电化学生物传感器 2012

Sensitive electrochemical sensor of tryptophan based on Ag@C core-shell nanocomposite modified glassy carbon electrode.

Analytica chimica acta Mao S, Li W, Long Y, Tu Y, Deng A
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组成图示

Sensitive electrochemical sensor of t... 传感器构成示意图

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传感器类型

电化学生物传感器

检测对象

色氨酸(tryptophan, Trp);样品基质:磷酸盐缓冲液(PBS)、氨基酸注射液、大鼠血清

检测原理

Trp在Ag@C/GC电极表面首先通过碳壳表面羟基、羧基等带电官能团与电极发生静电吸附和富集,提高底物可及性。随后Trp在Ag@C修饰电极上发生直接不可逆电化学氧化,Ag核提供高导电性和电催化活性,碳壳保护Ag核并降低电子转移阻力。氧化过程涉及约2个电子,峰电流随扫描速率平方根线性增加,表明为扩散控制。在优化pH 2.0的PBS中,LSV氧化峰电流随Trp浓度升高而增大,因此可通过峰电流定量Trp。

检测灵敏度

LOD: 4.0 × 10−8 M (S/N = 3);线性范围: 1.0 × 10−7–1.0 × 10−4 M;灵敏度斜率: 51691 μA/M;相关系数: 0.998

效应效果

该电极对Trp选择性良好:8种氨基酸(半胱氨酸、赖氨酸、缬氨酸、亮氨酸、丝氨酸、苏氨酸、组氨酸、异亮氨酸)100倍浓度无干扰;抗坏血酸(AA)、尿酸(UA)和多巴胺10倍浓度不干扰。实际样品采用标准加入法测定氨基酸注射液和大鼠血清中Trp,回收率为97%–104%。操作稳定性RSD为3.9%(10次测定1.0×10−4 M Trp),批间重现性RSD为4.1%(5个独立电极),1个月后保留93%初始活性。与文献方法相比,其LOD为4.0×10−8 M、线性范围1.0×10−7–1.0×10−4 M,具有较低检出限和较宽线性范围。

传感器的构成

  • 基底/换能器电极:玻璃碳电极(GC,直径3 mm),经氧化铝抛光和1.0 M H2SO4循环伏安预处理,提供导电基底与电子转移动力。
  • 纳米材料修饰层:Ag@C核壳纳米复合材料(Ag核/C壳,粒径约200–400 nm),由葡萄糖与AgNO3水热法制备,滴涂10 μL乙醇悬浮液,提供电催化与富集界面。
  • 识别/富集界面:碳壳表面羟基、羧基等官能团(C–OH、C=O/C=C),通过静电作用吸附富集Trp;无抗体/适配体等生物识别元件。
  • 信号标记物:无外源标记物;Trp直接氧化产生氧化峰电流。
  • 电解质/缓冲液:0.1 M PBS(pH 2.0),作为支持电解质并提供适宜氧化环境。

中文摘要

本文报道了一种基于Ag@C核壳纳米复合材料修饰玻璃碳电极(Ag@C/GC)的简单电化学方法,用于检测色氨酸(Trp)。Ag@C核壳纳米颗粒通过一步水热法合成,并经扫描电子显微镜(SEM)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FTIR)表征。电化学行为研究表明,Ag@C/GC电极对Trp氧化具有良好电催化活性,Trp在电极上发生直接电化学过程。其性能提升归因于Ag核与碳壳的协同作用:碳壳保护Ag核、提高底物可及性和Trp–电极界面相互作用,Ag核则提供高导电性和电催化活性。在优化条件下,氧化峰电流与Trp浓度在1.0×10−7至1.0×10−4 M范围内呈线性关系,检出限为4.0×10−8 M(S/N=3)。该电极还用于实际样品中Trp测定,结果令人满意,表明该方法灵敏、简便,具有生物传感和电分析应用潜力。

英文摘要

We here reported a simple electrochemical method for the detection of tryptophan (Trp) based on the Ag@C modified glassy carbon (Ag@C/GC) electrode. The Ag@C core-shell structured nanoparticles were synthesized using one-pot hydrothermal method and characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and Fourier transform-infrared spectroscopy (FTIR). The electrochemical behaviors of Trp on Ag@C/GC electrode were investigated and exhibited a direct electrochemical process. The favorable electrochemical properties of Ag@C/GC electrode were attributed to the synergistic effect of the Ag core and carbon shell. The carbon shell cannot only protect Ag core but also contribute to the enhanced substrate accessibility and Trp-substrate interactions, while nano-Ag core can display good electrocatalytic activity to Trp at the same time. Under the optimum experimental conditions the oxidation peak current was linearly dependent on the Trp concentration in the range of 1.0×10(-7) to 1.0×10(-4) M with a detection limit of 4.0×10(-8) M (S/N=3). In addition, the proposed electrode was applied for the determination of Trp concentration in real samples and satisfactory results were obtained. The technique offers enhanced sensitivity and may trigger the possibilities of the Ag@C nanocomposite towards diverse applications in biosensor and electroanalysis.