Ultrasmall gold decorated bimetallic metal–organic framework based nanoprobes for enhanced chemodynamic therapy with triple amplification

Abstract

Chemodynamic therapy (CDT) has shown potential for important applications in tumor precision therapy, but insufficient endogenous hydrogen peroxide (H₂O₂), overexpressed glutathione (GSH) and a weak Fenton-reaction rate greatly reduced the efficacy of CDT. Herein, a metal–organic framework (MOF) based bimetallic nanoprobe with self-supplying H₂O₂ was developed for enhancing CDT with triple amplification, in which ultrasmall gold nanoparticles (AuNPs) were deposited on Co-based MOFs (ZIF-67), and manganese dioxide (MnO₂) nanoshells were coated to form a ZIF-67@AuNPs@MnO₂ nanoprobe. In the tumor microenvironment, MnO₂ depleted overexpressed GSH to produce Mn²⁺, and the bimetallic Co²⁺/Mn²⁺ nanoprobe accelerated the Fenton-like reaction rate. Moreover, by catalyzing glucose via ultrasmall AuNPs, the self-supplying H₂O₂ further promoted hydroxyl radical (˙OH) generation. Compared with those of ZIF-67 and ZIF-67@AuNPs, the ˙OH yield of ZIF-67@AuNPs@MnO₂ obviously increased, due to which the cell viability decreased to 9.3%, and the tumor completely disappeared, indicating the enhanced CDT performance of the ZIF-67@AuNPs@MnO₂ nanoprobe.