Biomimetic Asymmetric Polymer Brush Coatings Bearing Fencelike Conformation Exhibit Superior Protection and Antifouling Performance.

Antifouling surfaces with optimized conformation and compositional heterogeneities are presented with the goal of improving the efficacy of surface protection. The approach exploits the adhesive group (thiol or catechol chain end) to anchor asymmetric polymer brushes (APBs) bearing amphiphilic side chains with synergistic nonfouling and fouling-release abilities onto the surface. The conformation of the APB surface is close to the fencelike structure, which mimics lubricating protein lubricin, endowing the surface with capacity of enhanced protection and antiadhesivity, even facing the high compression of fouling. By utilizing a poly(Br-acrylate-alkyne) macroagent comprising alkynyl and 2-bromopropionate groups, we prepared a series of APB surfaces based on polyacrylate-g-poly(ethylene oxide)/poly(pentafluorophenyl methacrylate) (PA-g-PEO/PPFMA) APBs to explore the influence of the content of the fluorinated segment and bioinspired topological polymer chemistry on their antifouling performance. The APB surfaces can not only provide compositional heterogeneities of PEO and fluorinated segments in each side chain but also give a high surface coverage because of the characteristic of high grafting density of macromolecular brushes. It was found for the first time, as far as we are aware, the fencelike APB surface shows excellent antifouling performance with less protein adsorption (up to 91% off) and cell adhesion (up to 84% off) in comparison with the controlled substrate under relatively long incubation time.