Enhanced Catalytic Cycle of Glucose Oxidation and Reactive Species with ROS and RHS Generation Mediated by Galvanic Engineering of Dual Atomic Sites on Covalent Organic Frameworks Demonstrating Synergistic Bimetal Tumor Treatment

Abstract

This study introduces a novel approach to cancer treatment using covalent organic frameworks (COFs) with dual atomic metal sites, employing a galvanic reaction to integrate both gold (Au) and iridium (Ir) onto COF (COF/Au_x/Ir_1-x). The integration of these metals enables a synergistic catalytic cycle that enhances glucose oxidation and the generation of reactive oxygen species (ROS) and reactive halogen species (RHS). Au catalyzes glucose oxidation, producing gluconic acid and hydrogen peroxide (H₂O₂), while Ir decomposes H₂O₂ into superoxide anion (O₂⁻) and, in the presence of chloride ions (Cl⁻), generates hypochlorous acid (HOCl). The dual metal atomic sites facilitate a feedback cycle where H₂O₂ is efficiently converted back to oxygen (O₂), amplifying ROS and RHS generation within cancer cells. By fine-tuning the Au: Ir ratio through the galvanic reaction, optimal catalytic performance is achieved, creating a highly effective tumor treatment strategy. This work represents the first application of dual metal atomic sites on COFs for cancer therapy, demonstrating significant potential for catalysis-based biomedical applications. The synergistic interactions between Au and Ir enhance catalytic efficiency, offering a new approach to exploiting endogenous cancer cell metabolites for targeted and efficient cancer treatment.

Keywords: catalase; covalent organic frameworks; dual‐atom catalyst; galvanic replacement; glucose oxidase; haloperoxidase.