Deciphering Augmented Dual‐ROS‐Driven Biofilm Eradication by Facilitating Long‐Range Spatial Charge Decoupling in Polymer Carbon Dots

Abstract

ABSTRACT Developing carbon dots (CDs) with reactive oxygen species (ROS) production capability provides an attractive approach to address the dilemma of biofilm eradication caused by the robust extracellular polymeric substance (EPS) matrix. The challenge for the exploration of highly potent CDs is to circumvent the severe thermodynamic and kinetic paradox to transform surrounding substrates into ultra‐reactive ROS. To address this conundrum, we propose a long‐pathway electron‐accepting strategy promoting the absolute spatial charge decoupling by the elaborate marriage of carbonized core and polynaphthalenediimide (PNDI) network, which significantly boosts the superoxide anion (·O 2 − ) and hydroxyl radical (·OH) dual‐ROS generation of the constructed polymer CDs. Systematic mechanism exploration reveals that ultrafast intramolecular charge transfer after photoirradiation enables energetic long‐life electrons to migrate along the PNDI highway for abundant ·O 2 − production. Intriguingly, this profound separation firmly anchors uncompensated highly oxidative holes at the extraordinarily deep highest occupied molecular orbital level of the carbon core, successfully unlocking the thermodynamic threshold for direct ·OH generation. This tailored dual‐ROS storm induces catastrophic EPS matrix degradation and massacres the embedded pathogens, achieving near‐complete (∼99.9%) eradication of Escherichia coli and Staphylococcus aureus biofilms. This work establishes a potent nanoplatform and provides profound mechanistic insights for tackling global biofilm‐associated threats.