Multiscale simulations of polyzwitterions in aqueous bulk solutions and brush array configurations

Abstract

Zwitterionic polymers are very promising candidates for antifouling materials that exhibit high chemical stability as compared to polyethylene glycol-based systems. A number of simulation and experimental studies have emerged over recent years for the investigation of sulfobetaine-based zwitterionic polymers. Investigating the structural and thermodynamic properties of such polymers requires access to broad time and length regimes, thus necessitating the development of multiscale simulation strategies. The present article advocates a mesoscopic dissipative particle dynamics (DPD) model capable of addressing a wide range of time and length scales. The mesoscopic force field was developed hand-in-hand with atomistic simulations based on the OPLS force field through a bottom-up parameterization procedure that matches the atomistically calculated strand-length, strand-angle and pair distribution functions. The DPD model is validated against atomistic simulations conducted in this work, and against relevant atomistic simulation studies, theoretical predictions and experimental correlations from the literature. Properties examined include the conformations of SPE polymers in dilute bulk aqueous solution, the density profile and thickness of brush arrays as functions of the grafting density and chain length. In addition, we compute the potential of mean force of an approaching hydrophilic or hydrophobic foulant via umbrella sampling as a function of its position relative to the poly-zwitterion-covered surface. The aforementioned observables lead to important insights regarding the conformational tendencies of grafted polyzwitterions and their antifouling properties.