基于二维Ti3C2T x 纳米片/导电科琴黑复合材料聚甲基丙烯酸分子印迹电化学传感器的构建及多巴胺检测

doi:10.7503/cjcu20250040

高等学校化学学报 ›› 2025, Vol. 46 ›› Issue (7): 20250040.doi: 10.7503/cjcu20250040

基于二维Ti₃C₂T _x 纳米片/导电科琴黑复合材料聚甲基丙烯酸分子印迹电化学传感器的构建及多巴胺检测

任书芳¹, 郭童², 王子涵¹, 刘亚慧¹, 陈雨¹, 曾俊菱¹()

^1.甘肃政法大学甘肃省证据科学技术研究与应用重点实验室, 司法警察学院, 兰州 730070
^2.陕西省榆林市公安局法制支队, 榆林 719000

收稿日期:2025-02-14 出版日期:2025-07-10 发布日期:2025-04-28
作者简介:曾俊菱, 女, 博士, 副教授, 主要从事微量物证、电分析化学及纳米材料在物证技术中应用方面的研究. E⁃mail： zjl6993@gsupl.edu.com
基金资助:
国家自然科学基金(22164003);甘肃政法大学校级科研创新项目(GZF2024XZDA02);甘肃政法大学校级科研创新项目(GZF2024XZD15);高校教师创新基金(2024B-111)

Construction of Molecular Imprinted Electrochemical Sensor Based on 2D Ti₃C₂T _x Nanosheet/Conductive Kochen Black Composite Polymethacrylic Acid and the Detection of Dopamine

REN Shufang¹, GUO Tong², WANG Zihan¹, LIU Yahui¹, CHEN Yu¹, ZENG Junling¹()

^1.Key Laboratory of Evidence Science Research and Application of Gansu Province，Judicial Police Academy，Gansu University of Political Science and Law，Lanzhou 730070，China
^2.Legal Affairs Division of the Public Security Bureau of Yulin City，Yulin 719000，China

Received:2025-02-14 Online:2025-07-10 Published:2025-04-28
Supported by:
the National Natural Science Foundation of China(22164003);the Campus Level Research and Innovation Project of Gansu University of Political Science and Law, China(GZF2024XZDA02);the Innovation Fund of University Teacher, China(2024B-111)

摘要/Abstract

摘要：

构建了基于二维Ti₃C₂T _x 纳米片/导电科琴黑复合材料的聚甲基丙烯酸分子印迹电化学传感器, 用于多巴胺（DA）检测. 利用湿法刻蚀技术和超声机械混合法制备了二维Ti₃C₂T _x 纳米片（d-Ti₃C₂T _x ）/导电科琴黑（KB）复合材料；以DA为模板分子, 甲基丙烯酸为功能单体, 利用电化学沉积技术在d-Ti₃C₂T _x /KB修饰电极表面制备了选择性识别DA分子的分子印迹聚合物膜. 采用X射线衍射、场发射扫描电子显微镜及透射电子显微镜分析了材料的成分及形貌结构, 用循环伏安法以铁氰化钾为电子探针考察了修饰电极的电化学性能, 用脉冲伏安法（DPV）考察了电极对DA的电化学响应性能. 对检测条件如修饰材料质量比、功能与单体之比、电沉积圈数、富集时间及pH等参数进行了优化. 检测结果显示, 所构筑的传感器对DA有较高的DPV电化学响应性, 线性检测范围为1×10^-6~1×10^-2 mol/L, 检出限为4.228 μmol/L（S/N=3）. 该传感器具有良好的抗干扰性和重复性. 采用标准加入法检测了非侵入性尿液样品中的DA, 加标回收率为82.5%~93.75%, RSD均低于5%. 构筑的传感器具有较高的灵敏度和可靠性, 为DA检测提供了可借鉴和参考的方法和思路.

关键词: 多巴胺, 电化学传感器, 分子印迹, MXenes, Ti₃C₂T _x, 科琴黑

Abstract:

In this paper， we constructed a poly（methacrylic acid） molecularly imprinted electrochemical sensor based on two-dimensional Ti₃C₂T_x nanosheets/conductive carbon black（KB） composite for the detection of dopamine（DA）. In the beginning， two-dimensional Ti₃C₂T _x nanosheets/conductive KB composites were prepared by wet etching and ultrasonic mechanical mixing techniques and DA was used as the template molecule and methacrylic acid as the functional monomer. Afterwards， a molecularly imprinted polymer film selective for DA was fabricated on the surface of the d-Ti₃C₂T _x /KB modified electrode by electrochemical deposition. The composition and morphology of the materials were analyzed by X-ray diffraction（XRD）， field emission scanning electron microscopy（FESEM） and transmission electron microscopy（TEM）. The electrochemical performance of the modified electrode was investigated by cyclic voltammetry using potassium ferricyanide as an electron probe. The electrochemical response of the electrode to DA was examined by pulse voltammetry. The detection conditions such as the mass ratio of the modified material， the ratio of the template molecule and functional monomer to the cross-linker， the number of electrochemical deposition cycles， the enrichment time， and pH were optimized. The detection results showed that the constructed sensor had a high electrochemical response to DA， with a detection range of 1×10^-6—1×10^-2 mol/L and a minimum detection limit of 4.228 μmol/L（S/N=3）. The sensor exhibited good anti-interference and repeatability. DA in urine samples was detected by the standard addition method， with recovery rates ranging from 82.5% to 93.75% and RSDs all below 5%. The DA detection molecularly imprinted electrochemical sensor constructed in this experiment has high sensitivity and reliability， providing a method and idea for the detection of DA samples.

Key words: Dopamine, Electrochemical sensor, Molecular imprinting, MXenes, Ti₃C₂T _x, Ketjen black

中图分类号:

O657.11

TrendMD:

任书芳, 郭童, 王子涵, 刘亚慧, 陈雨, 曾俊菱. 基于二维Ti₃C₂T _x 纳米片/导电科琴黑复合材料聚甲基丙烯酸分子印迹电化学传感器的构建及多巴胺检测. 高等学校化学学报, 2025, 46(7): 20250040.

REN Shufang, GUO Tong, WANG Zihan, LIU Yahui, CHEN Yu, ZENG Junling. Construction of Molecular Imprinted Electrochemical Sensor Based on 2D Ti₃C₂T _x Nanosheet/Conductive Kochen Black Composite Polymethacrylic Acid and the Detection of Dopamine. Chem. J. Chinese Universities, 2025, 46(7): 20250040.

图/表 6

Fig.1 XRD patterns of the prepared material(A), FESEM images of d⁃Ti3C2T x (B), KB(C) and d⁃Ti3C2T x /KB(D), the high⁃magnification FESEM image of d⁃Ti3C2T x /KB(E) and the FETEM image of d⁃Ti3C2T x /KB(F)

Fig.2 CV curves of electrodes modified with different conductive carrier materials(A) and MIP and NIP membranes(B), CV peak currents of electrodes modified with different materials(C), DPV curves of different modified electrodes for the detection of 0.1 mmol/L DA(D), CV curves of GCE at different scan rates(E), CV curves of the electrode modified with d⁃Ti3C2T x /KB at different scan rates(F), the linear relationship between the CV peak current of GCE at different scan rates and the square root of the scan rate(G) and the linear relationship between the CV peak current of the electrode modified with d⁃Ti3C2T x /KB at different scan rates and the square root of the scan rate(H)MIP1： MIP membrane before elution； MIP2： MIP membrane after elution； NIP1： NIP membrane before elution； NIP2： NIP membrane after elution.

Fig.3 CV peak currents of d⁃Ti3C2T x and KB with different mass ratios(A), DPV peak currents of electrodes modified with different ratios of monomers to templates(B), DPV peak currents of MIP membrane electrodes with different numbers of polymerization cycles(C), DPV peak currents of the MIP⁃modified electrode at different elution time(D), peak currents of the detection of DA after the modified electrode was incubated in DA solution for different time(E), DPV curves of the detection of DA at different pH in PBS(F), the relationship diagram between the DPV peak current of the detection of DA at different pH values in PBS(G) and the relationship diagram of the change of the DPV oxidation potential of the detection of DA with different pH values in PBS(H)The insets are the corresponding CV or DPV curves.

Fig.4 DPV response curves at different DA concentrations(1×10⁻², 1×10⁻³, 1×10⁻⁴, 1×10⁻⁵ and 1×10⁻⁶ mol/L)(A), the linear relationship fitting diagram for DA in the range of 1×10⁻⁶—1×10⁻² mol/L(B), the DPV curves of MIP and NIP sensors toward DA(0.1 mmol/L) and structural analogs of acetaminophen(AP), glucose(GL)(0.1 mmol/L)(C), bar chart of peak current(D), the DPV response diagram using 5 parallel MIP/d⁃Ti3C2T x /KB/GCE in PBS solution containing 0.1 mmol/L DA(E), bar chart of peak current (F)

Table 1 Determination of the concentration of DA and the calculated recovery in human urine by MIP/d-Ti3C2Tx/KB/GCE

Simulated sample	Added/（mmol·L^-1）	Detected/（mmol·L^-1）	Recovery（%）	RSD（%， n=3）
Human urine	0	0	0	0
	0.100	0.087	87.00	2.7
	0.040	0.033	82.50	4.3
	0.016	0.015	93.75	4.5

Fig.5 Representative DPU curves of human urine after adding DA using standard addition method

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基于二维Ti₃C₂T _x 纳米片/导电科琴黑复合材料聚甲基丙烯酸分子印迹电化学传感器的构建及多巴胺检测

Construction of Molecular Imprinted Electrochemical Sensor Based on 2D Ti₃C₂T _x Nanosheet/Conductive Kochen Black Composite Polymethacrylic Acid and the Detection of Dopamine

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