传感器类型
电化学生物传感器
检测对象
过氧化氢(hydrogen peroxide, H2O2)、葡萄糖(glucose, D-glucose);样品基质:磷酸盐缓冲液(PBS, pH 7.4)
检测原理
该传感器以Au/Pd纳米立方体-SWCNT网络为工作电极。H2O2检测中,H2O2在0.5 V下于Au/Pd纳米立方体和SWCNT表面发生电催化氧化:H2O2→2H+ + O2 + 2e−,氧化电流随H2O2浓度升高而增大;H2SO4/NaOH预处理增加SWCNT缺陷和含氧基团,增强电子传输。葡萄糖检测中,GOx催化D-glucose + O2 + H2O生成D-葡萄糖酸和H2O2,随后H2O2在电极表面氧化产生电流,电流与葡萄糖浓度成正比。Au/Pd纳米立方体提供电催化活性、低电阻接触和酶固定微环境,实现信号放大。
检测灵敏度
LOD: H2O2 2.3 nM (S/N = 3);葡萄糖 1.3 μM (S/N = 3);线性范围: 葡萄糖 10 μM–50 mM;灵敏度: H2O2 2.6 mA mM−1 cm−2,葡萄糖 5.2 μA mM−1 cm−2
效应效果
该传感器在PBS中对H2O2和葡萄糖均呈线性安培响应。葡萄糖检测限1.3 μM,线性范围10 μM–50 mM,灵敏度5.2 μA mM−1 cm−2,响应时间<6 s;H2O2检测限2.3 nM,灵敏度2.6 mA mM−1 cm−2。与AuNP、对齐SWCNT阵列、Au-MWCNT阵列和Au纳米线葡萄糖传感器相比,其检测限、线性范围和响应时间更优;例如Au/cystamine/GOx为8.2 μM、0.02–5.7 mM、8 s,GOx/AuNWs-chitosan为5.0 μM、0.01–10 mM、8 s。作者认为其适合糖尿病血糖检测及多种临床生物标志物安培检测,并可扩展至微传感器/单细胞应用。原文未报告选择性、抗干扰、稳定性、RSD和实际样品回收率。
传感器的构成
- 基底/导电层:Si/SiO2片上热蒸发Ti(100 nm)/Al(100 nm)/Fe(1 nm)/Al(400 nm)金属膜,Ti作底电极与粘附层,Fe催化SWCNT生长
- 模板层:多孔阳极氧化铝PAA/AAO,孔径约20 nm、间距约100 nm,提供SWCNT生长孔道与支撑
- 换能网络层:单壁碳纳米管SWCNT,从PAA孔内生长并横向铺展,形成低密度互连网络,作为纳米电极与电子传输通道
- 金属接触层:Pd纳米线填充PAA孔,连接Ti底电极与SWCNT,提供低电阻电接触
- 纳米立方体层:Pd纳米立方体在SWCNT缺陷位点电沉积形成,增强H2O2电催化并提供Au生长模板
- 金包覆层:Au薄层电沉积包覆Pd纳米立方体,提供生物相容性、抗氧化/抗污和巯基功能化位点
- 面积定义层:Al2O3 400 nm光刻覆盖非活性区,定义电极面积并优化信噪比
- 连接/识别层:硫醇连接子dithiobis(succinimidyl undecanoate)或生物素化PEG烷硫醇,将GOx或链霉亲和素共价固定到Au表面
- 识别元件:葡萄糖氧化酶GOx或链霉亲和素streptavidin,催化葡萄糖氧化或捕获生物素标记物
中文摘要
本文报道了一种由单壁碳纳米管(SWCNT)网络负载金包覆钯(Au/Pd)纳米立方体构成的电化学生物传感器。该传感器在安培法检测过氧化氢(H2O2)时表现出高灵敏度(2.6 mA mM−1 cm−2)和低估计检出限(2.3 nM,S/N=3)。通过硫醇连接,荧光标记链霉亲和素可选择性固定在纳米立方体表面,验证了Au/Pd纳米立方体的生物功能化能力。进一步将葡萄糖氧化酶(GOx)固定于纳米立方体表面,实现葡萄糖的安培检测。葡萄糖检出限为1.3 μM(S/N=3),线性范围为10 μM至50 mM,显著优于类似碳纳米管基生物传感器。该结构制备简单、可扩展,并兼容多种生物功能化方案,适用于糖尿病患者血糖检测及多种临床重要生物标志物的安培检测。
英文摘要
Networks of single-walled carbon nanotubes (SWCNTs) decorated with Au-coated Pd (Au/Pd) nanocubes are employed as electrochemical biosensors that exhibit excellent sensitivity (2.6 mA mM(-1) cm(-2)) and a low estimated detection limit (2.3 nM) at a signal-to-noise ratio of 3 (S/N = 3) in the amperometric sensing of hydrogen peroxide. Biofunctionalization of the Au/Pd nanocube-SWCNT biosensor is demonstrated with the selective immobilization of fluorescently labeled streptavidin on the nanocube surfaces via thiol linking. Similarly, glucose oxidase (GOx) is linked to the surface of the nanocubes for amperometric glucose sensing. The exhibited glucose detection limit of 1.3 muM (S/N = 3) and linear range spanning from 10 muM to 50 mM substantially surpass similar CNT-based biosensors. These results, combined with the structure's compatibility with a wide range of biofunctionalization procedures, would make the nanocube-SWCNT biosensor exceptionally useful for glucose detection in diabetic patients and well suited for a wide range of amperometric detection schemes for clinically important biomarkers.