Heterojunction MnO₂-nanosheet-decorated Ag nanowires with enhanced oxidase-like activity for the sensitive dual-mode detection of glutathione

Abstract

The biocatalytic design of nanomaterials with enzyme-like activity is considered a reliable and promising toolkit for the generation of diagnostic agents in complex biological microenvironments. However, the preparation of nanomaterials while maintaining a high catalytic activity in tumor cells (pH 6.0-6.5) poses a prominent challenge. Herein, we constructed a biomimetic enzyme-trigged dual-mode system with colorimetry at 652 nm and photothermal biosensors to detect glutathione based on hollow MnO₂-nanosheet-decorated Ag nanowires (Ag@MnO₂) as an oxidase-like nanozyme. As expected, Ag@MnO₂ catalyzed the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the absence of H₂O₂, leading to a blue-colored oxidized TMB (oxTMB) that displayed oxidase-like activity in pH 6.0. Interestingly, the portable dual-mode colorimetry and photothermal method for GSH was developed based on the redox reaction between GSH and oxTMB. This detection method exhibited a wide linear range of 0.1-55 μM for GSH with a low detection limit of 0.08 μM. This work highlights a new insight into nanotechnology by taking advantage of biomimetic design in biological analysis.