电化学生物传感器 2012

Novel snowflake-like Pt-Pd bimetallic clusters on screen-printed gold nanofilm electrode for H2O2 and glucose sensing.

Biosensors & bioelectronics Niu X, Chen C, Zhao H, Chai Y, Lan M
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组成图示

Novel snowflake-like Pt-Pd bimetallic... 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(H2O2,0.1 M PBS缓冲液及加标样品)、葡萄糖(glucose,0.1 M PBS缓冲液及模拟血液样品)

检测原理

该传感器以SPGFE为导电基底,表面电沉积雪花状Pt–PdBNC形成三维多孔催化界面。葡萄糖检测时,GOx特异性催化葡萄糖氧化并生成H2O2;H2O2在Pt–PdBNC表面发生电催化还原,电子经金膜传递至工作电极,在恒电位下产生还原电流。Pt与Pd的合金协同效应及三维结构提供更多活性位点并促进电子转移,使电流随葡萄糖浓度升高而线性增大。直接检测H2O2时,Pt–PdBNC同样通过电催化还原H2O2产生电流,电流大小与H2O2浓度成正比。

检测灵敏度

H2O2: LOD: 0.87 mM;线性范围: 0.005–6 mM;灵敏度: 804 mA M−1 cm−2;R^2 = 0.9962。葡萄糖: 线性范围: 0–16 mM;LOD: 10 mM;R^2 = 0.9981。

效应效果

H2O2检测响应时间快,2 s内达到稳态电流的95%;单电极重复测量0.5 mM H2O2的RSD为4.2%,电极间RSD为7.1%;0.5 mM抗坏血酸、多巴胺、尿酸和葡萄糖对0.5 mM H2O2无明显干扰,并可在加标样品中可靠检测。葡萄糖传感器对5 mM葡萄糖的电极间RSD为5.1%;0.5 mM半乳糖、果糖、木糖、核糖和抗坏血酸无干扰,H2O2会显著增加电流。模拟血液样品测得6.13±0.17 mM(n=3),作者认为其线性范围较宽且LOD令人满意,具有实际样品检测潜力。

传感器的构成

  • 基底/换能器电极:丝网印刷金纳米膜电极(SPGFE),金膜厚约75±5 nm,提供导电基底与电化学换能界面
  • 纳米材料修饰层:雪花状Pt–Pd双金属纳米团簇(Pt–PdBNC),由H2PtCl6和PdCl2经恒电位/多电位阶跃电沉积形成,提供三维多孔催化界面并增强H2O2电催化还原
  • 识别元件:葡萄糖氧化酶(GOx,EC 1.1.3.4),固定于Pt–PdBNC表面,特异性催化葡萄糖氧化生成H2O2
  • 固定/封闭剂:戊二醛(glutaraldehyde)与牛血清白蛋白(BSA)交联固定GOx,提高酶稳定性并减少非特异吸附
  • 信号转换层:Pt–PdBNC催化H2O2电还原,将酶反应产生的H2O2转化为可测电流信号
  • 工作介质:0.1 M PBS(pH 6.9),提供离子导电环境并维持GOx活性

中文摘要

本文报道了在丝网印刷金纳米膜电极(SPGFE)上,通过恒电位/多电位阶跃电沉积策略电化学还原前驱体,制备新型雪花状Pt–Pd双金属纳米团簇(Pt–PdBNC)修饰电极。所制备的Pt–PdBNC具有三维多孔结构,暴露大量活性位点,并因Pt与Pd的协同效应显著增强中性介质中H2O2的电催化还原性能,优于Pt和Pd单金属纳米团簇。在优化条件下,SPGFE/Pt–PdBNC对H2O2在0.005–6 mM范围内呈线性响应,灵敏度达804 mA M−1 cm−2,并具有良好的选择性。进一步将葡萄糖氧化酶(GOx)固定于Pt–PdBNC结构上,制备的葡萄糖生物传感器对葡萄糖检测表现出良好性能。

英文摘要

Novel snowflake-like Pt-Pd bimetallic nanoclusters (Pt-PdBNC) were synthesized on a screen-printed gold nanofilm electrode (SPGFE) substrate by electrochemically reducing precursors with a new constant potential/multi-potential step deposition strategy. The electrocatalytic behavior of the modified electrode (SPGFE/Pt-PdBNC) towards H(2)O(2) was investigated. The results indicate that the as-prepared Pt-PdBNC significantly enhances the electrochemical reduction of H(2)O(2) in neutral media, exhibiting preferable electrocatalytic performance compared to Pt and Pd monometallic nanoclusters. Under optimum conditions, SPGFE/Pt-PdBNC offers linear responses for H(2)O(2) in the concentration range from 0.005 to 6 mM with an ultrahigh sensitivity of 804 mA M(-1) cm(-2) and excellent selectivity. Furthermore, glucose oxidase was immobilized on the Pt-PdBNC structure, and the fabricated biosensor presents favorable properties for glucose sensing.