盐酸阿霉素分子印迹传感器的制备及识别特性

doi:10.7503/cjcu20150938

摘要/Abstract

摘要：

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.

关键词: 分子印迹聚合物, 电化学传感器, 3, 4-乙烯二氧噻吩, 盐酸阿霉素

Abstract:

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^-6 mol/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%.

Key words: Molecularly imprinted polymer, Electrochemical sensor, 3, 4-Ethylene dioxythiophene, Doxorubicin hydrochloride

中图分类号:

O657.1

TrendMD:

张燕, 郑晶, 王娟, 郭满栋. 盐酸阿霉素分子印迹传感器的制备及识别特性. 高等学校化学学报, 2016, 37(5): 860.

ZHANG Yan, ZHENG Jing, WANG Juan, GUO Mandong. Preparation and Properties of Doxorubicin Hydrochloride Sensor Based on Molecularly Imprinted Polymer^†. Chem. J. Chinese Universities, 2016, 37(5): 860.

图/表 11

Fig.1 Structures of DOX and EDOT

Scheme 1 Schematic diagram for the preparation of the MIP electrode

Fig.2 CV curves for the electrochemical polymerization of EDOT in the absence(A) and presence(B) of DOX in PBS Scan rate: 50 mV/s; cycling number: (A) 10; (B) 7.

Fig.3 CV curves of the electrodes in 0.1 mol/L KCl containing 5 mmol/L K3[Fe(CN)6](A) and electrochemical impedance spectroscopy of the electrodes(B)(A) a. Au/CME; b. PEDOT/Au/CME; c. AuNPs-CS/PEDOT/Au/CME; d. DOX-MIPs/AuNPs-CS/PEDOT/Au/CME; e. MIPs/AuNPs-CS/PEDOT/Au/CME; f. NMIPs/AuNPs-CS/PEDOT/Au/CME. (B) ■ Au/CME;▼ DOX-MIPs/AuNPs-CS/PEDOT/Au/CME; ● PEDOT/Au/CME; ▲ AuNPs-CS/PEDOT/Au/CME.

Fig.4 SEM images of MIP-modified electrode(A), eluted electrode(B) and NIP-modified electrode(C)

Fig.5 Influence of the adsorption time on the response of the sensor

Fig.6 DPV curves of MIP/AuNPs-CS/PEDOT/Au/CME after adsorption in different concentrations of DOX(A) and linear relationship of current peak difference vs. DOX concentration on MIP/AuNPs-CS/PEDOT/Au/CME(B)

Table 1 Comparison of detection results of DOX by this method and literature methods

Method	Linear range/(mol·L^-1)	10⁸ Detection limit	Ref.
High performance liquid chromategraphy	1.7×10^-7—1.7×10^-5	17.0	[1]
Capillary electrophoresis	1.0×10^-6—1.0×10^-5	29.0	[2]
Fluorescence spectroscopy	7.8×10^-8—5.2×10^-6	2.3	[3]
The proposed method	6.9×10^-7—4.3×10^-6	5.0	[4]
Flow injection chemilumin-escence method-escence method	4.0×10^-7—1.0×10^-6	6.5	This work

Fig.7 Structures of substance used in interference experiments

Fig.8 Current response of different substances on MIP sensor and NIP sensora. DOX; b. VLB; c. 5FU; d. ACD.

Table 2 Determination result of DOX in blood serum samples

10⁶ Concentration added/ (mol·L^-1)	Current response/μA			10⁶ Concentration detected mol/L	Recovery(%)	RSD(%)
10⁶ Concentration added/ (mol·L^-1)	First			10⁶ Concentration detected mol/L	Second	Third
1	-4.96	-4.80	-4.86	9.4	96.0	1.66
3	-7.32	-7.23	-7.15	3.2	106.7	1.39
5	-8.95	-8.80	-8.83	4.86	97.2	0.90
7	-11.04	-10.90	-10.86	7.13	101.9	0.86

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