Abstract
Artificial enzymes mimicking natural processes offer promising solutions for treating infections, but their development faces challenges in synthesis complexity and therapeutic performance. We present a modular-assembly strategy to construct hierarchical MOF@COF heterostructures through covalent interface engineering, bypassing the need for function-specific monomer synthesis while amplifying functionality. By growing porphyrin-based COF shell on amino-functionalized Fe-MIL-88A MOF core, we achieved a morphology-controlled core-shell architecture with well-defined heterojunctions. This hybrid integrates the MOF's dual peroxidase- and catalase-like activities with the COF's photoactivity, enabling cascade therapeutic effects. MOF@COF selectively converts endogenous H(2)O(2) into bactericidal ⋅OH and O(2) within infected tissues, enhancing photodynamic therapy through improved light harvesting and charge separation while alleviating hypoxia-induced resistance. As a broad-spectrum antimicrobial agent, MOF@COF simultaneously utilizes and remodels the infectious microenvironment, significantly accelerating wound healing. This work demonstrates a rational design approach for biocompatible artificial enzymes with synergistic catalytic sites, advancing self-reinforcing therapeutic strategies for infection treatment.