Formation of OTS self-assembled monolayers at chemically treated titanium surfaces

Enhanced biocompatibility of titanium implants highly depends on the possibility of achieving high degrees of surface functionalization for a low immune response and/or enhanced mineralization of bioactive minerals, such as hydroxyapatite. In this respect, surface modification with Self Assembled Monolayers (SAMs) has a great potential in delivering artificial surfaces of improved biocompatibility. Herein, the effectiveness of common chemical pre-treatments, i.e. hydrogen peroxide (H2O2) and Piranha (H2SO4 + H2O2), in facilitating surface decontamination and hydroxylation of titanium surfaces to promote further surface functionalization by SAMs is investigated. The quality of the octadecyltrichlorosilane (OTS) based SAM appeared to strongly depend upon the surface morphology, the density and nature of surface hydroxyl sites resulting from the oxidative pre-treatments. Contrary to common belief, no further hydroxylation of the titanium substrate was observed after the selected chemical pre-treatments, but the number of hydroxyl groups available on the surface was decreased as a result of the formation of a titanium oxide layer with a gel-type structure. Further examinations by atomic force microscopy, infrared spectroscopy and X-ray photoelectron spectroscopy also revealed that mild oxidizing conditions were sufficient to remove surface contamination without detrimental effects on surface hydroxylation state and surface roughness. Furthermore, the adsorption of the alkylsiloxane molecules forming the SAM film is believed to proceed through hydrolysis at surface acidic hydroxyl groups rather than randomly. This site dependent adsorption process has significant implications for further functionalization of titanium based implants. It also highlights the difficulty of achieving an OTS based SAM at the surface of titanium and question the quality of SAMs reported at titanium surfaces so far.