Molecular modeling of the carbohydrate corona formation on a polyvinyl chloride nanoparticle and its impact on the adhesion to lipid bilayers

The pervasive presence of nanoplastics (NPs) in the environment has gained increasing attention due to their accumulation in living organisms. These emerging contaminants inevitably interact with extracellular polymeric substances along respiratory or gastrointestinal tracts, and diverse organic coating on the surface of NPs, known as bio- or eco-corona, is formed. Although its impact on altering the NP properties and potential cell internalization has been extensively examined, studies on its role in NP partitioning in the cell membrane are elusive yet. In this work, molecular dynamics is used to investigate the formation of chitosan (CT) corona centered on a polyvinyl chloride (PVC) nanoparticle and the uptake of the resulting complex onto lipid membranes. Coarse-grained models compatible with the newly developed Martini 3.0 force field are implemented for the two polymers employing the atomistic properties as targets in the parameterization. The reliability of the coarse-grained polymer models is demonstrated by reproducing the structural properties of the PVC melt and of solvated CT strands, as well as by determining the conformation adopted by the latter at the NP surface. Results show that the spontaneous binding of CT chains of high and intermediate protonation degrees led to the formation of soft and hard corona that modulates the interaction of PVC core with model membranes. The structural changes of the corona adsorbed at the lipid-water interface enable a subsequent transfer of the NP to the center of the saturated lipid membranes and a complete or partial transition to a snorkel conformation depending on the hydrophilic/hydrophobic balance in the CT-PVC complex. Overall, the computational investigation of the coarse-grained model system provides implications for understanding how the eco-corona development influences the uptake and implicit toxicology of NPs.