电化学生物传感器 2012

Hydrogen peroxide and glucose biosensor based on silver nanowires synthesized by polyol process.

The Analyst Yang X, Bai J, Wang Y, Jiang X, He X
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组成图示

Hydrogen peroxide and glucose biosens... 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

过氧化氢(H2O2,PBS缓冲液)、葡萄糖(glucose,PBS缓冲液及人血清/血液)

检测原理

PVP-AgNWs/GCE在−0.3 V下对H2O2具有电催化还原活性,H2O2在银纳米线表面发生电子转移并被还原,产生与H2O2浓度成正比的还原电流;纳米线网络提供高导电性和较大界面,增强电流响应。葡萄糖检测时,GOD作为识别元件选择性催化葡萄糖与O2反应生成葡萄糖酸和H2O2,生成的H2O2随即在PVP-AgNWs表面被电化学还原,形成安培电流。因此葡萄糖浓度越高,H2O2生成量越大,还原电流越强。低工作电位可避免血液中常见电活性物质干扰,壳聚糖层有助于固定GOD并提高稳定性。

检测灵敏度

H2O2:LOD: 2.30 mM (S/N=3);线性范围: 0.02–3.62 mM;R = 0.998。葡萄糖(PBS):线性范围: 2–20 mM;灵敏度: 22.43 mA mM−1 cm−2;R = 0.987。葡萄糖(人血清加标):线性范围: 1.5–6.5 mM;灵敏度: 15.86 mA mM−1 cm−2;R = 0.998。

效应效果

H2O2传感器响应时间小于2 s,对1 mM H2O2连续5次测量RSD为3.9%,7天后电流仅下降8.4%;低工作电位下共存电活性物质无明显干扰,且检出限低于多种AgNP修饰电极。葡萄糖传感器对5 mM葡萄糖连续6次测量RSD为4.4%,第2天和第5天分别保留96%和81%初始响应;0.5 mM抗坏血酸、尿酸和多巴胺对5 mM葡萄糖响应无明显影响。人血清加标实验线性范围为1.5–6.5 mM,灵敏度15.86 mA mM−1 cm−2,作者认为优于AuNPs-石墨烯复合生物传感器,适用于人血糖检测。

传感器的构成

  • 基底/换能器电极:玻璃碳电极(GCE),经氧化铝抛光和超声清洗,作为工作电极与导电基底。
  • 纳米材料修饰层:PVP保护的银纳米线(PVP-AgNWs),滴涂干燥成膜,提供导电网络、高比表面积和H2O2电催化还原活性。
  • 识别元件:葡萄糖氧化酶(GOD),滴涂固定于PVP-AgNWs/GCE表面,选择性催化葡萄糖氧化生成H2O2;H2O2传感器无此层。
  • 封闭/保护层:壳聚糖(chitosan,0.2%),滴涂干燥,用于固定GOD并降低干扰。
  • 信号中间体:H2O2,由GOD催化葡萄糖产生,也可作为直接检测物,在PVP-AgNWs表面发生电化学还原。
  • 缓冲介质:磷酸盐缓冲液(PBS),提供离子导电和pH稳定;葡萄糖检测需O2饱和,H2O2检测需N2饱和。

中文摘要

本文采用多元醇法以聚乙烯吡咯烷酮(PVP)为保护剂合成银纳米线(PVP-AgNWs),并将其作为新型电极材料构建传感器。以过氧化氢(H2O2)和葡萄糖为分析物评价其传感性能。PVP-AgNWs修饰的玻璃碳电极(PVP-AgNWs/GCE)对H2O2还原表现出显著电催化活性,安培响应时间小于2 s,催化电流在20 μM–3.62 mM范围内与H2O2浓度呈线性关系(R=0.998),信噪比为3时检出限为2.30 mM。进一步将葡萄糖氧化酶(GOD)固定于PVP-AgNWs/GCE表面,制备葡萄糖生物传感器。该传感器可用于人血清中葡萄糖检测,灵敏度为15.86 mA mM−1 cm−2,并具有良好的选择性和稳定性。结果表明,PVP-AgNWs为构建无酶H2O2传感器和酶促葡萄糖生物传感器提供了新的电极材料。

英文摘要

Silver nanowires synthesized through a polyol process using polyvinylpyrrolidone as protection (PVP-AgNWs) were used as a new electrode material for constructing a sensor. Hydrogen peroxide (H(2)O(2)) and glucose were used as analytes to demonstrate the sensor performance of the PVP-AgNWs. It is found that the PVP-AgNWs-modified glassy carbon electrode (PVP-AgNWs/GCE) exhibits remarkable catalytic performance toward H(2)O(2) reduction. This sensor has a fast amperometric response time of less than 2 s and the catalytic current is linear over the concentration of H(2)O(2) ranging from 20 μM to 3.62 mM (R = 0.998) with a detection limit of 2.3 μM estimated on a signal-to-noise ratio of 3. A glucose biosensor was constructed by immobilizing glucose oxidase (GOD) onto the surface of the PVP-AgNWs/GCE. The resultant glucose biosensor can be used for glucose detection in human blood serum with a sensitivity of 15.86 μA mM(-1) cm(-2) and good selectivity and stability.