Qu Guorun, Zheng Sulian, Liu Yumin, Xie Wei, Wu Aibo, Zhang Dabing
Medical School, Southeast University, 87 Dingjiaqiao Road, Nanjing 210009, Jiangsu Province, PR China.
J Chromatogr B Analyt Technol Biomed Life Sci. 2009 Oct 1;877(27):3187-93. doi: 10.1016/j.jchromb.2009.08.012. Epub 2009 Aug 18.
Molecularly imprinted polymers (MIPs) prepared in water-containing systems are more appropriate as adsorption materials in analyte extraction from biological samples. However, water as a polar solvent involved in the synthesis of MIPs frequently disrupts non-covalent interactions, and causes non-specific binding. In this study Fe(2+) was used as mediator to prepare MIPs, targeting tetracyclines (TCs) of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC), with TC as template molecule and methacrylic acid (MAA) as functional monomer. The subsequent binding assay indicated that Fe(2+) was responsible for substantially improved specific binding in recognition of TCs by decreasing the non-specific binding. Spectrophotometric analysis suggested the existence of the strong interactions among TC, metal ions and MAA in the mixture of methanol and water. Moreover, mass spectrometric measurements verified that Fe(2+) could bridge between TC and MAA to form a ternary complex of one TC, one Fe(2+) and four MAAs with a mass of 844.857. Furthermore, combined with molecularly imprinted solid-phase extraction (MISPE) for sample pretreatment, HPLC-UV analysis data revealed good performance of the obtained MIPs as adsorbents. The recoveries of TC, OTC and CTC in urine samples were 80.1-91.6%, 78.4-89.3% and 78.2-86.2%, respectively. This research strategy provides an example for preparation of desirable water-compatible MIPs extracting target drugs from aqueous samples by introducing metal ion as mediator into conventional polymerization system.
在含水体系中制备的分子印迹聚合物（MIPs）作为从生物样品中提取分析物的吸附材料更为合适。然而，水作为参与MIPs合成的极性溶剂，经常会破坏非共价相互作用，并导致非特异性结合。在本研究中，以Fe(2+)作为介质制备MIPs，以四环素（TC）、土霉素（OTC）和金霉素（CTC）的四环素类药物（TCs）为目标，以TC为模板分子，甲基丙烯酸（MAA）为功能单体。随后的结合试验表明，Fe(2+)通过降低非特异性结合，在识别TCs时显著提高了特异性结合。分光光度分析表明，在甲醇和水的混合物中，TC、金属离子和MAA之间存在强相互作用。此外，质谱测量证实，Fe(2+)可以在TC和MAA之间架桥，形成一种由一个TC、一个Fe(2+)和四个MAA组成的三元复合物，质量为844.857。此外，结合分子印迹固相萃取（MISPE）进行样品预处理，HPLC-UV分析数据显示，所制备的MIPs作为吸附剂具有良好的性能。尿样中TC、OTC和CTC的回收率分别为80.1-91.6%、78.4-89.3%和78.2-86.2%。本研究策略为通过将金属离子作为介质引入传统聚合体系，制备从水性样品中提取目标药物的理想水相容性MIPs提供了一个实例。
