计算机模拟辅助特丁津分子印迹聚合物的制备及应用

doi:10.16085/j.issn.1000-6613.2022-1404

摘要/Abstract

摘要：

建立了烟叶中两种三嗪类除草剂残留的分子印迹固相萃取-高效液相色谱（MISPE-HPLC）检测方法。利用计算机模拟技术筛选最佳功能单体，确定模板（TER）与单体（AA）的最优结合比例，以模拟结果为依据，采用沉淀聚合制备了特丁津分子印迹聚合物。对比了计算机模拟复合物与实验制备的TER-MIPs红外光谱图，分析表明，两者的主要吸收基团出峰位置一致。考察了MIPs对模板分子的吸附性能，结果显示，MIPs对TER及其结构类似物具有良好的特异性吸附能力。将TER-MIPs作为固相萃取填料，制备TER-MISPE柱对加标烟叶进行前处理，用高效液相色谱（HPLC）分析前处理液。结果表明，MISPE对特丁津及特丁通的富集效果较好，两种三嗪类除草剂的回收率为84.29%~96.64%，RSD为1.19%~1.70%（n=3），该方法满足烟叶中特丁津及特丁通两种三嗪类农药残留的同时检测，为烟叶及复杂基质农作物中三嗪类除草剂的分析检测提供了支撑。

关键词: 特丁津, 分子模拟, 聚合物, 吸附, 农药残留

Abstract:

A method of molecularly imprinted solid phase extraction combined with high performance liquid chromatography (MISPE-HPLC) was developed for the determination of two triazine herbicide residues in tobacco leaves. An optimal functional monomer was firstly selected and then the optimum polymerization ratio of the template molecule (TER) to the functional monomer (AA) was determined by computer simulation technology. Based on the simulation results, the molecularly imprinted polymers of terbutylazine were prepared by precipitation polymerization. Comparing the infrared spectra of the computer-simulated complex with the experimentally prepared TER-MIPs, the analysis showed that the main absorbing groups of them had the same peak positions. The adsorption performances of MIPs to the template molecule and its structural analogs were investigated. It was found that MIPs had good specific adsorption capacities for TER and its structural analogs. TER-MIPs was used as a solid phase extraction filler to prepare a TER-MISPE column for pretreatment of spiked tobacco leaves and the samples were analyzed by HPLC. The results indicated that MISPE had better enrichment effect on terbutylazine and terbumeton. The average recoveries of the two triazine herbicides were between 84.29% and 96.64% and the relative standard deviations (RSD) were 1.19%—1.70% (n=3). The method can meet the requirements of simultaneous determination of terbutylazine and terbumeton triazine pesticide residues in tobacco leaves, providing support for the analysis and detection of triazine herbicides in tobacco leaves and crops with complex substrates.

Key words: terbutylazine, molecular simulation, polymers, adsorption, pesticide residues

中图分类号:

O657.7

杨发容, 顾丽莉, 刘洋, 李伟雪, 蔡洁云, 王惠平. 计算机模拟辅助特丁津分子印迹聚合物的制备及应用[J]. 化工进展, 2023, 42(6): 3157-3166.

YANG Farong, GU Lili, LIU Yang, LI Weixue, CAI Jieyun, WANG Huiping. Preparation and application of molecularly imprinted polymers of terbutylazine assisted by computer simulation[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3157-3166.

图/表 17

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模板/单体	质子供体	所在位置	质子受体	所在位置	氢键数目
TER	H25、H28	亚氨基	N4、N6	三嗪环	4
AA	H9	羧基	O1、O2	羧基	3
MAA	H12	羧基	O1、O2	羧基	3
AM	H8	氨基	O1	羰基	2
4-VP	—	—	N1	吡啶环	1
2-VP	—	—	N8	吡啶环	1
MMA	—	—	O4	羰基	1
4-VYL	H19	羧基	O2	羧基	2

模板/单体	质子供体	所在位置	质子受体	所在位置	氢键数目
TER	H25、H28	亚氨基	N4、N6	三嗪环	4
AA	H9	羧基	O1、O2	羧基	3
MAA	H12	羧基	O1、O2	羧基	3
AM	H8	氨基	O1	羰基	2
4-VP	—	—	N1	吡啶环	1
2-VP	—	—	N8	吡啶环	1
MMA	—	—	O4	羰基	1
4-VYL	H19	羧基	O2	羧基	2

复合物	结合能/kJ·mol^-1	氢键数目	模板与单体结合比例
TER-AA	124.833	3	1∶3
TER-2VP	38.265	1	1∶1
TER-4VP	77.533	2	1∶2
TER-4VYL	83.981	2	1∶2
TER-AM	57.656	1	1∶1
TER-MAA	53.167	1	1∶1
TER-MMA	60.711	2	1∶2

复合物	结合能/kJ·mol^-1	氢键数目	模板与单体结合比例
TER-AA	124.833	3	1∶3
TER-2VP	38.265	1	1∶1
TER-4VP	77.533	2	1∶2
TER-4VYL	83.981	2	1∶2
TER-AM	57.656	1	1∶1
TER-MAA	53.167	1	1∶1
TER-MMA	60.711	2	1∶2

亲和位点类型	拟合参数	TER-MIPs
高亲和位点	Scatchard模型方程	y=-0.00924x+0.05551
	相关系数（R²）	0.99992
	K/µg·mL^-1	108.23
	Q_max/µg·mg^-1	6.01
低亲和位点	Scatchard模型方程	y=-0.00184x+0.04593
	相关系数（R²）	0.69822
	K/µg·mL^-1	543.47
	Q_max/µg·mg^-1	24.96