Designing Triangular Silver Nanoplates with GSH/GSSG Surface Mixed States as Novel Nanoparticle-based Redox Mediators for Electrochemical Biosensing

Herein, a dual signal-quenched electrochemical (EC) biosensing strategy utilizing surface-engineered trisodium citrate (TSC)–glutathione (GSH)/oxidized glutathione (GSSG)-capped triangular silver nanoplates (Tri-Ag NPsTSC–GSH/GSSG) as a novel nanoparticle-based redox mediator was explored for biomarker determination. In contrast with conventional redox mediators, Tri-Ag NPsTSC–GSH/GSSG provided more admirable EC performance along with a lower oxidation potential (∼0.14 V). Taking advantage of the split-type mode, the immune response in a 96-well microplate was independent from EC detection, which could effectively eliminate the biological interference and thereby greatly enhance the sensitivity. As for the surface engineering process of Tri-Ag NPs, it was composed of partial GSH replacement and the formation of the GSH/GSSG surface mixed state. Primarily, the signal response of Ag NPsTSC–GSH decreased due to the hindrance of GSH on electron transfer. Moreover, varying proportions of GSH/GSSG could further impede the oxidation process of Tri-Ag NPsTSC–GSH/GSSG and eventually realize efficient dual signal quenching of this system. Notably, the ZIF-67@MIL-88B-GOx nanocomposite as the label was applied for a cascade reaction system with GSH peroxidase-like activities to form the optimal GSH/GSSG proportion, causing sensitive changes in signal response with a range of different antigen concentrations. On this basis, the fabricated biosensor provided measurable outputs of aflatoxin B1 concentrations in a linear range of 0.0005–50 ng/mL with a low detection limit of 0.61 pg/mL (S/N = 3). All of the results indicated that the novel biosensor could be a promising analytical tool for future biomarker detection.