Crosslinking Polymer Brushes with Ethylene Glycol-Containing Segments: Influence on Physicochemical and Antifouling Properties

The introduction of different types and concentrations of crosslinks within poly­(hydroxyethyl methacrylate) (PHEMA) brushes influences their interfacial, physicochemical properties, ultimately governing their adsorption of proteins. PHEMA brushes and brush-hydrogels were synthesized by surface-initiated, atom-transfer radical polymerization (SI-ATRP) from HEMA, with and without the addition of di­(ethylene glycol) dimethacrylate (DEGDMA) or tetra­(ethylene glycol) dimethacrylate (TEGDMA) as crosslinkers. Linear (pure PHEMA) brushes show high hydration and low modulus and additionally provide an efficient barrier against nonspecific protein adsorption. In contrast, brush-hydrogels are stiffer and less hydrated, and the presence of crosslinks affects the entropy-driven, conformational barrier that hinders the surface interaction of biomolecules with brushes. This leads to the physisorption of proteins at low concentrations of short crosslinks. At higher contents of DEGDMA or in the presence of longer TEGDMA-based crosslinks, brush-hydrogels recover their antifouling properties due to the increase in interfacial water association by the higher concentration of ethylene glycol (EG) units.