Atomistic Simulations of Hydration and Antibiofouling Behavior of Amphiphilic Polymer Brush Surfaces Functionalized with TMAO and Short Fluorocarbon

Developing fouling-resistant materials is of paramount interest in marine industries and biomedical applications. In this work, we studied the interfacial hydration and surface–protein interactions of the amphiphilic brush surface functionalized with hybrid hydrophilic trimethylamine N -oxide (TMAO) and hydrophobic pentafluoroethyl groups using a combination of atomistic molecular dynamics simulations and free-energy computations. Our results show that while the interfacial hydration density of the amphiphilic surface slightly decreases with the introduction of small fluorocarbons compared to that of the pure TMAO-functionalized surface, the amphiphilic surface remains relatively strong in resisting protein adsorption. The nanosized clustering of hydrophobic fluorine atoms on the top of the amphiphilic brush surface introduces weak protein adsorption; however, due to the strong interfacial hydration and weak hydrophobic interaction, the amphiphilic surface exhibits sufficient antibiofouling activities. Our fundamental studies will be critical for the discovery of marine fouling-resistant coating surfaces.