the affinity but also allows the fine-tuning on the macroporous structure of MIP monolith.
本报告提供了首例使用枢轴概念制备具有酮洛芬印迹的整体分子印迹聚合物（MIP）的实例，其中金属离子被用作功能单体和模板之间的媒介，以实现更高的印迹保真度。为了解决预聚合体系中的金属离子问题，开发了一种新的三元致孔剂二甲亚砜-甲苯-异辛烷，用于制备具有高孔隙率和良好渗透性的 MIP 整体柱。研究了聚合参数（如金属离子的性质、模板与金属离子的比例和交联度）对金属离子介导的 MIP 整体柱的渗透性、形态和亲和力的影响。实验表明，Ni(2+)、Co(2+)和 Zn(2+)可作为枢轴制备 KET 印迹整体柱。与不含金属离子的整体 MIP 相比，所有离子介导的大孔 MIP 整体柱均表现出增强的渗透性、容量因子和选择性因子。在 Co(2+)介导的 MIP 整体柱上获得了高渗透性（1.06×10(-7)mm(2))，在 Ni(2+)介导的 MIP 整体柱上获得了大的选择性因子（3.84）。构建了化学计量置换模型来研究金属离子介导的 MIP 的识别机制。结果表明，金属离子作为枢轴不仅提高了亲和力，而且还可以对 MIP 整体柱的大孔结构进行微调。
