使用双金属纳米复合材料快速灵敏地检测全血样品中氧化型谷胱甘肽。

Rapid and sensitive electrochemical detection of oxidized form of glutathione in whole blood samples using Bi-metallic nanocomposites.

机构信息

Biomaterials Research Laboratory (BMRL), Department of Chemical Engineering, College of Engineering and Technology, SRM Institute of Science and Technology, Kattankulathur, 603203, Chengalpattu, Tamil Nadu, India; Department of Mechanical Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka, Tenpaku-cho, Toyohashi, Aichi, 441-8580, Japan.

Department of Physics and Nanotechnology, College of Engineering and Technology, SRM Institute of Science and Technology, Kattankulathur, 603203, Chengalpattu, Tamil Nadu, India.

出版信息

Chemosphere. 2024 Jan;346:140517. doi: 10.1016/j.chemosphere.2023.140517. Epub 2023 Oct 23.

DOI:10.1016/j.chemosphere.2023.140517

PMID:37879374

Abstract

We report a facile one-pot synthesis of bimetallic nickel-gold (Ni-Au) nanocomposite for ultra-sensitive and selective electrochemical detection of oxidized glutathione (GSSG) by electrochemical deposition on fluorine doped tin oxide (FTO) substrate. The electrodeposition of Ni-Au nanocomposite on FTO was confirmed by various characterization techniques such as field emission scanning electron microscopy (FE-SEM), X-ray diffractometer (XRD) and Fourier transform infra-red (FTIR) spectroscopy. The cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) was utilized for the electrochemical characterization of glutathione reductase (GR)/Ni-Au/FTO working electrode at each stage of modification. The GR enzyme immobilized on the Ni-Au/FTO working electrode via glutaraldehyde cross-linking exhibited excellent selectivity against GSSG in the presence of nicotinamide adenine dinucleotide phosphate (NADPH). The immobilized GR enzyme breaks down the GSSG to reduced glutathione (GSH) and converting NADPH to NADP whereby generating an electron for the electrochemical sensing of GSSG. The synergistic behavior of bimetals and good electro-catalytic property of the fabricated sensor provided a broad linear detection range from 1 fM to 1 μM with a limit of detection (LOD) of 6.8 fM, limit of quantification (LOQ) of 20.41 fM and sensitivity of 0.024 mA/μM/cm. The interference with other molecules such as dopamine, glycine, ascorbic acid, uric acid and glucose was found to be negligible due to the better selectivity of GR enzyme towards GSSG. The shelf-life and response time of the fabricated electrode was found to be 30 days and 32 s, respectively. The real sample analysis of GSSG in whole blood samples showed average recovery percentage from 95 to 101% which matched well with the standard calibration plot of the fabricated sensor with relative standard deviation (RSD) below 10%.

摘要

我们报告了一种简便的一锅法合成双金属镍金（Ni-Au）纳米复合材料，通过电化学沉积在掺氟氧化锡（FTO）基底上，用于超灵敏和选择性电化学检测氧化型谷胱甘肽（GSSG）。通过场发射扫描电子显微镜（FE-SEM）、X 射线衍射仪（XRD）和傅里叶变换红外（FTIR）光谱等各种表征技术证实了 Ni-Au 纳米复合材料在 FTO 上的电沉积。通过戊二醛交联将谷胱甘肽还原酶（GR）固定在 Ni-Au/FTO 工作电极上，在每个修饰阶段都利用循环伏安法（CV）和电化学阻抗谱（EIS）对 GR/Ni-Au/FTO 工作电极进行电化学表征。在烟酰胺腺嘌呤二核苷酸磷酸（NADPH）存在下，固定在 Ni-Au/FTO 工作电极上的 GR 酶对 GSSG 表现出优异的选择性。固定化的 GR 酶将 GSSG 分解为还原型谷胱甘肽（GSH），并将 NADPH 转化为 NADP，从而为 GSSG 的电化学传感产生一个电子。双金属的协同作用和所制传感器的良好电催化性能提供了从 1 fM 到 1 μM 的宽线性检测范围，检测限（LOD）为 6.8 fM，定量限（LOQ）为 20.41 fM，灵敏度为 0.024 mA/μM/cm。由于 GR 酶对 GSSG 的更好选择性，与多巴胺、甘氨酸、抗坏血酸、尿酸和葡萄糖等其他分子的干扰可以忽略不计。所制电极的保质期和响应时间分别为 30 天和 32 秒。全血样品中 GSSG 的实际样品分析显示，平均回收率为 95%至 101%，与所制传感器的标准校准曲线吻合良好，相对标准偏差（RSD）低于 10%。