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%。Abstract 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"5 mol /L with a detection limit of 6． 7× 10"8 mol /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 from 94． 1% to 101． 1%． ; 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