Diazonium Salt-Derived 4-(Dimethylamino)phenyl Groups as Hydrogen Donors in Surface-Confined Radical Photopolymerization for Bioactive Poly(2-hydroxyethyl methacrylate) Grafts

Abstract

In this paper we describe a novel methodology for grafting polymers via radical photopolymerization initiated on gold surfaces by aryl layers from diazonium salt precursors. The parent 4-(dimethylamino)benzenediazonium salt was electroreduced on a gold surface to provide 4-(dimethylamino)phenyl (DMA) hydrogen donor layers; free benzophenone in solution was used as a photosensitizer to strip hydrogen from the grafted DMA. This system permitted efficient surface initiation of photopolymerization of 2-hydroxyethyl methacrylate. The resulting poly(2-hydroxyethyl methacrylate) (PHEMA) grafts were found to be very adherent to the surface as they resist total failure after being soaked in the well-known paint stripper methyl ethyl ketone. The PHEMA grafts were reacted with 1,1'-carbonyldiimidazole to yield carbamate groups that are able to react readily with amino groups from proteins. The final surface consisted of protein-functionalized PHEMA grafts where bovine serum albumin (BSA) protein is specifically linked to the grafts by covalent bonds. We used X-ray photoelectron spectroscopy to monitor the chemical changes at the gold surface all along the process from the neat gold to the end-protein-functionalized polymer grafts: the PHEMA graft thickness ranged from 7 to 27 nm, and the activation by 1,1'-carbonyldiimidazole reached 37% of the OH groups, which was sufficient for 90% surface coverage of the grafts by BSA. This work conclusively provides a new approach for bridging reactive and functional polymers to surfaces via aryl diazonium salts in a simple, fast, and efficient approach of importance in biomedical and other applications.