基于金属卟啉的分子印迹聚合物的合成及其对三唑类杀菌剂识别性能研究

SYNTHESIS OF METALLOPORPHYRIN-BASED MOLECULARLY IMPRINTED POLYMER AND ITS RECOGNITION PROPERTIES FOR TRIAZOLE FUNGICIDES

以三唑类杀菌剂氟环唑为印迹分子,5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基卟啉锌为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了新型的基于金属卟啉的分子印迹聚合物.紫外-可见光谱研究表明印迹分子与功能单体在聚合前形成1∶1配合物.通过选择性吸附和固相萃取表征研究了该印迹聚合物对氟环唑及具有类似化学结构的三唑类杀菌剂的识别能力,并与非印迹聚合物进行了比较,结果表明印迹聚合物具有良好的特异性识别性能,同时,印迹聚合物的交联度及吸附溶剂的极性对印迹效果有着显著影响.

A novel kind of metalloporphyrin-based molecularly imprinted polymers was prepared to epoxiconzole, a triazole fungicide template, using 5- （4-methacryloxyphenyl）- 10, 15,20-triphenylporphinatozinc （ Ⅱ ） as the functional monomer and ethylene glycol dimethaerylate as the cross-linker. The interaction between the functional monomer and the triazole fungicide template as well as four other triazole analogs was quantitatively investigated with UV-visible titration spectroscopy, which reveals the formation of 1 ： 1 complex in the system. The interaction was attributed to the coordination between the central zinc ion of the porphyrin and triazole ring in the fungicide. Selective rebinding and solid phase extraction measurements were used to characterize the recognition properties of the obtained polymer. It was found that the metalloporphyrin-based molecularly imprinted polymer exhibited specific affinity to the template molecule in comparison with other triazole fungicide analogs. The effect of polymer crosslinking degree on the molecular recognition properties was investigated, showing the specific affinity was enhanced with a certain extent of cross-linking. It was noted that the rebinding properties of the molecularly imprinted polymer was greatly influenced by the polarity of the binding solvent. The rebinding amount of the triazole fungicide in dichloromethane was determined to be about ten times of that in methanol.