Poly(N,N-dimethylamino) ethyl methacrylate-grafted silicon: protein resistance and response to carbon dioxide

Abstract

This thesis work focused on polymer modification of silicon surface to improve its resistance to protein adsorption. Surface modification was achieved through surface-initiated atom transfer radical polymerization (SI-ATRP) grafting of poly(N,N-dimethyl amino) ethyl methacrylate (PDMAEMA). Since PDMAEMA is CO2-responsive, CO2 cleaning of the modified surface was also investigated. SI-ATRP was chosen to graft PDMAEMA brushes on silicon surface for high graft densities and its good control of polymer molecular weight and polydispersity. Surface characterization of PDMAEMA-modified silicon surfaces included hydrophilicity, layer thickness and surface chemical elemental composition. Protein adsorption experiments were carried out to evaluate the protein resistance of the modified surfaces. Albumin adsorption from single protein solution, as well as from human plasma, decreased significantly after PDMAEMA grafting, and the adsorbed amount decreased with increasing polymer chain length. The maximum decrease in adsorption of 90% relative to the unmodified silicon, was reached at a graft layer thickness of 40 nm (measured in the dry state). Protein resistance in plasma showed PDMAEMA -modified silicon provided significant resistance to most of the tested proteins. Compared to the PEO-modified surface, the PDMAEMA surface showed much greater resistance to albumin adsorption, but, surprisingly, it adsorbed relatively large amounts of vitronectin and prothrombin. Vitronectin may have been degraded in contact with PDMAEMA-modified surface. Also, it was the only surface out of the four, which adsorbed significant amounts of prothrombin. These unexpected observations indicate further investigation will be required to fully assess the protein-resistant properties of these PDMAEMA surfaces. CO2-induced protein desorption was also studied. Cleaning experiments were performed by bubbling CO2 into vials containing the protein-adsorbed PDMAEMA-modified surface after 2 h protein solution exposure. Radiolabelling of albumin showed that the CO2 cleaning effectiveness was related with the PDMAEMA thickness. It was found that a surface with graft thickness 20 nm (dry) responded more strongly to CO2 than one with 15 nm thickness. Western blotting results confirmed that CO2 contributed to protein desorption from the PDMAEMA surface.