三唑酮分子印迹纳米球的制备及应用

Preparation and application of triazolone molecularly imprinted nano-spheres

建立了烟叶中8种三唑类杀菌剂残留的分子印迹固相萃取-超高效液相色谱-串联质谱(MISPE-UPLC-MS/MS)检测方法。实验中,运用计算机模拟技术筛选最佳功能单体及溶剂,并确定最优聚合反应配比,估算了TDF-MAA的自组装过程与红外光谱图,热力学分析表明TDF-MAA自组装为吸热非自发过程,预聚合反应温度拟定为30℃;采用沉淀聚合法制备了三唑酮分子印迹聚合物纳米颗粒,颗粒粒径分布均匀,平均粒径为200nm;该纳米颗粒对模板分子及其结构类似物具有良好的特异性吸附能力,针对模板分子的分离印迹因子达到2.42;将加标烟叶样品经该纳米颗粒组装的固相萃取柱进行前处理,用UPLC-MS/MS分析前处理液,烟叶中8种三唑类杀菌剂的固相萃取回收率为70.14%~105.43%,检出限为4.82~11.97ng/mL,相对标准偏差(RSD)为0.26%~2.27%(n=6),实现了复杂基质烟叶中多种三唑类杀菌剂的同时检测。

A molecularly imprinted solid phase extraction-ultraviolet high performance liquid chromatography-tandem mass spectrometry(MISPE-UPLC-MS/MS)method was developed for the determination of eight triazole fungicide residues in tobacco leaves.Firstly,computer simulation technology was used to evaluate the interaction energies of the complex formed by the triazolone template molecule with five different functional monomers based on the optimize configuration of each monomer respectively.Triazolone and functional monomer complexes were put into five solutions with different polarity to calculate the solvation energy,and the results were verified through experiments to select the best solvent.The self-assembly process and infrared spectrum of TDF-MAA were estimated by computer.The theoretical analysis showed that TDF-MAA self-assembled was an endothermic non-spontaneous process,and the prepolymerization temperature was determined to be 30℃.The results provided key messages to select the suitable monomers and reaction ratios.Then,triazolone molecularly imprinted spheres were prepared by precipitation polymerization.Finally,the molecularly imprinted spheres were pretreated as a solid phase extraction filler and combined with solid phase extraction technology to be applied in the detection of triazole fungicides in tobacco samples,and a new detection method for triazole fungicides was established.The results showed that the prepared molecularly imprinted spheres had uniform particle size distribution and average particle size of 200nm.The nanospheres had good specific adsorption capacity for template molecules and their structural analogs,and the molecular imprinting factor for template was not less than 2.42.The recovery range for the eight triazole fungicides in spiked tobacco samples was 70.14%-105.43%,and the detection limit was 4.82-11.97ng/mL.The relative standard deviation(RSD)was 0.26%-2.27%(n=6).With its unique advantages,the MIPs-SPE-UPLCMS/MS method provided a multi-residue analytical platform that can meet the requirements for simultaneous detection of trace triazole fungicides in tobacco leaves.