Triple-Enzyme Mimetic Flexible-Interlaced Ferromagnetic Porous-Organic-Polymer for Self-Adaptive Antibacterial Cascade Therapy via Microenvironment-Reprogramming and Photosensitizer-Aggregation-Suppression

作者：Dandan Xu, Sue Cao, Weiwei Bian, Xiaoming Shi, Dong Zhang, Baolong Zhou, Kun Li, Yan Jiang, Yijun Liu, Yuyu Wang, Junjie Li, Xinkai Han · 发表于：ACS Applied Polymer Materials · 年份：2025 · DOI：10.1021/acsapm.5c00977 · 被引用次数：3 · 研究领域：Nanoplatforms for cancer theranostics、Advanced Nanomaterials in Catalysis、Nanoparticle-Based Drug Delivery

The complex pathological microenvironment of infected wounds impedes antimicrobial efficacy while accelerating bacterial resistance. To overcome this, an oxygen-evolving polyphenol-based magnetic porous polymer (FcPor-POP) was engineered through the covalent conjugation of ferrocene-derived enzymatic units and photoactive polyphenol-porphyrin via phenolic-aldehyde condensation. The concurrently introducing antiquenching structural motifs, realized by flexible saturated carbon linkages, sandwich-like interleaved units, as well as a hydrogen-bond interlocked structure, effectively suppress photoactivity loss induced by π–π aggregation. The FcPor-POP system achieves adaptive antibacterial action through hierarchically coordinated spatiotemporal mechanisms. Pathological microenvironmental cues dynamically trigger enzymatic activity switching. Under acidic pH, the ferrocene units and in situ-formed Fe 3 O 4 nanoparticles exhibit peroxidase-like (POD) activity, converting H 2 O 2 to cytotoxic • OH (accelerated by photothermal heating). Upon H 2 O 2 depletion, oxidase-like (OXD) activity dominates, leveraging multivalent iron centers to produce O 2 •–, preserving enzyme-like antibacterial function. Targeted ROS delivery is enabled by phenolic hydroxyl groups that anchor to bacterial membranes via H-bonding, combined with rough surface topography enhancing physical adhesion. This minimizes the distance between ROS generation sites (Fe centers/photosensitizers) and bacterial targets, ...