基于石墨烯的毒死蜱分子印迹电化学传感器的制备及对毒死蜱的测定  

Electrochemical Sensor for Determination of Chlorpyrifos Based on Graphene Modified Electrode and Molecularly Imprinted Polymer

作　　者：谭学才[1] 吴佳雯[1] 胡琪[1] 李晓宇[1] 李鹏飞[1] 余会成[1] 李小燕[1] 雷福厚 

机构地区：[1]广西民族大学化学化工学院,广西林产化学与工程重点实验室,广西高校食品安全与药物分析化学重点实验室,南宁530008

出　　处：《分析化学》2015年第3期387-393,共7页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金(Nos.21365004;21065001);广西自然科学基金重点项目(No.2013GXNSFDA019006);广西教育厅科研基金重点项目(No.2013ZD019);广西高等学校高水平创新团队及卓越学者资助计划(桂教人[2014]7号);广西民族大学研究生创新基金(No.GXUN-chx2013092)项目资助~~

摘　　要：利用分子印迹技术,以马来松香丙烯酸乙二醇酯为交联剂,使用自由基热聚合法在石墨烯修饰的玻碳电极表面合成毒死蜱（CPF）分子印迹聚合膜,制得了CPF分子印迹电化学传感器。采用循环伏安法、线性扫描伏安法和电化学交流阻抗法等,考察了此CPF分子印迹膜的电化学性能。在最佳检测条件下,传感器的峰电流与CPF浓度在2.0×10^-7-1.0×10^-5mol/L范围内呈线性关系,线性方程为Ip（μA）=^-7.1834-0.2424C（μmol/L）,相关系数r2=0.9959,检出限为6.7×10^-8mol/L（S/N=3）。构建了CPF分子印迹电化学传感器的动力学吸附模型,测得印迹传感器的印迹因子β=2.59,结合速率常数k=12.2324 s。传感器表现出良好的重现性和稳定性,并成功用于实际水样和蔬菜样品中CPF的测定,加标回收率为94.1%-101.4%。Graphene and a novel cross-linker（ ethylene glycol maleic rosinate acrylate） were used to prepare molecularly imprinted electrochemical sensors with high sensitivity. A molecular imprinting polymer（ MIP）film was created on a graphene-modified glassy-carbon electrode for determination of chlorpyrifos（ CPF） using free radical polymerization method. The electrochemical properties of the MIP and non-imprinted polymer（ NIP） sensors were investigated via cyclic voltammetry（ CV）,linear sweep voltammetry,and electrochemical impedance spectroscopy（ EIS）. The surface morphology of the imprinted film was characterized by scanning electron microscopy（ SEM）. Under the optimal experimental conditions,the peak currents were proportional to the concentrations of chlorpyrifos in the range of 2. 0 ×10 ^-7-1. 0 ×10^- 5mol / L with a detection limit of 6. 7 ×10 ^-8mol / L（ S / N = 3）. The linear equation was Ip（ μA） = ^- 7. 1834-0. 2424C（ μmol/L）（ R2= 0. 9959）.Adsorption model of the molecular imprinted sensor was investigated,and the measured imprinting factor β of the sensor was 2. 59,with the binding rate constant k of 12. 2324 s. The developed electrochemical sensor based on graphene modified electrode and molecularly imprinted polymer exhibited good repeatability and stability,and was successfully used to determine CPF in water and vegetable samples with recoveries from94. 1% to 101. 1%.

关 键 词：毒死蜱 石墨烯 分子印迹聚合物 电化学传感器 马来松香丙烯酸乙二醇酯 

分 类 号：O657.1[理学—分析化学] TP212[理学—化学]