Confinement-Enrichment-Driven Cascade Catalysis in a Self-Assembled Nanozyme Reactor for Synergistic Antibiofouling and Biocorrosion Inhibition.

Abstract

Marine biofouling, initiated by microbial colonization and biofilm formation, causes severe infrastructure deterioration and hydrodynamic drag. Although reactive oxygen/nitrogen species (ROS/RNS)-mediated nanozymes offer a unique and highly promising platform for anti-biofouling, their overall catalytic performance is often hindered by weakening interfacial catalytic kinetics within thick biofilms. Here we report a simple yet efficient self‑assembled CAGA nanozyme reactor that takes advantage of glucose as confined reactant to maintain high local reactant concentrations, and a branched copper‑L‑arginine (CA) core to facilitate interfacial mass transfer and substrate enrichment. More significantly, Au nanoparticles (AuNPs)-decorated hyaluronic acid (HA) shell further enables microenvironment-responsive activation of multienzyme-mimicking activities. This intelligent design orchestrates a confinement-enrichment-catalysis cascade process inside the CAGA nanozyme reactor, thus amplifying its ROS/RNS output for biofilm eradication. Density functional theory (DFT) confirms Cu active sites lower the energy barrier for L-Arg oxidation, promoting nitric oxide and peroxynitrite (NO and ONOO^-) formation. Antimicrobial experiments coupled with RNA-sequencing transcriptomics validate this impressive antibacterial performance, attributed to the synergistic effects of amplified redox imbalance and cuproptosis-like pathways. This hybrid CAGA nanozyme reactor remarkably suppresses microbiologically influenced corrosion (MIC) and exhibits excellent antifouling performance in practical coatings, providing a rational paradigm for developing next-generation antibiofouling strategies.