基于镍钼硫化物纳米花修饰碳纳米管的脑利钠肽电化学免疫传感器的构建

李燕; 朱长慧; 代玉雪; 李志英

doi:10.16495/j.1006-3757.2023.03.007

基于镍钼硫化物纳米花修饰碳纳米管的脑利钠肽电化学免疫传感器的构建

doi: 10.16495/j.1006-3757.2023.03.007

1.
济南大学化学化工学院，山东济南　250022
2.
山东农业工程学院资源与环境工程学院，山东济南　250100
3.
新沂市时集中学，江苏徐州　221418

详细信息

作者简介:
李燕（1979−），女，实验师，主要从事电化学传感器的构建、环境污染物的处理等，E-mail：chm_liy@ujn.edu.cn

通讯作者:
代玉雪（1988−），女，讲师，主要从事电化学传感器的构建以及环境能源类催化剂的研发等，E-mail：daiyuxue_sd@163.com

中图分类号: O657. 1
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- 被引次数: 0
出版历程
- 收稿日期: 2023-04-29
- 录用日期: 2023-07-25
- 修回日期: 2023-07-25
- 刊出日期: 2023-09-25

Construction of Electrochemical Immunosensor for Ultrasensitive Determination of Brain Natriuretic Peptide Based on Nanocomposite of Nickel Molybdenum Sulfide Supported on Carbon Nanotubes

LI Yan^1
,,
ZHU Changhui³,
DAI Yuxue^{2
, ,},
LI Zhiying¹

1.
School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China
2.
College of Resources and Environmental Engineering, Shandong Agriculture and Engineering University, Jinan 250100, China
3.
Xinyi Shiji Secondary School, Xuzhou 221418, Jiangsu China

摘要

摘要: 制备了一种三维多孔镍钼硫化物纳米花修饰碳纳米管（CNT）的复合材料（NiMoS@CNT）. 通过扫描电子显微镜和X射线衍射表征所合成材料的形貌和结构. 利用循环伏安法和计时电流法对所制备材料的电化学催化性能进行研究. 基于NiMoS@CNT对过氧化氢（H₂O₂）优异的电催化性能，构建了一种检测脑利钠肽的夹心型电化学传感器. 在最优条件下，电流响应强度和脑利钠肽质量浓度的对数在0.20~20 ng/mL范围内呈线性关系. 结果表明免疫传感器具有高的灵敏度、选择性和稳定性，可用于实际样品的检测.
- 电化学传感器 /
- 脑利钠肽 /
- 碳纳米管 /
- 镍钼硫化物
Abstract: A three-dimensional porous nickel molybdenum sulfide nanoflowers supported on carbon nanotubes (CNT) composite materials (NiMoS@CNT) was prepared. The morphology and structure of the synthesized materials were characterized by scanning electron microscopy and X-ray diffraction. The cyclic voltammetry and chronoamperometry were used to study the electrochemical catalytic performance of the prepared materials. Based on the excellent electrocatalytic performance of NiMoS@CNT for hydrogen peroxide, a sandwich electrochemical sensor for detecting brain natriuretic peptide (BNP) was constructed. Under the optimal conditions, the current response intensity and the logarithm of mass concentration of brain natriuretic peptide was linear in the range of 0.20~20 ng/mL. The immunosensor has a high sensitivity, selectivity and stability, and can be used for the detection of BNP in actual samples.
- electrochemical immunosensor /
- brain natriuretic peptide /
- carbon nanotubes /
- nickel molybdenum sulfide

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图 1 夹心型免疫传感器制备示意图

Figure 1. Schematic diagram of processing of sandwich immunosensor

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图 2 （A）NiS、（B）MoS₂和（C）（D）NiMoS@CNT的SEM图

Figure 2. SEM images of (A) NiS, (B) MoS₂ and (C) (D) NiMoS@CNT

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图 3 （a）NiMoS@CNT、（b）NiS和（c）MoS₂的XRD图

Figure 3. XRD spectra of (a) NiMoS@CNT, (b) NiS and (c) MoS₂

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图 4 在 PBS（pH=7.4）中加入5 mmol/L H₂O₂的（A）计时电流曲线和（B）循环伏安扫描曲线

（a）GCE，（b）NiS/GCE，（c）MoS₂/GCE，（d）NiMoS@CNT/GCE

Figure 4. (A) Chronoamperometry curves and (B) cyclic voltammetry curves of (a) GCE, (b) NiS/GCE, (c) MoS₂/GCE, (d) NiMoS@CNT/GCE in PBS solution (pH=7.4) containing 5 mmol/L H₂O₂

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图 5 （a）GCE、（b）CNT-Ab1/GCE、（c）BSA/CNT-Ab1/GCE、（d）BNP/BSA/CNT-Ab1/GCE、（e）NiMoS@CNT-Ab2/BNP/BSA/CNT-Ab1/GCE在含有2 mmol/L K₃[Fe(CN)₆]和0.1 mol/L KCl的PBS（pH=7.4）溶液中的循环伏安曲线图

Figure 5. Cyclic voltammetry curves of (a) GCE, (b) CNT-Ab1/GCE, (c) BSA/CNT-Ab1/GCE, (d) BNP/BSA/CNT-Ab1/GCE and (e) NiMoS@CNT-Ab2/ BNP/BSA/CNT-Ab1/GCE in PBS (pH=7.4) solution containing 2 mmol/L K₃[Fe(CN)₆] and 0.1 mol/L KCl

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图 6 （A）PBS溶液pH对传感器电流的影响（10 ng/mL BNP），（B）CNT-Ab1质量浓度对传感器电流的影响（10 ng/mL BNP），（C）NiMoS@CNT-Ab2质量浓度对传感器电流的影响（10 ng/mL BNP）

Figure 6. Effect of (A) pH of PBS solution, (B) concentration of CNT-Ab1 and (C) concentration of NiMoS@CNT-Ab2 on response of prepared immunosensor to detect 10 ng/mL BNP

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图 7 （A）检测不同质量浓度BNP的免疫传感器的电化学信号，（B）检测不同浓度BNP的免疫传感器的标准曲线

（a）~（g）BNP质量浓度分别为0.20、0.50、1.0、3.0、5.0、10和20 ng/mL

Figure 7. (A) Chronoamperometry curves of immunosensor for detecting different concentrations of BNP, (B) calibration plots of immunosensor to detect different concentrations of BNP

(a) ~ (g) BNP concentrations of 0.20, 0.50, 1.0, 3.0, 5.0, 10 and 20 ng/mL, respectively

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图 8 （A）5根不同电极上制备的传感器用于检测10.0 ng/mL BNP的电化学信号，（B）传感器制备当天以及放置4、8、12、16天后用于检测10.0 ng/mL BNP的电化学信号，（C）传感器对10.0 ng/mL BNP、10.0 ng/mL BNP+1.0 μg/mL AFP、10.0 ng/mL BNP+1.0 μg/mL glucose、10.0 ng/mL BNP+1.0 μg/mL AA、10.0 ng/mL BNP+1.0 μg/mL CEA的电化学信号

Figure 8. (A) Electrochemical signals of immunosensor prepared on 5 different electrodes to detect 10.0 ng/mL BNP, (B) electrochemical signals of immunosensor to detect 10.0 ng/mL BNP on day of sensor preparation and after 4, 8, 12 and 16 days of placement, (C) electrochemical signals of immunosensor for 10.0 ng/mL BNP, 10.0 ng/mL BNP+1.0 μg/mL AFP, 10.0 ng/mL BNP+1.0 μg/mL glucose, 10.0 ng/mL BNP+1.0 μg/mL AA, 10.0 ng/mL BNP+1.0 μg/mL CEA

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表 1 不同方法检测BNP的比较

Table 1. Comparison of different methods for detecting BNP

方法	线性范围	检测限	参考文献
Abbott AxSym BNP 检测法	0~4 000 pg/mL	−	[19]
电化学免疫传感器	0.014~15 ng/mL	4 pg/mL	[10]
电位分辨电化学发光免疫传感器	5 pg/mL~20 ng/mL	3.8 pg/mL	[20]
电化学免疫法	1~10 ng/mL	0.56 pg/mL	[11]
电化学方法	0.20~20 ng/mL	0.057 ng/mL	本研究

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表 2 实际样品的检测（n=5）

Table 2. Recovery of prepared immunosensor (n=5)

样品BNP质量浓度/(ng/mL)	添加BNP质量浓度/(ng/mL)	平均质量浓度/(ng/mL)	RSD/%	回收率/%
0.37	2.00	2.32	3.04	97.50
0.37	5.00	5.43	2.56	101.20

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