Molecular assembly of extracellular polymeric substances regulating aggregation of differently charged nanoplastics...

Extracellular polymeric substances (EPS) represent an interface between microbial cells and aquatic environment, where nanoplastics acquire coatings to alter their fate and toxicity. However, little is known about molecular interactions governing modification of nanoplastics at biological interfaces. Molecular dynamics simulations combining experiments were conducted to investigate assembly of EPS and its regulatory roles in the aggregation of differently charged nanoplastics and interactions with bacterial membrane. Driven by hydrophobic and electrostatic interactions, EPS formed micelle-like supramolecular structures with hydrophobic core and amphiphilic exterior. Different components, depending on their hydrophobicity and charge, were found to promote or suppress EPS assembly. Neutral and hydrophobic nanoplastics showed unbiased adsorption of EPS species, while cationic and anionic nanoplastics were distinct and attracted specific molecules of opposite charges. Compared with isolated EPS, assembled EPS concealed hydrophobic groups to be less adsorbed by nanoplastics. Aggregation of nanoplastics was alleviated by EPS due to electrostatic repulsion plus steric hindrance. ESP suppressed binding of cationic nanoplastics to the bacterial membrane through reducing the surface charge. Neutral and anionic nanoplastics showed weak membrane association, but their binding interactions were promoted by EPS. The structural details revealed here provided molecular level insights into modifications of nanoplastics at the eco-environment interface.