Fluorinated Covalent Organic Frameworks Based Dual‐Functional Pellicle for Synergistic Prevention and Treatment of Dental Caries

ABSTRACT Dental caries is a common oral disease primarily caused by dental plaque, with the formation of acquired pellicle being a prerequisite for plaque maturation. Current treatment strategies for dental plaque mainly focus on inhibiting the adhesion and colonization of cariogenic bacteria, but lack effective approaches to suppress acquired pellicle formation. Here, we report a new class of fluorinated covalent organic frameworks (F‐COFs) to construct a dual‐functional artificial pellicle for preventing dental caries. We demonstrate that F‐COFs exhibit a stronger affinity for enamel than the 15‐amino‐acid N‐terminal sequence of statherin (SN15) and preferentially form an artificial acquired pellicle on the tooth surface. This artificial pellicle prevents further adsorption of salivary proteins, thereby inhibiting the adhesion of cariogenic bacteria and enabling efficient bactericidal activity under light irradiation. Mechanistic investigation reveals that F‐COFs exhibit a higher interaction energy on the hydroxyapatite (HAP) (001) surface due to hydrogen bonding than SN15, forming an artificial acquired pellicle that significantly inhibits salivary pellicle formation at the source. This artificial pellicle inhibits the adhesion and colonization of cariogenic bacteria and exhibits excellent reactive oxygen species (ROS) generation capacity under light irradiation, effectively killing cariogenic bacteria. Hence, the dual‐functional feature endows F‐COFs with prevention efficiencies of 94.61% and 100% for initial lesions as well as moderate and extensive lesions, respectively, demonstrating better performance than other reported anti‐caries biomaterials. Overall, the development of a dual‐functional artificial acquired pellicle in this work offers new prospects for non‐invasive and precisely targeted inhibition of acquired pellicle and dental plaque, thus providing a novel approach for the treatment and prevention of dental caries.