Design, Synthesis, and Application of a Difunctional Y-Shaped Surface-Tethered Photoinitiator.

Mixed homopolymer brushes have unique interfacial properties that can be exploited for both fundamental studies and applications in technology. Herein, the synthesis of a new catechol-based biomimetic Y-shaped binary photoinitiator (Y-photoinitiator) and its applications for surface modification with polymer brushes through both "grafting to" and "grafting from" strategies are reported. The "leg" of the Y consists of a catechol group as surface anchoring moiety. The arms are photoinitiator moieties that can be "addressed" independent of each other by radiation of different wavelengths. Using ultraviolet and visible light successively, each arm of the Y-photoinitiator was activated, thereby allowing the synthesis of Y-shaped block copolymer brushes with dissimilar polymer chains. The suitability of the Y-photoinitiator for surface modification was first investigated using N-vinylpyrrolidone and styrene as the model monomers for successive UV-photoiniferter-mediated polymerization and visible-light-induced polymerization, respectively. Switching of the wetting properties of the Y-shaped block copolymer brush poly( N-vinylpyrrolidone)- block-poly(styrene) (PVP- b-PS)-grafted surfaces by contact with different solvents was also investigated. To further exploit this novel Y-photoinitiator for the preparation of functional interfaces, Y-shaped block copolymer brushes poly(1-(2-methacryloyloxyhexyl)-3-methylimidazolium bromide)- block-poly( N-vinylpyrrolidone- co-glycidyl methacrylate) (PIL(Br)- b-P(NVP- co-GMA)) were also prepared and subsequently functionalized with the cell-adhesive arginine-glycine-aspartic acid (RGD) peptides by reaction with the glycidyl groups (PILPNG-RGD). The PILPNG-RGD grafted surfaces showed excellent cell-adhesive, bacteriostatic, and bactericidal properties. Thus, it can be concluded that further exploitation of this novel Y-photoinitiator for graft polymerization should allow the preparation of a wide range of functional interfaces with tailored properties.