三唑酮分子印迹纳米球的制备及应用

doi:10.16085/j.issn.1000-6613.2019-1538

摘要/Abstract

摘要：

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。

关键词: 分子印迹聚合物, 固相萃取, 吸附, 分子模拟, 纳米粒子, 三唑类杀菌剂

Abstract:

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-UPLC-MS/MS method provided a multi-residue analytical platform that can meet the requirements for simultaneous detection of trace triazole fungicides in tobacco leaves.

Key words: molecularly imprinted polymers, solid phase extraction, adsorption, molecular simulation, nanoparticles, triazole fungicide

中图分类号:

O658

李子怡, 李志君, 顾丽莉, 师君丽, 陈昱安, 韩毅, 佟振浩, 孔光辉. 三唑酮分子印迹纳米球的制备及应用[J]. 化工进展, 2020, 39(7): 2706-2714.

Ziyi LI, Zhijun LI, Lili GU, Junli SHI, Yu’an CHEN, Yi HAN, Zhenhao TONG, Guanghui KONG. Preparation and application of triazolone molecularlyimprinted nano-spheres[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2706-2714.

参考文献

1	胡艳云, 徐慧群, 姚剑, 等. 分子印迹固相萃取-液相色谱-质谱法测定果蔬中20种三唑类农药残留[J]. 分析化学, 2014, 42(2): 227-232.
1	HU Yanyun, XU Huiqun, YAO Jian, et al. Selective detection of 20 triazoles residues in food uusing molecularly imprinted solid phase extraction coupled with liquid chromatography tandem mass spectrometry[J]. Chinese J. Anal. Chem., 2014, 42(2): 227-232.
2	杨益军. 全球(中国)农药市场的现状及趋势分析[J]. 今日农药, 2017(10): 31-35.
2	YANG Yijun. Status and trend analysis of global pesticide market[J]. Agrochemicals Today, 2017(10): 31-35.
3	FARAJZADEH M A, MOGADDAM M R A, GHORBANPOUR H. Development of a new microextraction method based on elevated temperature dispersive liquid-liquid microextraction for determination of triazole pesticides residues in honey by gas chromatography-nitrogen phosphorus detection[J]. Journal of Chromatography A, 2014, 1347: 8-16.
4	沈伟健, 桂茜雯, 余可垚, 等. 气相色谱-负化学离子源质谱测定大豆和玉米中12种三唑类杀菌剂的残留量[J]. 色谱, 2009, 27(1): 91-95.
4	SHEN Weijian, GUI Qianwen, YU Keyao, et al. Determination of 12 azole fungicide residues in beans and corn by offline disperse solid phase extraction and gas chromatography-negative chemical ionization mass spectrometry[J]. Chinese Journal of Chromatography, 2009, 27(1): 91-95.
5	ZHAO F N, SHEN Y X, ZHANG C, et al. Selective solid-phase extraction based on molecularly imprinted technology for the simultaneous determination of 20 triazole pesticides in cucumber samples using high-performance liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography B: Analytical Technologies in the Biomedical & Life Sciences, 2017, 1064: 134-150.
6	LIU A F, SHEN Z S, TIAN Y, et al. Thin-layer chromatography coupled with high performance liquid chromatography fordetermining tetrabromobisphenol A/S and their derivatives in soils[J]. Journal of Chromatography A, 2017, 1526: 151-156.
7	王天顺, 范业赓, 杨玉霞, 等. 气相色谱-质谱法同时测定蔗汁中的莠去津与莠灭净残留量[J]. 分析测试学报, 2011, 30(10): 1153-1156.
7	WANG T S, FAN Y G, YANG Y X, et al. Simultaneous determination of atrazine and ametryn residues in sugarcane juice by gas chromatography-mass spectrometry[J]. Journal of Instrumental Analysis, 2011, 30(10): 1153-1156.
8	李继革, 王玉飞, 施家威, 等. 固相萃取-气相色谱-串联质谱法测定水果中11种三唑类杀菌剂[J]. 色谱, 2012, 30(3): 262-266.
8	LI Jige, WANG Yufei, SHI Jiawei, et al. Determination of 11 triazole fungicides in fruits using solid phase extraction and gas chromatographytandem mass spectrometry[J]. Chinese Journal of Chromatography, 2012, 30(3): 262-266.
9	王菲, 李彤, 马辰. 超高效液相色谱-串联质谱法测定中药材中三唑类杀菌剂及三嗪类除草剂的残留量[J]. 色谱, 2013, 31(3): 191-199.
9	WANG Fei, LI Tong, MA Chen. Determination of triazole fungicide and triazine herbicide residues in Chinese herbs by ultra-performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2013, 31(3): 191-199.
10	ANDREU V, PICó Y. Determination of currently used pesticides in biota[J]. Analytical & Bioanalytical Chemistry, 2012, 404 (9): 2659-2681.
11	ALATAWI R A S, MONIER M, ELSAYED N H. Chiral separation of (+/-)-methamphetamine racemate using molecularly imprinted sulfonic acidfunctionalized resin[J]. Journal of Colloid and Interface Science, 2018, 531: 654-663.
12	HU Mailing, JIANG Ming, WANG Peng, et al. Selective solid-phase extraction of tebuconazole in biological and environmental samples using molecularly imprinted polymers[J]. Analytical & Bioanalytical Chemistry, 2007, 387(3): 1007-1016.
13	佘永新, 王静, 赵风年, 等. 三唑类农药分子印迹聚合物微球固相萃取柱及其应用: CN106317325A[P]. 2017-01-11.
13	SHE Yongxin, WANG Jing, ZHAO Fengnian,et al. Triazole pesticide molecularly imprinted polymer microspheres, solid phase extraction column and its application: CN106317325A[P]. 2017-01-11.
14	LI Z G, WANG J J, CHEN X, et al. A novel molecularly imprinted polymer-solid phase extraction method coupled with high performance liquid chromatography tandem mass spectrometry for the determination of nitrosamines in water and beverage samples[J]. Food Chemistry, 2019, 292: 267-274.
15	HAN Y, GU L L, ZHANG M X, et al. Computer-aided design of molecularly imprinted polymers for recognition of atrazine[J]. Computational and Theoretical Chemistry， 2017, 1121: 29-34.
16	SIOMON S, DURAN M, DANNENBERG J J. How does basis set superposition error change the potential surfaces for hydrogen-bonded dimers?[J]. Journal of Chemical Physics, 1996, 105(24): 11024-11031.
17	姚伟, 高志贤, 房彦军, 等. 沉淀聚合法制备咖啡因分子印迹聚合物微球[J]. 化工进展, 2007, 26(6): 120-123, 128.
17	YAO Wei, GAO Zhixian, FANG Yanjun, et al. Preparation of homoharringtonine imprinted polymer by precipitation polymerization[J]. Chemical Industry and Engineering Progress, 2007, 26(6): 120-123, 128.
18	肖淑娟, 李红霞, 于守武. 分子印迹固相萃取法提取花生壳中木犀草素[J]. 化工进展, 2010, 29(2): 106-109.
18	XIAO Shujuan, LI Hongxiao, YU Shouwu. Solid-phase extraction of luteolin from peanut hull using molecular imprinted polymers[J]. Chemical Industry and Engineering Progress, 2010, 29(2): 106-109.
19	吴萍, 蔡爽, 郭建良, 等.三硝基甲苯分子印迹微球的制备与应用[J]. 化工进展, 2018, 37(2): 644-650.
19	WU Ping, CAI Shuang, GUO Jianliang, et al. Preparation and application of TNT molecularly imprinted microspheres[J]. Chemical Industry and Engineering Progress, 2018, 37(2): 644-650.
20	李辉, 符再德, 石慧, 等.沉淀聚合法制备高三尖杉酯碱印迹聚合物[J]. 化工进展, 2009, 28(10): 1787-1791.
20	LI Hui, FU Zaide, SHI Hui, et al. Preparation of homoharringtonine imprinted polymer by precipitation polymerization[J]. Chemical Industry and Engineering Progress, 2009, 28(10): 1787-1791.
21	程杏安, 叶静敏. 结晶紫分子印迹微球的合成及其性能[J]. 精细化工, 2019, 36(9): 1803-1808.
21	CHENG Xingan, YE Jingmin. Synthesis and properties of crystal violet molecularly imprinted polymer microspheres[J]. Fine Chemicals, 2019, 36(9): 1803-1808.
22	陈晓龙, 李耀, 阚建全. 花椒麻味物质分子印迹预组装体系的分子模拟与吸附性能[J]. 中国食品学报, 2019, 19(5): 82-90.
22	CHEN Xiaolong, LI Yao, KAN Jianquan. Molecular simulation and adsorption properties of the molecularly imprinted polymer of numb-taste components[J]. Journal of Chinese Institute of Food Science and Technology, 2019, 19(5): 82-90.
23	LASáKOVá M, JANDERA P. Molecularly imprinted polymers and their application in solid phase extraction[J]. Journal of Separation Science, 2015, 32(5/6): 799-812.
24	PARDESGI S, DHODAPKAR R, KUMAR A. Molecularly imprinted microspheres and nanoparticles prepared using precipitation polymerisation method for selective extraction of gallic acid from Emblica officinalis[J]. Food Chemistry, 2014, 146(1): 385-393.
25	LI Z B, LIU J, LIU J X, et al. Determination of sulfonamides in meat with dummy-template molecularly imprinted polymer-based chemiluminescence sensor[J]. Analytical and Bioanalytical Chemistry, 2019, 411(14): 3179-3189.
26	CAI Y, HE X, CUI P L, et al. Preparation of a chemiluminescence sensor for multi-detection of benzimidazoles in meat based on molecularly imprinted polymer[J]. Food Chemistry, 2019, 280: 103-109.
27	ZANUY D, FABREGAT G, FERREIRA C A, et al. A molecular dynamics study on glucose molecular recognition by a non-enzymatic selective sensor based on a conducting polymer[J]. Physical Chemistry Chemical Physics, 2019, 21: 8099-8107.
28	孙智纯, 王兵, 皇甫风云, 等. 香草醛分子印迹膜的制备及识别性能研究[J]. 高校化学工程学报, 2016(3): 661-667.
28	SUN Zhichun, WANG Bing, HUANGFU Fengyun, et al. Preparation and recognition properties of vanillin molecularly imprinted membranes[J]. Journal of Chemical Engineering of Chinese Universities, 2016(3): 661-667.
29	郑平, 姚剑, 徐业平. 分子印迹固相萃取技术及其在食品安全分析中的应用[M]. 合肥: 合肥工业大学出版社, 2011: 30-40.
29	ZHENG Ping, YAO Jian, XU Yeping. Development and application of molicular imprinting solid phase extraction technology for food safty analysis[M]. Hefei: Hefei University of Technology Press, 2011: 30-40.
30	刘维娟. 用于三唑类杀菌剂多残留同时测定的分子印迹固相萃取研究[D]. 天津: 南开大学, 2010.
30	LIU Weijuan. Determination of triazole fungicides by molecularly imprinted solid-phase extraction[D]. Tianjin: Nankai University, 2010.

[1]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[2]	张祚群, 高扬, 白超杰, 薛立新. 二次界面聚合同步反扩散原位生长ZIF-8纳米粒子制备聚酰胺混合基质反渗透（RO）膜[J]. 化工进展, 2023, 42(S1): 364-373.
[3]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[4]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[5]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[6]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[7]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[8]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[9]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[10]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[11]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.
[12]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[13]	欧阳素芳, 周道伟, 黄伟, 贾凤. 新型耐迁移橡胶防老剂的研究进展[J]. 化工进展, 2023, 42(7): 3708-3719.
[14]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.
[15]	白亚迪, 邓帅, 赵睿恺, 赵力, 杨英霞. 变温吸附碳捕集机组标准化测试方案探讨及性能实验[J]. 化工进展, 2023, 42(7): 3834-3846.