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:0.1 M 磷酸盐缓冲液(PBS, pH 7.4),文中亦讨论体内检测中的尿酸、抗坏血酸干扰
检测原理
葡萄糖氧化酶(GOD)通过疏水作用和静电作用固定于壳聚糖包裹单壁碳纳米管(SWCNT–CHI)膜中。当葡萄糖进入电极界面时,GOD 催化葡萄糖氧化生成葡萄糖酸和过氧化氢,其 FAD 辅因子发生氧化还原变化。由于小直径 SWCNT 提供导电通道,CHI 提供生物相容微环境,FAD 中心与玻璃碳电极之间发生直接电子转移,无需外加电子媒介体。在 -400 mV 安培电位下,电子转移产生电流,电流随葡萄糖浓度升高而增大;低检测电位可避免尿酸、抗坏血酸等干扰。
检测灵敏度
LOD: 0.01 mM;线性范围: 1–10 mM(结论部分报告为 1–15 mM);R^2 = 0.998
效应效果
该传感器在 -400 mV 下对葡萄糖响应迅速,稳定响应时间约 10–15 s,并表现出良好抗干扰能力,文中未观察到尿酸、抗坏血酸等干扰。重现性良好,10.0 mM 葡萄糖九次重复测量相对标准偏差小于 3.0%。单支传感器连续使用一周后灵敏度仅下降约 10%,4 ℃保存 15 d 后催化电流几乎无下降,作者归因于网络状纳米复合膜限制 GOD 流失。论文未报告实际样品加标回收率或与 ELISA、HPLC、qPCR 等方法的对比,但作者认为该平台可用于食品分析和生物过程监测中的葡萄糖检测。
传感器的构成
- 基底电极:玻璃碳电极(GC),提供导电基底与电子转移界面
- 纳米修饰层:壳聚糖包裹单壁碳纳米管复合膜(SWCNT–CHI),分散小直径 SWCNT,提供导电通道、高比表面积和生物相容微环境
- 识别元件:葡萄糖氧化酶(GOD),通过疏水作用和静电作用吸附于 SWCNT–CHI 膜,催化葡萄糖氧化并实现直接电子转移
- 信号标记物:无外加标记物(直接电子转移,GOD 的 FAD 中心直接传递电子)
- 缓冲介质:0.1 M 磷酸盐缓冲液(PBS, pH 7.4),维持 GOD 催化活性与电化学环境
- 电极体系:三电极体系(工作电极 GOD/SWCNT–CHI/GC、Pt 对电极、SCE 参比电极),完成循环伏安与安培检测
中文摘要
本文以壳聚糖(CHI)选择性包裹的单壁碳纳米管(SWCNTs)构建用于葡萄糖氧化酶(GOD)直接电子转移(DET)和生物传感的电化学平台。扫描电镜和拉曼光谱表明,小直径 SWCNTs 优先被 CHI 包裹并分散于膜中,在电极表面以小束状存在。在磷酸盐缓冲液中,GOD 与电极间观察到直接电子转移,形式电位约 -460 mV(vs. SCE);异相电子转移速率常数和 GOD 表面覆盖量分别约为 3.0 s−1 和 1.3×10−10 mol/cm2。固定化 GOD 仍保留催化葡萄糖氧化的活性。该 GOD/SWCNT–CHI 膜基传感器在 -400 mV 检测电位下响应迅速、线性范围宽、检出限低,并具有良好的抗干扰能力。其分析性能提升归因于单个 SWCNTs 的独特性质和 CHI 的生物相容性。
英文摘要
Single-walled carbon nanotubes (SWCNTs) selectively wrapped by a water-soluble, environmentally friendly, biocompatible polymer chitosan (CHI) were employed for the construction of a bioelectrochemical platform for the direct electron transfer (DET) of glucose oxidase (GOD) and biosensing purposes. Scanning electron microscopy and Raman spectroscopy were used to investigate the properties of the SWCNT-CHI film. The results show that the preferentially wrapped small-diameter SWCNTs are dispersed within the CHI film and exist on the surface of the electrode as small bundles. The DET between GOD and the electrode surface was observed with a formal potential of about ca. -460 mV vs. SCE in phosphate buffer solution. The heterogeneous electron transfer rate constant and the surface coverage of GOD are estimated to be 3.0 s(-1) and 1.3 x 10(-10)mol/cm(2), respectively. The experimental results demonstrate that the immobilized GOD retains its catalytic activity towards the oxidation of glucose. Such a GOD/SWCNT-CHI film-based biosensor not only exhibits a rapid response time, a wide linear rang and a low detection limits at a detection potential of -400 mV but also shows the effective anti-interference capability. Significantly improved analytical capabilities of the GOD/SWCNT-CHI/GC electrode could be ascribed to the unique properties of the individual SWCNTs and to the biocompatibility of CHI.