All-atom molecular dynamics simulations showing the dynamics of small organic molecules in water-solvated polyelectrolyte brush layers

Polyelectrolyte brushes can introduce functionality to surfaces and because of this, these brushes have been studied extensively. In many applications, these brushes are used in solutions that contain a variety of molecules. While the interaction between polyelectrolyte brushes and molecules has been studied via coarse-grained simulations and experiments, such interaction has not been studied in molecular detail. An understanding of interactions in such molecular detail may prove crucial in the design of future brush coatings that can enable desired adsorption of different organic and biological molecules. Therefore, we present a first all-atom molecular dynamics simulations study of poly(sodium acrylate) brushes in contact with a small organic molecule, γ-butyrolactone. Within this molecular framework, we study the interaction of this lactone molecule with the brush layer and study the ensuing absorption and dynamics of the lactone inside the brush layer. The lactone is found to prefer to remain in the bulk solution; however, when absorbed, lactone molecules are found to have significantly reduced mobilities as compared to that in the bulk solution and are able to massively influence the properties of the brush-entrapped water molecules. These findings provide unprecedented details about the absorption-driven changes to molecular structure and dynamics of the lactone molecules and the water molecules inside the brush layer and can only be uncovered by our all-atom MD simulations. Such explicit and atomistically-resolved information, taking into account the specific chemical nature of the interacting systems, is rare in the context of designing polymer and PE brush-based coatings. Thus, we anticipate that our findings will be crucial in the design of future brush coatings aimed at providing adsorption platforms for different organic and biomolecules.