Interfacial deposition of Ag nanozyme on metal-polyphenol nanosphere for SERS detection of cellular glutathione

The low polarization and low Raman cross section characteristics of glutathione (GSH) make it challenging to directly detect GSH molecules through surface enhanced Raman scattering (SERS) technology. Development of nanostructures for indirect detection of GSH applied to the SERS platform is of great interest. Herein, silver nanoparticles (Ag NPs)/copper-polyphenol colloidal spheres (denoted as CuTA@Ag) with adjustable Ag NPs coverage are prepared by deposition of Ag NPs on the metal-polyphenol colloidal spheres via an interfacial polyphenol reduction method. The size and density of the Ag NPs deposited on the out layer can be readily adjusted by tailoring the concentrations of silver precursor. It leads to activity difference for the nanozyme and SERS characteristics. The SERS properties of the obtained CuTA@Ag are studied using oxTMB, catalytic products of nanozyme, as the probing molecules. They provide satisfactory SERS performance with a low detection limit of 10-7 M (S/N = 3) and linear determination in the 1-100 μM range for GSH. Moreover, it is further able to detect the glutathione content in cancer cells with well accurate and reproducible capability, catching the signs of rising cancer marker levels. This work proposes structurally tunable nanomaterials platform for a catalytic-based SERS assay, which is expected to utilize the high sensitivity of SERS tool for GSH detection in the cellular environment.