三氟氯氰菊酯分子印迹电化学传感器的制备及性能研究与应用

doi:10.11944/j.issn.1000-0518.2019.08.180414

摘要/Abstract

摘要：

以三氟氯氰菊酯为模板分子,邻苯二胺和邻氨基苯酚为复合功能单体,通过电聚合法制备了能够特异识别模板分子及其结构类似物的分子印迹电化学传感器。采用循环伏安法和方波伏安法优化了制备和检测条件,对传感器的印迹效应和分析性能进行了研究,并建立了农产品中三氟氯氰菊酯农药残留的快速分析方法。在最佳条件下,三氟氯氰菊酯在1.0×10^-7~1.0×10^-5 mol/L浓度范围内线性关系良好,检出限(S/N=3)为3.0×10^-8 mol/L,样品加标平均回收率在84.8%~94.7%之间,相对标准偏差(RSD)为1.1%~4.8%(n=5)。该传感器对三氟氯氰菊酯以及结构类似物有良好的选择性、稳定性和重现性,而且操作简便、检测快速、灵敏、成本低,具有良好的应用前景。

关键词: 三氟氯氰菊酯, 分子印迹聚合物, 电化学传感器, 快速分析

Abstract:

A novel molecularly imprinted electrochemical sensor with specific recognition ability to template molecules and its structural analogs were prepared by electro-polymerization. Cyhalothrin was used as the template molecule and o-phenylenediamine and o-aminophenol as composite functional monomers. The imprinting effect and analytical performance of the sensor were characterized by cyclic voltammetry and square wave voltammetry. A rapid analysis method was established for determination of cyhalothrin residues in agricultural products. Under the optimal conditions, the linear relationship of cyhalothrin was good within the concentration range of 1.0×10^-7~1.0×10^-5 mol/L, and the detection limit(S/N=3) was 3.0×10^-8 mol/L, the average recoveries of spiked sample were between 84.8% and 94.7%, and the relative standard deviations(RSDs) were 1.1%~4.8%(n=5). This sensor has advantages of simple operation, detection speediness, high sensitivity, low cost, good selectivity, stability and reproducibility, which provides it a good application prospect.

Key words: cyhalothrin, molecular imprinting polymer, electrochemical sensor, rapid analysis

秦思楠, 唐录华, 高文惠. 三氟氯氰菊酯分子印迹电化学传感器的制备及性能研究与应用[J]. 应用化学, 2019, 36(8): 958-967.

QIN Sinan, TANG Luhua, GAO Wenhui. Cyhalothrin Molecularly Imprinted Electrochemical Sensor:Preparation, Performance and Application[J]. Chinese Journal of Applied Chemistry, 2019, 36(8): 958-967.

参考文献

[1]	CHEN Linglong.Residues and Environmental Behavior of Lambda-Cyhalothrin in Tea and Soil[D]. Changsha:Hunan Normal University,2011(in Chinese). 陈玲珑. 高效氯氟氰菊酯在茶叶和土壤中的残留及环境行为研究[D]. 长沙:湖南师范大学,2011.
[2]	YU Chun,LI Jun,YANG Guanghong, et al. Acute Toxicity Study of 2.5% Lambda-Cyhalothrin Emulsion[J]. Guizhou Med J,2013,37(1):66-68(in Chinese). 于春,李军,杨光红,等. 2.5%高效氯氟氰菊酯水乳剂的急性毒性研究[J]. 贵州医药,2013,37(1):66-68.
[3]	Maund S J,Hamer J,Warinton J S, et al. Aquatic Ecotoxicology of the Pyrethroid Insecticide Lambda-Cyhalothrin:Considerations for Higher-Tier Aquatic Risk Assessment[J]. Pest Manage Sci,2015,54(4):408-417.
[4]	GAO Jingpeng,CHEN Hanming,MA Yajun.Establishment of Diagnostic Doses of Three Pyrethroid Insecticides for Detecting Resistance in Aedes albopictus(Diptera:Culicidae) in China[J]. Acta Entomol Sin,2018,61(1):18-24(in Chinese). 高景鹏,陈翰明,马雅军. 我国白纹伊蚊对三种拟除虫菊酯类杀虫剂抗性检测诊断剂量的建立[J]. 昆虫学报,2018,61(1):18-24.
[5]	Daniel B K N,Norbert N T,Francis N,et al. Ecotoxicological Effects of Imidacloprid and Lambda-Cyhalothrin(Insecticide) on Tadpoles of the African Common Toad, Amietophrynus regularis(Reuss, 1833)(Amphibia:Bufonidae)[J]. Ital J Sci Eng,2017,1(2):49-53.
[6]	Rodrigues E N L,Mendonca Jr M D S M,Fritz L L,et al. Effect of the Insecticide Lambda-Cyhalothrin on Rice Spider Populations in Southern Brazil[J]. Zoologia,2013,30(6):615-622.
[7]	Boonchiangma S,Ngeontae W,Srijaranai S.Determination of Six Pyrethroid Insecticides in Fruit Juice Samples Using Dispersive Liquid-Liquid Microextraction Combined with High Performance Liquid Chromatography[J]. Talanta,2012,88(15):209-215.
[8]	Jiang C,Sun Y,Yu X, et al. Liquid-Solid Extraction Coupled with Magnetic Solid-Phase Extraction for Determination of Pyrethroid Residues in Vegetable Samples by Ultra Fast Liquid Chromatography[J]. Talanta,2013,114(10):167-175.
[9]	Yang G L,Wang W,Liang S M, et al. Pesticide Residues in Bayberry(Myrica rubra) and Probabilistic Risk Assessment for Consumers in Zhejiang, China[J]. J Integr Agric,2017,16(9):2101-2109.
[10]	LIU Yongxia.Degradation Dynamics and Residual Amount of Cyhalothrin in Ya Pear Fruit[D]. Baoding:Hebei Agricultural University,2008(in Chinese). 刘永霞. 三氟氯氰菊酯在鸭梨果实中的降解动态及残留量研究[D]. 保定:河北农业大学,2008.
[11]	Li Y,Dong W F,Wang X, et al. Determination of 9 Synthetic Pyrethroids in Brown Rice by Gas Chromatography-Mass Spectrometry[J]. J Food Safe Food Qual,2015,6(1):65-71.
[12]	Chen G F,Liu F,Zhang X B, et al. Determination of Thiamethoxam and Lambda-Cyhalothrin Residue in Wheat Field by GC-MS/MS[J]. Mod Agrochem,2015,14(5):39-41.
[13]	Xue C,Han Q,Wang Y, et al. Amperometric Detection of Dopamine in Human Serum by Electrochemical Sensor Based on Gold Nanoparticles Doped Molecularly Imprinted Polymers[J]. Biosens Bioelectron,2013,49(22):199-203.
[14]	Sooraj M P,Nair A S,Pillai S C, et al. CuNPs Decorated Molecular Imprinted Polymer on MWCNT for the Electrochemical Detection of l-DOPA[J]. Arab J Chem,2018.
[15]	GAO Wenhui,PANG Jun,WANG Jiaojiao, et al. Preparation and Recognition Performance of Biphenyl Triazole Alcohol Molecularly Imprinted Electrochemical Sensor[J]. Mod Food Sci Technol,2015,31(1):96-100(in Chinese). 高文惠,庞军,王姣姣,等. 联苯三唑醇分子印迹电化学传感器的制备及识别性能研究[J]. 现代食品科技,2015,31(1):96-100.
[16]	ZHAO Lingyu,GAO Lin,PANG Jun, et al. Preparation and Application of Molecularly Imprinted Electrochemical Sensor for the Detection of Tetramethrin and Its Performance[J]. Food Sci,2017,38(8): 283-289(in Chinese). 赵玲钰,高林,庞军,等. 胺菊酯分子印迹电化学传感器的制备及性能[J]. 食品科学,2017,38(8):283-289.
[17]	TAN Xuecai,MAI Zhibin,ZOU Xiaoyong, et al. Study on the Determination of Chitosan by Using Alizarin Red as an Electrochemical Activity Probe[J]. J Instrum Anal,2005,24(6):32-36(in Chinese). 谭学才,麦智彬,邹小勇,等. 以茜素红为电活性探针测定壳聚糖的研究[J]. 分析测试学报,2005,24(6):32-36.
[18]	CHI Damin,SU Liqiang,DENG Qianshan, et al. Research Progress in Molecular Selection Methods for Molecular Imprinting Functions[J]. Chem J,2009,23(12):55-57(in Chinese). 迟大民,苏立强,邓茜珊,等. 分子印迹功能单体选择方法研究进展[J]. 化工时刊,2009,23(12):55-57.
[19]	WANG Shuaishuai,ZHU Qiujin.Ultraviolet Spectrum Research of the Preparation Ratio of Template Molecule in Histamine Molecularly Imprinted Polymers[J]. China Brew,2016,35(11):149-152(in Chinese). 王帅帅,朱秋劲. 组胺分子印迹聚合物中模板分子制备比例的紫外光谱学研究[J]. 中国酿造,2016,35(11):149-152.
[20]	SHI Yang,LIU Junbo,TANG Shanshan, et al. Molecular Imprinted Interaction Between Salbutamol and Each of Different Functional Monomers[J]. J Jilin Univ(Sci Ed),2014,52(5):1059-1066(in Chinese). 石杨,刘俊渤,唐珊珊,等. 沙丁胺醇与不同功能单体分子的印迹作用[J]. 吉林大学学报(理学版),2014,52(05):1059-1066.
[21]	MA Liang,DAI Fangfang,ZHOU Yao, et al. Development of a Type II Pyrethroid Molecularly Imprinted Membrane Based on Electrochemical Technology[J]. Mod Food Sci Technol,2016,32(2):121-129(in Chinese). 马良,戴芳芳,周瑶,等. 基于电化学技术的Ⅱ型拟除虫菊酯分子印迹膜的研制[J]. 现代食品科技,2016,32(2):121-129.
[22]	ZHAO Lingyu,WANG Jiaojiao,GAO Wenhui.Preparation of Cyhalothrin Molecularly Imprinted Solid-Phase Extraction Membrane and Its Application in Food Detection[J]. Chem Bull,2019,82(1):80-86(in Chinese). 赵玲钰,王姣姣,高文惠. 氟氯氰菊酯分子印迹固相萃取膜的制备及其在食品检测中的应用[J]. 化学通报,2019,82(1):80-86.