戊唑醇-三唑酮双模板分子印迹聚合物在烟叶农残检测中的应用

doi:10.16085/j.issn.1000-6613.2022-0086

摘要/Abstract

摘要：

以戊唑醇（TBZ）和三唑酮（TDF）为双模板分子，甲基丙烯酸（MAA）为功能单体，乙二醇二甲基丙烯酸酯（EGDMA）为交联剂，按摩尔比为1∶4∶20制备了戊唑醇-三唑酮双模板分子印迹聚合物（MIPs）。考察了MIPs的吸附动力学、静态吸附及亲和位点特征和选择识别性能。结果表明，MIPs可在2.5h内达到吸附平衡，Scatchard分析得出MIPs存在高低两类亲和位点，且具有良好的组选择性和特异选择性。以MIPs作为固相萃取填料，制备分子印迹固相萃取柱（MISPE）用于烟叶样品前处理，并建立MISPE-超高效液相色谱-串联质谱法检测烟叶中（戊唑醇、三唑酮、腈菌唑和三唑醇）残留的方法。结果显示，MISPE柱对戊唑醇、三唑酮、腈菌唑和三唑醇的富集效果较好，平均回收率为72%~110.3%，相对标准偏差在2.38%~7.92%（n=3）。该方法简单、选择性高，可实现对烟叶中三唑类杀菌剂残留的准确分析。

关键词: 戊唑醇, 三唑酮, 双模板, 分子印迹聚合物, 固相萃取, 农药残留, 吸附

Abstract:

A bi-templates molecularly imprinted polymers (MIPs) was prepared by using tebuconazole (TBZ) and triadimefon (TDF) as co-templates, methacrylic acid (MAA) as the functional monomer, and ethylene glycol dimethacrylate (EGDMA) as the crosslinker with the molar ratio of templates to MAA and EGDMA of 1∶4∶20. The adsorption kinetics, static adsorption, and affinity site characteristics and selectivity of the MIPs were investigated. The results showed that the adsorption equilibrium of dynamic adsorption was reached within 2.5 hours, implying a rapid adsorption kinetics. Scatchard analysis indicated that there were two types of affinity sites in the MIPs, and the MIPs had a good group and specific selectivity for triazole fungicides. A molecularly imprinted solid phase extraction column (MISPE) was prepared with the MIPs as fillers for tobacco sample pretreatment, and MISPE-ultra-high performance liquid chromatography-tandem mass spectrometry method was established for detecting residues of tebuconazole, triadimefon, myclobutanol and triadimenol in tobacco leaves. The results showed that the MISPE column had good enrichment effect on tebuconazole, triadimefon, myclobutanol and triadimenol. The average recoveries were between 72% and 110.3%, and the relative standard deviations (RSD) were 2.38%—7.92%, (n=3). The method can easily and selectively realize accurate analysis of triazole fungicides residues in tobacco leaves.

Key words: tebuconazole, triadimefon, bi-template, molecularly imprinted polymer, solid phase extraction, pesticide residue, adsorption

中图分类号:

O657.7

景联鹏, 顾丽莉, 师君丽, 李增良, 杨发容, 李国栋. 戊唑醇-三唑酮双模板分子印迹聚合物在烟叶农残检测中的应用[J]. 化工进展, 2022, 41(11): 6029-6037.

JING Lianpeng, GU Lili, SHI Junli, LI Zengliang, YANG Farong, LI Guodong. Application of tebuconazole-triadimefon bi-template molecularly imprinted polymer for detection of pesticide residues in tobacco leaves[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6029-6037.

图/表 15

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模板与单体	失电子位点	所在位置	得电子位点	所在位置	至多结合氢键数
TBZ	H38	三唑环	N5和O2	三唑环、羟基	3
AA	H9	羧基	O1和O2	羧基	3
AM	H7和H8	氨基	O1	羰基	3
MAA	H12	羧基	O1和O2	羧基	3
TFMAA	H12	羧基	O4和O5	羧基	3

模板与单体	失电子位点	所在位置	得电子位点	所在位置	至多结合氢键数
TBZ	H38	三唑环	N5和O2	三唑环、羟基	3
AA	H9	羧基	O1和O2	羧基	3
AM	H7和H8	氨基	O1	羰基	3
MAA	H12	羧基	O1和O2	羧基	3
TFMAA	H12	羧基	O4和O5	羧基	3

复合物	结合能/kJ·mol^-1	氢键数目	模板与单体印迹比例
TBZ-AA	136.805	3	1∶3
TBZ-AM	65.177	2	1∶2
TBZ-MAA	139.237	3	1∶3
TBZ-TFMAA	56.511	1	1∶1

复合物	结合能/kJ·mol^-1	氢键数目	模板与单体印迹比例
TBZ-AA	136.805	3	1∶3
TBZ-AM	65.177	2	1∶2
TBZ-MAA	139.237	3	1∶3
TBZ-TFMAA	56.511	1	1∶1

亲和位点类型	拟合参数	TBZ	TDF
低亲和位点	Scatchard模型方程	y=-0.01187x+0.153	y=-0.01457x+0.15069
	相关系数（R² ）	0.9126	0.9821
	K/mg·L^-1	84.246	68.63
	Q_max/mg·g^-1	12.89	10.34
高亲和位点	Scatchard模型方程	y=-0.09883x+0.36277	y=-0.10042x+0.57355
	相关系数（R² ）	0.7512	0.9827
	K/mg·L^-1	10.118	9.958
	Q_max/mg·g^-1	3.67	5.71