An Au@CuS@CuO2 nanoplatform with peroxidase mimetic activity and self-supply H2O2 properties for SERS detection of GSH

Xiang-Cheng Lin; Jian Liu; Miaomiao Hu; Lingjun Song; Minzhe Li; Qinjie Kou; Rong Huang; Lixian Sun; Changchun Wen

doi:10.1016/j.saa.2025.126376

An Au@CuS@CuO₂ nanoplatform with peroxidase mimetic activity and self-supply H₂O₂ properties for SERS detection of GSH

Spectrochim Acta A Mol Biomol Spectrosc. 2025 Nov 5:340:126376. doi: 10.1016/j.saa.2025.126376. Epub 2025 May 10.

Authors

Xiang-Cheng Lin¹, Jian Liu², Miaomiao Hu³, Lingjun Song², Minzhe Li², Qinjie Kou⁴, Rong Huang⁵, Lixian Sun², Changchun Wen⁶

Affiliations

¹ Guangxi Key Laboratory of Information Materials, School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, China. Electronic address: xclin2008@163.com.
² Guangxi Key Laboratory of Information Materials, School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, China.
³ Guangxi Key Laboratory of Information Materials, School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, China; State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China.
⁴ Department of Clinical Laboratory, The Second Affiliated Hospital of Kunming Medical University, Kunming 650000, China.
⁵ Department of Transfusion, The Third Xiangya Hospital, Central South University, Changsha 410013, China.
⁶ State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China. Electronic address: wcchun@163.com.

PMID: 40378484
DOI: 10.1016/j.saa.2025.126376

Abstract

The abnormal fluctuations of glutathione (GSH) in vivo often reflect disease progression and are closely linked to human metabolism and physiological functions. Highly sensitive and selective detection of GSH is crucial for guiding early diagnosis and treatment; however, achieving this remains a significant challenge. In this study, we developed an enzyme activity sensor platform for the efficient detection of GSH. This platform utilizes Au@CuS core-shell materials loaded with CuO₂ nanoparticles to create a composite nanosensor system. Under slightly acidic conditions, CuO₂ on the nanomaterial's surface decomposes into H₂O₂ and Cu²⁺ ions. The generated H₂O₂ then reacts with tetramethylbenzidine (TMB) in the presence of peroxidase-like CuS to yield oxidized tetramethylbiphenyl (_OXTMB), which generates a distinctive Raman signal. Upon addition of GSH to the system, the unique _OXTMB signal diminishes due to GSH's strong antioxidant capacity and the consequent consumption of _OXTMB. This sensing method enables sensitive detection of GSH, with a detection limit as low as 1.2 × 10^-13 mol∙L^-1. This approach holds promise for providing researchers with rapid and precise in vitro analysis of GSH, serving as an indicator for early disease diagnosis and real-time evaluation of treatment efficacy.

Keywords: CuO(2); Glutathione (GSH); Peroxidase; Surface-enhanced Raman spectroscopy (SERS); TMB.

MeSH terms

Benzidines / chemistry
Biomimetic Materials* / chemistry
Copper* / chemistry
Glutathione* / analysis
Gold* / chemistry
Humans
Hydrogen Peroxide* / chemistry
Limit of Detection
Metal Nanoparticles* / chemistry
Peroxidase* / chemistry
Peroxidase* / metabolism
Spectrum Analysis, Raman* / methods

Substances

Glutathione
Copper
Hydrogen Peroxide
Gold
cupric oxide
Peroxidase
3,3',5,5'-tetramethylbenzidine
Benzidines