盐酸阿霉素分子印迹传感器的制备及识别特性

Preparation and Properties of Doxorubicin Hydrochloride Sensor Based on Molecularly Imprinted Polymer

采用自组装以及电聚合的方法,在磷酸盐缓冲液(PBS)中以3,4-乙烯二氧噻吩(EDOT)为功能单体,盐酸阿霉素(DOX)为模板,在金电极表面电聚合制备DOX印迹敏感膜(MIPs),构建了一种选择性检测DOX的分子印迹电化学传感器.采用循环伏安法(CV)及交流阻抗法(EIS)对其性能进行了表征.优化实验条件后,在含0.005 mol/L K3[Fe(CN)_6]及0.1 mol/L KCl的PBS中,应用差分脉冲伏安法(DPV)测试了该传感器的响应性能.实验结果表明,该传感器检测DOX的线性范围为4.0×10^(-7)~1.0×10^(-6)mol/L,相关系数为0.9967,检出限(S/N=3)达6.5×10^(-8)mol/L;采用电化学洗脱法可使传感器再生,对DOX的测定具有良好重现性及稳定性;该传感器对于干扰物长春碱、放线菌素D及5-氟尿嘧啶有微弱的电流响应,显示出良好的选择性.将该传感器用于人体血样中盐酸阿霉素的分析,回收率为96.0%~106.7%,表明其具有潜在的实用价值.

An electrochemical sensor was developed for the determination of doxorubicin hydrochloride（ DOX）using the molecularly imprinted technique. A molecular imprinted polymer（ MIP） on the surface of a gold electrode was prepared by electropolymerization of 3,4-ethylenedioxythiop-hene（ EDOT） in the presence of DOX in the phosphate buffer solution. Under the optimum conditions,the properties of the electrochemical sensor modified with DOX-imprinted membrane were characterized by cyclic voltammetry,differential pulse voltammetry and electrochemical impedance spectroscopy. A linear relationship between oxidation peak current and DOX concentration was obtained over the range of 4. 0 × 10-7-1. 0 × 10-6mol/L with a correlation coefficient of 0. 9967 and a detection limit（ S/N = 3） of 6. 5 × 10-8 mol/L. After regeneration by washing with electrochemical method,the sensor showed excellent reproducibility and good stability. The MIP electrode exhibited very weak response to vinblastine,actinomycin D and fluorouracile,proving a good selectivity. The imprinted sensor was applied to the determination of doxorubicin hydrochloride in human blood serum samples with the relative standard deviation（ RSD） below 4% and recovery ranging from 96. 0% to 106. 7%.