Neighboring Carboxylic Acid Boosts Peroxidase‐Like Property of Metal‐Phenolic Nano‐Networks in Eradicating Streptococcus mutans Biofilms

Developing nature-inspired nanomaterials with enzymatic activity is essential in combating bacterial biofilms. Here, it is reported that incorporating the carboxylic acid in phenolic/Fe nano-networks can efficiently manipulate their peroxidase-like activity via the acidic microenvironment and neighboring effect of the carboxyl group. The optimal gallic acid/Fe (GA/Fe) nano-networks demonstrate highly enzymatic activity in catalyzing H₂ O₂ into oxidative radicals, damaging the cell membrane and extracellular DNA in Streptococcus mutans biofilms. Theoretical calculation suggests that the neighboring carboxyl group can aid the H₂ O₂ adsorption, free radical generation, and catalyst reactivation, resulting in superb catalytic efficiency. Further all-atom simulation suggests the peroxidation of lipids can increase the cell membrane fluidity and permeability. Also, GA/Fe nano-networks show great potential in inhibiting tooth decay and treating other biofilm-associated diseases without affecting the commensal oral flora. This strategy provides a facile and scale-up way to prepare the enzyme-like materials and manipulate their enzymatic activity for biomedical applications.