传感器类型
电化学生物传感器
检测对象
过氧化氢(H2O2,hydrogen peroxide);样品基质:磷酸盐缓冲液(PBS)及消毒剂样品
检测原理
该传感器以固定于 Sn–ZnNPs/MWNTs 膜中的血红蛋白(Hb)作为识别和电催化元件。Hb 血红素铁与电极之间发生直接电子转移,CV 中呈现准可逆氧化还原峰。当 H2O2 存在时,Hb[Fe(III)] 与 H2O2 反应生成 Compound I,Compound I 再与 H2O2 反应再生 Hb[Fe(III)] 并释放 O2;电极上 Hb[Fe(III)] 接受电子和质子还原为 Hb[Fe(II)],Hb[Fe(II)] 与 O2 结合后再经电子转移再生 Hb[Fe(III)],总反应为 H2O2+2H+ +2e−→2H2O。H2O2 浓度升高使催化还原电流增大,Sn–ZnNPs/MWNTs 通过高导电性、大比表面积和良好生物相容性促进电子传递,实现无标记电催化放大。
检测灵敏度
LOD: 0.11 μM (S/N = 3);线性范围: 0.5–840 μM;灵敏度: 29.2 μA mM−1;r = 0.9984
效应效果
该传感器抗干扰性良好:在1.0 mM H2O2存在下,0.15 mM抗坏血酸、5.0 mM葡萄糖和0.5 mM尿酸分别使还原电流降低1.2%、2.6%和3.8%,影响可忽略。同一电极对0.05 mM H2O2十次平行测定RSD为3.6%,五个独立制备电极间RSD为4.2%;每两天测试一次,两周后仍保持初始响应的88.2%。在消毒剂样品中测定H2O2,结果与KMnO4滴定法一致,如样品1本方法2.73×10−4 mol/L(RSD 4.3%)对滴定法3.21×10−4 mol/L(RSD 3.5%)。与文献H2O2生物传感器相比,其线性范围0.5–840 μM、检出限0.11 μM和KM 0.379 mM更优,作者认为该复合膜是构建H2O2生物传感器及离子液体中开发生物活性材料的有前景平台。
传感器的构成
- 基底电极:玻璃碳电极(GCE),抛光清洗后作为工作电极和电子转接基底
- 碳纳米管/壳聚糖层:酸化多壁碳纳米管(MWNTs)与壳聚糖(CS)混合液滴涂干燥,形成导电多孔膜,增大表面积并固定纳米颗粒
- 双金属纳米颗粒层:Sn–Zn 纳米颗粒(Sn–ZnNPs)在 Ethaline 离子液体中由 ZnCl2 和 SnCl2 电沉积于 MWNTs 表面,提供导电通道并促进 Hb 直接电子转移
- 识别/催化元件:血红蛋白(Hb)溶于 1 wt.% 壳聚糖(CS)后固定于 Sn–ZnNPs/MWNTs 膜中,催化 H2O2 还原
中文摘要
在 Ethaline 离子液体中同时电沉积 ZnCl2 和 SnCl2 于多壁碳纳米管(MWNTs)上,制备了 Zn–Sn 纳米颗粒/多壁碳纳米管(Zn–SnNPs/MWNTs)纳米复合膜。随后将血红蛋白(Hb)固定于该复合膜中,构建了新型过氧化氢(H2O2)生物传感器,并研究了 Zn–SnNPs 形貌及传感器分析性能。场发射扫描电镜观察到高密度、分布均匀的 Zn–SnNPs 球状颗粒,平均直径约 120 nm。伏安结果表明,传感器上 Hb 呈现一对清晰、准可逆氧化还原峰,形式电位 E0′ 为 −0.40 V,峰间电位差 ΔEp 为 0.086 V。此外,传感器对 H2O2 表现出优异电催化活性,表观 Michaelis–Menten 常数 KM 为 0.379 mM;Hb/Zn–SnNPs/MWNTs/GCE 的还原峰电流在 0.5–840 μM 范围内与 H2O2 浓度呈线性关系,相关系数 0.9984,检出限 0.11 μM(S/N=3)。结果表明,Zn–SnNPs/MWNTs 纳米复合膜是构建 H2O2 生物传感器的有前景平台,也为在离子液体中开发其他生物活性材料提供了途径。
英文摘要
The Zn-Sn nanoparticles/multiwall carbon nanotubes (Zn-SnNPs/MWNTs) nanocomposite film was prepared by electrodeposition of ZnCl(2) and SnCl(2) on MWNTs simultaneously in Ethaline ionic liquids. Then, based on immobilizing hemoglobin (Hb) within a novel Zn-SnNPs/MWNTs nanocomposite film (Hb/Zn-SnNPs/MWNTs), a novel hydrogen peroxide (H(2)O(2)) biosensor was constructed. Meantime, the morphology of the Zn-SnNPs and analytical characteristics of the biosensor were investigated. A high density and well-distributed Zn-SnNPs spheres with an average diameter of 120 nm was observed by field emission scanning electron microscopy. The voltammetric results of the biosensor showed a pair of well-defined and quasi-reversible redox peaks of Hb with a formal potential (E(0')) of -0.40 V and a peak-to-peak separation (ΔE(p)) of 0.086 V. Moreover, the biosensor exhibited an excellent electrocatalytic activity to H(2)O(2) with a K(M) value of 0.379 mM; the reduction peak currents of Hb on the Hb/Zn-SnNPs/MWNTs/GCE were linearly related to H(2)O(2) in the range from 0.5 to 840 μM with a correlation coefficient of 0.9984 and a detection limit of 0.11 μM (S/N=3). Results demonstrated that Zn-SnNPs/MWNTs nanocomposite film was promising a new platform for the construction of H(2)O(2) biosensors and provided a way to develop other biologic active materials in ionic liquids.