College of Chemistry, Guangdong University of Petrochemical Technology, Guandu Road, Maoming, Guangdong, 525000, PR China; School of Life and Environmental Sciences, Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin, Guangxi, 541004, PR China.
School of Life and Environmental Sciences, Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin, Guangxi, 541004, PR China.
Anal Chim Acta. 2022 Aug 15;1221:340102. doi: 10.1016/j.aca.2022.340102. Epub 2022 Jun 20.
Golgi protein 73 (GP73) is a new type of marker that can specifically detect hepatocellular carcinoma (HCC). Herein, a dual-signal sandwich-type electrochemical aptasensor for GP73 determination was constructed on the basis of hemin-reduced graphene oxide-manganese oxide (H-rGO-MnO) nanozymes. Gold@poly(o-phenylenediamine) (Au@POPD) nanohybrids with a large specific surface area and conductance were co-electro-deposited onto a screen-printed electrode (SPE) surface to immobilize GP73 capture aptamer 2 (Apt2). H-rGO-MnO nanozymes were used not only to immobilize amino functionalised GP73 aptamer 1 (Apt1) as the detection probe, but also to serve as an in-situ redox signal indicator because of the redox reaction of Hemin (Fe(Ш)/Hemin(Fe(II)). In addition, given their excellent peroxidase-like activity, H-rGO-MnO nanozymes can catalyse the decomposition of HO and oxidation of substrate (3,3',5,5'-tetramethylbenzidine, TMB) to oxTMB, which is used as another redox signal. In the presence of the target GP73, the two aptamers specifically bind to the target, thereby affecting two electrochemical signals. Under optimal conditions, the dual-signal sandwich-type electrochemical aptasensor had a salient analytical performance. The two electrochemical redox signals linearly increase with the logarithm of the GP73 concentration in the range of 0.01-100.0 ng/mL with the limit of detection (LOD) of 0.0071 ng/mL and sensitivity of 2.441 μA/μM/cm. Moreover, the recovery of human serum samples ranged from 98.66% to 121.11%. Furthermore, the two redox signals can simultaneously corroborate each other, thereby preventing missed diagnosis and misdiagnosis. All the results can provide new insights into the clinically effective determination of HCC.
高尔基体蛋白 73（GP73）是一种新型的肝癌（HCC）特异性标志物。在此，基于血红素还原氧化石墨烯-氧化锰（H-rGO-MnO）纳米酶构建了用于 GP73 测定的双信号夹心型电化学适体传感器。具有大比表面积和电导率的金@聚邻苯二胺（Au@POPD）纳米杂化物被共电沉积到丝网印刷电极（SPE）表面上，以固定 GP73 捕获适体 2（Apt2）。H-rGO-MnO 纳米酶不仅用于固定氨基功能化的 GP73 适体 1（Apt1）作为检测探针，而且还由于血红素（Fe(Ш)/Hemin(Fe(II))的氧化还原反应而用作原位氧化还原信号指示剂。此外，由于其优异的过氧化物酶样活性，H-rGO-MnO 纳米酶可以催化 HO 的分解和底物（3,3',5,5'-四甲基联苯胺，TMB）的氧化成 oxTMB，oxTMB 用作另一个氧化还原信号。在存在靶标 GP73 的情况下，两个适体特异性地与靶标结合，从而影响两个电化学信号。在最佳条件下，双信号夹心型电化学适体传感器具有突出的分析性能。两个电化学氧化还原信号随 GP73 浓度在 0.01-100.0ng/mL 的对数范围内线性增加，检出限（LOD）为 0.0071ng/mL，灵敏度为 2.441μA/μM/cm。此外，人血清样品的回收率在 98.66%至 121.11%之间。此外，两个氧化还原信号可以相互佐证，从而防止漏诊和误诊。所有结果都可以为 HCC 的临床有效测定提供新的见解。
