传感器类型
电化学生物传感器
检测对象
葡萄糖(glucose, Glc);样品基质:PBS缓冲液、血清
检测原理
葡萄糖扩散进入CS-GA-GOx多孔酶层,被GOx特异性催化氧化,消耗O2并生成葡萄糖酸和H2O2。生成的H2O2穿过Nafion抗干扰膜到达PtPd-MWCNTs催化层;在0.6 V(vs SCE)下,PtPd双金属纳米粒子对H2O2进行电催化氧化,产生与H2O2浓度成正比的电子转移电流。由于H2O2生成速率受GOx-葡萄糖反应控制,稳态安培电流随葡萄糖浓度增加而增大,在0.062–14.07 mM内呈线性。Nafion膜排斥负电干扰物,CS-GA-GOx三维网络促进底物扩散,PtPd-MWCNTs提高催化电流,从而实现低检出限和快速响应。
检测灵敏度
LOD: 0.031 mM;线性范围: 0.062–14.07 mM;灵敏度: 112 μA mM−1 cm−2;R^2 = 0.997
效应效果
该传感器在0.6 V下对葡萄糖响应快,5 s内达到95%稳态电流;5个电极对5 mM葡萄糖响应的RSD为3.7%。4 ℃干燥储存7天后保留95%电流,28天后约85%。Nafion膜使尿酸、抗坏血酸和果糖(各0.5 mM)的干扰可忽略。与商用ETK-20 Pt–C(灵敏度97 μA mM−1 cm−2,线性0.062–12.8 mM)和BASF Pd–C(47 μA mM−1 cm−2,线性0.062–5.99 mM)相比,PtPd-MWCNTs电极灵敏度112 μA mM−1 cm−2、线性0.062–14.07 mM更优。血清样品结果与YSI 2300 STAT Plus分析仪接近,作者认为可用于血糖/血清葡萄糖检测。
传感器的构成
- 基底/工作电极:玻碳电极(GCE),直径5 mm,抛光后作为电化学换能器
- 催化修饰层:PtPd双金属纳米粒子修饰多壁碳纳米管(PtPd-MWCNTs)催化剂,负载于Nafion中滴涂,提供H2O2电催化活性与电子传导
- 抗干扰/封闭层:Nafion膜(0.2 wt%),涂覆于催化层表面,排斥尿酸、抗坏血酸等负电干扰物
- 酶识别层:壳聚糖-戊二醛-葡萄糖氧化酶(CS-GA-GOx)生物复合膜,电沉积形成多孔三维网络,固定酶并促进扩散
- 识别元件:葡萄糖氧化酶(GOx),催化葡萄糖氧化生成H2O2
- 信号换能/催化元件:PtPd-MWCNTs催化H2O2电氧化,将酶反应转化为安培电流
中文摘要
本研究报道了一种基于新型铂钯双金属纳米粒子修饰多壁碳纳米管(PtPd-MWCNTs)的灵敏、选择性且稳定的安培葡萄糖生物传感器。采用改进的Watanabe法制备PtPd-MWCNTs,并用XRD和TEM表征。将PtPd-MWCNTs催化剂固定于Nafion膜中并修饰在玻碳电极上构建传感器;内层Nafion膜用于消除尿酸、抗坏血酸和果糖等常见干扰物。最后通过电沉积制备具有高孔隙率和有序三维网络结构的酶层(CS-GA-GOx)。所得传感器对葡萄糖响应良好,线性范围宽(0.062–14.07 mM),检出限低(0.031 mM),响应时间短(5 s内),灵敏度高(112 μA mM−1 cm−2),米氏常数Km为3.3 mM。此外,传感器重现性好、储存稳定性佳、抗干扰能力满意,并评估了其在实际血清样品分析中的应用。
英文摘要
A sensitive, selective and stable amperometric glucose biosensor employing novel PtPd bimetallic nanoparticles decorated on multi-walled carbon nanotubes (PtPd-MWCNTs) was investigated. PtPd-MWCNTs were prepared by a modified Watanabe method, and characterized by XRD and TEM. The biosensor was constructed by immobilizing the PtPd-MWCNTs catalysts in a Nafion film on a glassy carbon electrode. An inner Nafion film coating was used to eliminate common interferents such as uric acid, ascorbic acid and fructose. Finally, a highly porous surface with an orderly three-dimensional network enzyme layer (CS-GA-GOx) was fabricated by electrodeposition. The resulting biosensor exhibited a good response to glucose with a wide linear range (0.062-14.07 mM) and a low detection limit 0.031 mM. The biosensor also showed a short response time (within 5 s), and a high sensitivity (112 μA mM(-1)cm(-2)). The Michaelis-Menten constant (K(m)) was determined as 3.3 mM. In addition, the biosensor exhibited high reproducibility, good storage stability and satisfactory anti-interference ability. The applicability of the biosensor to actual serum sample analysis was also evaluated.