电化学发光(ECL)生物传感器 2010

Electrogenerated chemiluminescence of blue emitting ZnSe quantum dots and its biosensing for hydrogen peroxide.

Biosensors & bioelectronics Hu X, Han H, Hua L, Sheng Z
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组成图示

Electrogenerated chemiluminescence of... 传感器构成示意图

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传感器类型

电化学发光(ECL)生物传感器

检测对象

过氧化氢(hydrogen peroxide, H2O2);样品基质为猪肾细胞(pk-15)裂解液、Vero细胞裂解液和矿泉水

检测原理

该传感器没有特异性生物识别元件,直接利用H2O2对ZnSe QDs电化学发光的增强作用。在玻璃碳电极上从0.0至−1.4 V(vs Ag/AgCl)扫描时,ZnSe QDs被还原为QDs−;溶解氧O2被还原生成OOH−。H2O2在碱性条件下与OH−反应生成更多OOH−,QDs−与OOH−反应产生激发态QDs*,QDs*退激发射蓝光。H2O2浓度越高,OOH−生成越多,ECL光强越强。NaOH可诱导形成Zn(OH)2壳层,钝化表面陷阱并增强发光。PMT将光信号转换为电信号,实现H2O2定量检测。

检测灵敏度

LOD: 2.00 × 10−7 M (S/N = 3);线性范围: 6.10 × 10−7–3.12 × 10−4 M;灵敏度斜率: 0.0062 (y = 0.0062x + 1.7284);r = 0.9985 (n = 10)

效应效果

在5.00×10−5 M H2O2下重复测定RSD为2.70%(n=11),实际样品10次测定RSD均低于3.0%。矿泉水、pk-15细胞和Vero细胞加标回收率分别为100.37%–104.08%、99.44%–102.34%和102.29%–103.94%,95% CI不重叠零且p<0.01。与分光光度法、比色法、电化学传感器和紫外可见吸收法相比,该方法具有较低检出限和较宽线性范围,未报告长期稳定性与选择性实验,作者认为其可用于真实样品和生物检测。

传感器的构成

  • 工作电极:玻璃碳电极(GCE),作为ECL换能器,施加负电位使ZnSe QDs还原
  • 对电极:铂丝(Pt wire),构成三电极体系并维持电流回路
  • 参比电极:Ag/AgCl电极,提供电位基准
  • 发光纳米材料:GSH包覆ZnSe量子点(GSH-capped ZnSe QDs),平均粒径2.2 nm,作为ECL发光体
  • 缓冲介质:50 mM PBS(pH 7.4),维持反应环境
  • 共反应物:溶解氧(O2)与H2O2/OH−,生成OOH−并参与ECL反应
  • 表面钝化剂:NaOH,可形成Zn(OH)2壳层,钝化表面陷阱并增强ECL
  • 被测物:过氧化氢(H2O2),浓度升高时增加OOH−生成,增强ECL信号

中文摘要

本文报道了一种基于蓝色发射ZnSe量子点(ZnSe QDs)电化学发光(ECL)检测过氧化氢(H2O2)的新方法。在0.0至−1.4 V(vs Ag/AgCl)电位扫描下,ZnSe QDs在水溶液中产生较弱ECL发射;当存在H2O2或溶解氧时,ECL强度显著增强。在最佳条件下,H2O2的动态范围为6.10×10−7至3.10×10−4 M,检出限(S/N=3)为2.00×10−7 M;在5.00×10−5 M H2O2下相对标准偏差为2.70%(n=11)。作者还探讨了ZnSe QDs的ECL可能反应机制,并将该新型生物传感器用于猪肾细胞(pk-15)、Vero细胞和矿泉水中H2O2的检测。结果表明该方法重现性良好,具有实际样品检测潜力。

英文摘要

A novel method for the detection of hydrogen peroxide (H(2)O(2)) has been developed, based on electrogenerated chemiluminescence (ECL) of blue emitting ZnSe quantum dots (QDs) in aqueous solution. The weak ECL emission of ZnSe QDs was generated when the electrode potential was scanned from 0.0 to -1.4V (versus Ag/AgCl), and the ECL intensity was greatly enhanced in the presence of H(2)O(2) or dissolved oxygen. Under the optimal conditions, the dynamic range is from 6.10 x 10(-7) to 3.10 x 10(-4)M H(2)O(2), and the detection limit (at S/N=3) is 2.00 x 10(-7)M. The relative standard deviation (at 5.00 x 10(-5)M of H(2)O(2)) is 2.70% (n=11). A possible reaction mechanism of ECL of ZnSe QDs was also investigated. As a novel biosensor, it was used to detect H(2)O(2) in the pig kidney (pk-15) cell, vero cell and mineral water, respectively. Moreover, the proposed biosensor showed a good reproducibility and potential application in real samples.

关键词

电化学发光ZnSe量子点过氧化氢生物传感器蓝光发射