戊唑醇分子印迹传感器制备及其农药残留检测的电学传感机理分析
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摘要
以甲基丙烯酸为功能单体,戊唑醇(tebuconazole,TEB)为模板分子,乙二醇二甲基丙烯酸酯为交联剂,应用电化学聚合法制备了分子印迹电化学传感器(TEB-MIP/F-CNTs/GCE)。利用循环伏安法(cyclic voltammetry,CV)和交流阻抗法(electrochemical impedance spectroscopy,EIS)对新型传感器进行了表征,并用差分脉冲伏安法(differential pulse voltammetry,DPV)考察了新型传感器对戊唑醇的检测性能。结果表明:戊唑醇分子印迹电化学传感器具有一定特异性;传感器表观表面积比裸电极显著提高;新型传感器具有良好的印迹效果,相较于其他结构类似的三唑类化合物(如苯醚甲环唑),TEB-MIP/F-CNTs/GCE对戊唑醇表现出高效的识别能力,具有专一性和强选择性,且在C_(TEB)≤2.0×10~(-6)mol/L范围内传感器峰电流与C_(TEB)存在定量关系;数据模拟分析得到传感器的电学阻抗谱等效电路模型为R_1(CPE_1(R_2(CPE_2(R_3)))),计算各电极/传感器的等效电路中各元件参数,证明该模型能有效地模拟传感器检测戊唑醇的传感机理。该研究结果可为三唑类农药残留仿生免疫检测方法的建立提供技术支撑。
A newmolecularly imprinted membranes-based electrochemical sensor with high imprinted capacity to tebuconazole(TEB) was prepared by electrochemical polymerization. M ethacrylic acid was deposited onto the surface of glassy carbon electrode as a functional monomer along with template molecules TEB, and ethylene glycol dimethacrylate as a crosslinking agent. Through cyclic voltammetry(CV), differential pulse voltammetry(DPV) and electrochemical impedance spectroscopy(EIS),detection performance of the newsensor on tebuconazole was evaluated and theequivalent circuit model was constructed. The results showed that the newmolecularly imprinted electrochemical sensor was prepared successfully with high specificity. Compared with the bare electrode,the sensor's apparent surface area was increased significantly,and the imprinted effect of newsensors is good. Compared with other triazole compound(e. g. difenoconazole) with the similar structure,TEB-M IP/F-CNTs/GCE exhibited high effective and selective recognition ability for TEB.The quantitative relationship between the peak current of sensor and c_(TEB) was built at c_(TEB)≤2.0 ×10~(-6)mol / L; the electrical impedance equivalent circuit model of sensor was R_1( CPE_1( R_2( CPE_2( R_3)))) through data simulation analysis. The parameters of each element equivalent circuit suggested that R_1(CPE_1(R_2(CPE_2(R_3)))) equivalent circuit could effectively simulate the sensing mechanism of sensor when analyzing TEB. The results of this work provided basic information for developing a bionic immunoassay method of detecting triazole pesticide residues.
A newmolecularly imprinted membranes-based electrochemical sensor with high imprinted capacity to tebuconazole(TEB) was prepared by electrochemical polymerization. M ethacrylic acid was deposited onto the surface of glassy carbon electrode as a functional monomer along with template molecules TEB, and ethylene glycol dimethacrylate as a crosslinking agent. Through cyclic voltammetry(CV), differential pulse voltammetry(DPV) and electrochemical impedance spectroscopy(EIS),detection performance of the newsensor on tebuconazole was evaluated and theequivalent circuit model was constructed. The results showed that the newmolecularly imprinted electrochemical sensor was prepared successfully with high specificity. Compared with the bare electrode,the sensor's apparent surface area was increased significantly,and the imprinted effect of newsensors is good. Compared with other triazole compound(e. g. difenoconazole) with the similar structure,TEB-M IP/F-CNTs/GCE exhibited high effective and selective recognition ability for TEB.The quantitative relationship between the peak current of sensor and c_(TEB) was built at c_(TEB)≤2.0 ×10~(-6)mol / L; the electrical impedance equivalent circuit model of sensor was R_1( CPE_1( R_2( CPE_2( R_3)))) through data simulation analysis. The parameters of each element equivalent circuit suggested that R_1(CPE_1(R_2(CPE_2(R_3)))) equivalent circuit could effectively simulate the sensing mechanism of sensor when analyzing TEB. The results of this work provided basic information for developing a bionic immunoassay method of detecting triazole pesticide residues.
引文
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[19]彭畅,刘维娟,张春涛,等.识别三唑类农药的片段印迹聚合物的合成及在固相萃取中的应用[J].高等学校化学学报,2009,30(11):2159-2164.Peng Chang,Liu Weijuan,Zhang Chuntao,et al.Preparation of a fragment imprinted polymer for recognition of triazole pesticides and its application to solid-phase extraction[J].Chem J Chinese Univ,2009,30(11):2159-2164.(in Chinese)
[20]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.Gao Wenhui,Pang Jun,Wang Jiaojiao,et al.Preparation and recognition properties of a bitertanol electrochemical sensor based on molecular imprinting technology[J].Modern Food Sci Technol,2015,31(1):96-100.(in Chinese)
[21]胡陈果,王万录.碳纳米管的电化学性质及其应用研究[J].功能材料,2005,36(5):730-733.Hu Chenguo,Wang Wanlu.Investigation of electrochemical properties and their applications on CNT electrodes[J].J Functional Mat,2005,36(5):730-733.(in Chinese)
[22]Du D,Wang M H.Sensitive acetylcholinesterase biosensor based on assembly ofβ-cyclodextrins on to multiw all carbon nanotubes for detection of organophosphates pesticide[J].Sens Actuators:B,2010,146(1):337-341.
[23]郭明,梁东军,谭贤.农药残留检测用新型碳纳米管固载酶生物传感器的制备及其电学传感性能分析[J].农药学学报,2014,16(3):319-329.Guo M ing,liang Dongjun,Tan Xian.Preparation of new carbon nanotubes immobilized enzyme biosensor for pesticide residue detection and analysis of its electrochemical sensing properties[J].Chin J Pestic Sci,2014,16(3):319-329.(in Chinese)
[24]Calfuman K,Aguirre M J,Villagra D.Nafion/tetraruthenated porphyrin glassy carbon-modified electrode:characterization and voltammetric studies of sulfite oxidation in w ater-ethanol solutions[J].J Solid State Electrochem,2010,14(6):1065-1072.
[2]华乃震.杀菌剂戊唑醇的剂型与应用[J].农药,2013,52(11):781-786.Hua Naizhen.Formulation and application of fungicide tebuconazole[J].Agrochemicals,2013,52(11):781-786.(in Chinese)
[3]史长生.农药残留危害以及检测技术的分析[J].食品研究与开发,2009,31(9):218-221.Shi Changsheng.Pesticide residue hazards and the analysis of detection techniques[J].Food Res Devel,2009,31(9):218-221.(in Chinese)
[4]Wu Y T,Zhang Y H,Zhang M,et al.Selective and simultaneous determination of trace bisphenol A and tebuconazole in vegetable and juice samples by membrane-based molecularly imprinted solid-phase extraction and HPLC[J].Food Chem,2014,164(10):527-535.
[5]Yang J,Wang Q,Zhang M,et al.An electrochemical fungicide pyrimethanil sensor based on carbon nanotubes/ionic-liquid construction modified electrode[J].Food Chem,2015,187(11):1-6.
[6]Zhang W,Tang Y,Liu J,et al.An electrochemical sensor for detecting triglycerid based on biomimetic polydopamine and gold nanocomposite[J].J Mat Chem,2014,2(12):8490-8495.
[7]袁永海,李建平.电化学生物传感器在农药检测中的应用[J].分析测试学报,2006,25(5):121-127.Yuan Yonghai,Li Jianping.Applications of electrochemical biosensor for detecting pesticides[J].J Instrum Anal,2006,25(5):121-127.(in Chinese)
[8]孙春燕,李宏坤,平红,等.Au NPs/Sol-gel复合膜法固定乙酰胆碱酯酶生物传感器检测有机磷农药[J].高等学校化学学报,2011,32(11):2533-2538.Sun Chunyan,Li Hongkun,Ping Hong,et al.Determination of organophosphorus pesticides using a biosensor based on acetylcholinesterase immobilized by Au nanoparticles/sol-gel composite membrane[J].Chem J Chinese Univ,2011,32(11):2533-2538.(in Chinese)
[9]Gan T,Hu S S.Electrochemical sensors based on graphene materials[J].Microchim Acta,2011(175):1–19.
[10]张静,顾婷婷.直接电化学酶传感器的研究进展[J].辽宁科技大学学报,2009,32(5):460-465.Zhang Jing,Gu Tingting.Development of direct electrochemical enzyme sensor[J].J Univ Sci Tech Liaoning,2009,32(5):460-465.(in Chinese)
[11]Yang G,Zhao F.A novel electrochemical sensor for the determination of lidocaine based on surface-imprinting on porous three-dimensional film[J].J Mat Chem C,2014,2(12):10201-10208.
[12]郭明,谭贤,梁东军,等.吡虫啉分子印迹电化学传感器的制备及电学传感机理分析[J].农药学学报,2014,16(5):559-569.Guo M ing,Tan Xian,Liang Dongjun,et al.Preparation of imidacloprid imprinted electrochemical sensor and its electrical sensing mechanism[J].Chin J Pestic Sci,2014,16(5):559-569.(in Chinese)
[13]王艳玲,刘俊渤,孙佳妮,等.恩诺沙星与甲基丙烯酸分子印迹作用的理论研究[J].高分子学报,2013(12):1525-1530.Wang Yanling,Liu Junbo,Sun Jiani,et al.Theoretical studies on molecular imprinted interaction betw een enrofloxacin and methacrylic acid[J].Acta Polymerica Sinica,2013(12):1525-1530.(in Chinese)
[14]余会成,黄学艺,谭学才,等.基于电聚合的苯巴比妥分子印迹电化学传感器的制备及其应用研究[J].分析测试学报,2014,33(7):752-757.Yu Huicheng,Huang Xueyi,Tan Xuecai,et al.Preparation and application of phenobarbital electrochemical sensor based on molecular imprinted technique and electropolymerization membrane[J].J Instrum Anal,2014,33(7):752-757.(in Chinese)
[15]Gonzalez G P,Hernando P F,Alegria J S D.An optical sensor for the determination of digoxin inserum samples based on a molecularly imprinted polymer membrane[J].Analytica Chimica Acta.2009,638(2):209-212.
[16]Barrios C A,Zhenhe C,Navarro-Villoslada F,et al.M olecularly imprinted polymer diffraction grating as label-free optical bio(mimetic)sensor[J].Biosensors and Bioelectronics,2011,26(5):2801-2804.
[17]Liang R N,Zhang R M,Qin W.Potentiometric sensor based on molecularly imprinted polymer for determination of melamine in milk[J].Sensor and Actuators B:Chemical,2009,141(2):544-550.
[18]胡静,褚建功,高文惠.三唑醇分子印迹聚合物的制备及在食品检测中的应用[J].药物分析杂志,2011,31(12):2260-2265.Hu Jing,Chu Jiangong,Gao Wenhui.Preparation of triadimenol molecularly imprinted polymer and its application in food detection[J].Chinese J Pharmaceut Anal,2011,31(12):2260-2265.(in Chinese)
[19]彭畅,刘维娟,张春涛,等.识别三唑类农药的片段印迹聚合物的合成及在固相萃取中的应用[J].高等学校化学学报,2009,30(11):2159-2164.Peng Chang,Liu Weijuan,Zhang Chuntao,et al.Preparation of a fragment imprinted polymer for recognition of triazole pesticides and its application to solid-phase extraction[J].Chem J Chinese Univ,2009,30(11):2159-2164.(in Chinese)
[20]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.Gao Wenhui,Pang Jun,Wang Jiaojiao,et al.Preparation and recognition properties of a bitertanol electrochemical sensor based on molecular imprinting technology[J].Modern Food Sci Technol,2015,31(1):96-100.(in Chinese)
[21]胡陈果,王万录.碳纳米管的电化学性质及其应用研究[J].功能材料,2005,36(5):730-733.Hu Chenguo,Wang Wanlu.Investigation of electrochemical properties and their applications on CNT electrodes[J].J Functional Mat,2005,36(5):730-733.(in Chinese)
[22]Du D,Wang M H.Sensitive acetylcholinesterase biosensor based on assembly ofβ-cyclodextrins on to multiw all carbon nanotubes for detection of organophosphates pesticide[J].Sens Actuators:B,2010,146(1):337-341.
[23]郭明,梁东军,谭贤.农药残留检测用新型碳纳米管固载酶生物传感器的制备及其电学传感性能分析[J].农药学学报,2014,16(3):319-329.Guo M ing,liang Dongjun,Tan Xian.Preparation of new carbon nanotubes immobilized enzyme biosensor for pesticide residue detection and analysis of its electrochemical sensing properties[J].Chin J Pestic Sci,2014,16(3):319-329.(in Chinese)
[24]Calfuman K,Aguirre M J,Villagra D.Nafion/tetraruthenated porphyrin glassy carbon-modified electrode:characterization and voltammetric studies of sulfite oxidation in w ater-ethanol solutions[J].J Solid State Electrochem,2010,14(6):1065-1072.