金霉素分子印迹电化学传感器的制备与应用

doi:10.11949/0438-1157.20220199

摘要/Abstract

摘要：

金霉素（CTC）的滥用给自然环境和人类健康带来了严重的不良影响。建立了一种简便、经济、高效的CTC分子印迹电化学传感器。该传感器的分子印迹膜由邻苯二胺在还原型氧化石墨烯-聚乙烯亚胺复合物（RGO-PEI）修饰的玻碳电极上电聚合而成。采用扫描电子显微镜、红外吸收光谱和紫外可见吸收光谱对RGO-PEI复合材料进行了表征。RGO-PEI复合材料的高比表面积和丰富的氨基基团提高了该传感器检测的灵敏度和稳定性。在优化条件下，该传感器对CTC浓度响应的线性范围为（5.0 × 10^-7）~（1.0 × 10^-4）mol/L，检测限为 1.67 × 10^-7 mol/L （信噪比，S/N=3）。此外，该传感器对卡那霉素、土霉素和盐酸多西环素等干扰物质的响应很小，可用于实际样品中CTC的检测，回收率为102.7% ~ 104.7%，是一种简单、高效的电化学方法。

关键词: 金霉素, 分子印迹, 石墨烯, 电化学, 邻苯二胺

Abstract:

The abuse of chlortetracycline (CTC) has brought serious adverse effects on the natural environment and human health. In this paper, a simple, economical and efficient molecularly imprinted electrochemical sensor for CTC was developed. The sensor was constructed by the electropolymerization of o-phenylenediamine on a reduced graphene oxide-polyethyleneimine complex (RGO-PEI) modified glassy carbon electrode. The RGO-PEI composite was characterized by scanning electron microscopy, infrared spectrum and ultraviolet visible spectrum. The high specific surface area and richness of amino groups of the RGO-PEI composite make it an excellent candidate for the detection of CTC due to the improved detection sensitivity and the stability of the molecularly imprinted film. Under optimized conditions, the sensor exhibited a wide linear range of (5.0×10^-7)—(1.0×10^-4) mol/L with a detection limit of 1.67×10^-7 mol/L (S/N=3). Additionally, there was little response to interfering substances such as kanamycin, oxytetracycline and doxycycline hydrochloride. The proposed method was successfully used for the detection of CTC in real sample with the recoveries of 102.7％—104.7％, showing a simple and efficient electrochemical method in practical application.

Key words: chlortetracycline, molecularly imprinting, graphene, electrochemical, o-phenylenediamine

中图分类号:

O 657.14

韩双, 张楠, 王慧, 张璇, 杨金栾, 张蔓琳, 张志超. 金霉素分子印迹电化学传感器的制备与应用[J]. 化工学报, 2022, 73(8): 3758-3767.

Shuang HAN, Nan ZHANG, Hui WANG, Xuan ZHANG, Jinluan YANG, Manlin ZHANG, Zhichao ZHANG. Preparation and application of chlortetracycline electrochemical sensor based on molecularly imprinting technique[J]. CIESC Journal, 2022, 73(8): 3758-3767.

图/表 16

图1 CTC分子印迹电化学传感器的构建过程（邻苯二胺电聚合反应式和RGO-PEI反应式）

Fig.1 Schematic representation of the fabrication procedures of the CTC MIP sensor

图2 GO和RGO-PEI的SEM图像及RGO-PEI的EDX图像

Fig.2 SEM images of GO and RGO-PEI and EDX image of RGO-PEI

图3 GO和RGO-PEI的红外吸收光谱图

Fig.3 FTIR spectra of GO and RGO-PEI

图4 GO和RGO-PEI的紫外可见吸收光谱图

Fig.4 UV-Vis spectra of GO and RGO-PEI

图5 5.0 mmol/L o-PD在GCE/RGO-PEI修饰电极表面电聚合的循环伏安图

Fig.5 Cyclic voltammograms for the electropolymerization of 5.0 mmol/L o-PD on GCE/RGO-PEI in the presence (a) and in the absence (b) of CTC in pH4.8 acetate buffer (scan rate: 0.050 V/s)

图6 不同电极在5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl中的循环伏安图a—裸GCE; b—GCE/RGO-PEI; c—MIP GCE/RGO-PEI/PPD; d—洗脱之后的MIP GCE/RGO-PEI/PPD; e—重新吸附CTC的MIP GCE/RGO-PEI/PPD

Fig.6 Cyclic voltammograms of 5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl on the bare GCE (a), GCE/RGO-PEI (b), GCE/RGO-PEI after electropolymerization (c), MIP GCE/RGO-PEI/PPD after the removal of CTC (d), MIP GCE/RGO-PEI/PPD after incubation of CTC (e)

图7 不同扫描速率下MIP GCE/RGO-PEI/PPD 在5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl中的循环伏安图

Fig.7 Cyclic voltammograms of 5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl on the MIP GCE/RGO-PEI/PPD at different scan rates

图8 不同扫描速率与K3[Fe(CN)6]在MIP GCE/RGO-PEI/PPD上峰电流的关系曲线

Fig.8 Relationship between the scan rate and peak currents

图9 电聚合圈数的优化

Fig.9 Effect of the electropolymerization cycles on the peak current of the CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl (I0 is the current of the MIP GCE/RGO-PEI/PPD after elution; I is the current of the MIP GCE/RGO-PEI/PPD after incubation of CTC)

图10 pH的优化

Fig.10 Effect of pH on the peak current of CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl(ΔI = I0 - I)

图11 洗脱时间的优化

Fig.11 Effect of elution time on the peak current of CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl (I′ is the current of the GCE/RGO-PEI/PPD after electropolymerization)

图12 吸附时间的优化

Fig.12 Effect of incubation time on the peak current of CV response in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl

图13 MIP GCE/RGO-PEI/PPD在不同浓度CTC标准溶液中的线性扫描伏安图

Fig.13 Linear sweep voltammograms of 5.0 mmol/L K3[Fe(CN)6]/0.1 mol/L KCl at 0.050 V/s for CTC-free MIP films after rebinding CTC at different concentrations

图14 MIP GCE/RGO-PEI/PPD检测CTC的标准曲线

Fig.14 Linear calibration curve of ΔI with CTC concentrations

图15 MIP GCE/RGO-PEI/PPD对其他抗生素的抗干扰能力检验

Fig.15 The the current change of MIP GCE/RGO-PEI/PPD in the presence of 5.0 mmol/L K3[Fe(CN)6]/ 0.1 mol/L KCl after incubation in 25.0 μmol/L CTC, 25.0 μmol/L CTC +100.0 μmol/L kanamycin, 25.0 μmol/L CTC + 100.0 μmol/L DOC, 25.0 μmol/L CTC + 100.0 μmol/L OTC(ΔI0 = I0 -ICTC; ΔI = I0 -ICTC+others)

表1 湖水样品中CTC的回收实验

Table 1 Recoveries for CTC detection in lake samples

样品	加入量/(μmol/L)	测得量/(μmol/L)	回收率/%	平均回收率/%	RSD(n=3)/%
1	10.0	10.51, 10.71, 10.47	105.1, 107.1, 104.7	104.7	1.22
2	50.0	52.61, 51.41, 50.05	105.2, 102.8, 100.1	102.7	2.49

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