计算机模拟辅助三唑醇分子印迹聚合物的制备及应用

Computer simulation assisted preparation and application of triadimenol molecularly imprinted polymer

运用计算机模拟技术对三唑醇(TDM)分子印迹体系进行优化设计,确定出最优功能单体为甲基丙烯酸(MAA),且TDM与MAA结合摩尔比例为1∶3。通过热力学分析表明TDM-MAA自组装过程是非自发吸热反应,预聚合反应的适宜温度为30℃。基于计算机模拟结果,采用沉淀聚合法制备了粒径分布均一、比表面积大的三唑醇分子印迹聚合物纳米微球(TDM-MIPs);TDM-MIPs对TDM及其结构类似物具有良好的吸附性能。以TDM-MIPs为填充料,制备分子印迹固相萃取柱(MISPE)对加标烟叶样品进行前处理,采用超高效液相色谱-串联质谱(UPLC-MS/MS)检测,烟叶中4种三唑类杀菌剂的平均回收率为88.3%~100.68%,相对标准偏差为2.9%~9.3%。建立了TDM-MISPE-UPLC-MS/MS法同时检测烟叶中痕量TDM、三唑酮、腈菌唑和戊唑醇。

The computer simulation technology was used to design the pre-polymerization system of triadimenol(TDM)molecular imprinted polymer. The optimum functional monomer was methacrylic acid(MAA)and the molar ratio of TDM to MAA(TDM-MAA)was determined as 1∶3 during pre-polymerization. The thermodynamic analysis showed that TDM-MAA self-assembly was a non-spontaneous endothermic reaction process,and the suitable pre-polymerization reaction temperature was 30℃. Based on the results of the computer simulation,the triadimenol molecularly imprinted polymer nanoparticles(TDM-MIPs)with uniform particle size distributions and large specific surface area were prepared by precipitation polymerization,TDM-MIPs displayed adsorption performance for TDM and its structural analogues. Then the molecularly imprinted polymer was used as solid phase extraction filler to prepare molecular imprinted solid phase extraction(MISPE)column for pre-treatment of tobacco leave samples. Ultra-high performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS)method was used to detect and analyze the pre-treatment liquid of tobacco leaves,and the average recovery rates of four triazole fungicides were 88.3%-100.68% and the relative standard deviations(RSDs)were 2.9%-9.3%. The method of TDM-MISPE-UPLC-MS/MS was established to detect trace triadimenol,triadimefon,myclobutanil and tebuconazole in tobacco leaves simultaneously.