Push-Pull Electronic Effect and D-Band Center Bi-Modulated Bio-Heterojunction Enzyme Enables All-Stage Infected Wound Healing.

Abstract

Pathogenic infections pose a persistent threat to global public health, necessitating innovative antibacterial strategies with well-defined disinfection pathway. The antibacterial efficiency is confined in the contradiction between reactants adsorption and intermediates desorption. Here, the FeMoS₄/MXene bio-heterojunction enzyme (FM BioHJzyme) is proposed and constructed. Under the inspiration of near-infrared light (NIR), the heterostructures between the FeMoS₄ and MXene facilitates efficient electron-hole separation with localized electron accumulation at FeMoS₄ sites. Crucially, the electronic push-pull effect induced by Mo polarizes oxygen-containing reactants (H₂O₂, H₂O, O2) toward Fe active centers, enabling sequential electron capture for reactive oxygen species (ROS) generation. The results also reveal an enhancement in electron density at Fe sites compared to FeS/MXene controls, which is accompanied by a downshift in the Fe d-band center that reduces intermediates adsorption energy. The therapeutic efficacy is systematically evaluated using an S. aureus-infected full-thickness skin defect model. The bi-modulated FM BioHJzyme exhibits favorable antibacterial efficiency under NIR irradiation, while subsequent wound healing is facilitated through collagen deposition and angiogenesis in the following absence of NIR irradiation. This work offers a deep insight into the intricate mechanism-performance relationship of BioHJzyme platform in catalytic anti-bacterial application and proposes a sustainable approach of mechanism-guided materials design.