Structural and kinetic properties of laterally stabilized, oligo(ethylene glycol)-containing alkylthiolates on gold: a modular approach.
ABSTRACT The formation of highly ordered self-assembled monolayers (SAMs) on gold from an unusually long and linear compound HS(CH(2))(15)CONH(CH(2)CH(2)O)(6)CH(2)CONH(CH(2))(15)CH(3) is investigated by contact angle goniometry, ex situ null ellipsometry, cyclic voltammetry and infrared reflection-absorption spectroscopy. The molecules are found to assemble in an upright position as a complete monolayer within 60 min. The overall structure of the SAM reaches equilibrium within 24 h as evidenced by infrared spectroscopy, although a slight improvement in water contact angles is observed over a period of a few weeks. The resulting SAM is 60 A thick and it displays an advancing water contact angle of 112 degrees and excellent electrochemical blocking characteristics with typical current densities about 20 times lower as compared to those observed for HS(CH(2))(15)CH(3) SAMs. The dominating crystalline phases of the supporting HS(CH(2))(15) and terminal (CH(2))(15)CH(3) alkyl portions, as well as the sealed oligo(ethylene glycol) (OEG) "core," appear as unusually sharp features in the infrared spectra at room temperature. For example, the splitting seen for the CH(3) stretching and CH(2) scissoring peaks is normally only observed for conformationally trapped alkylthiolate SAMs at low temperatures and for highly crystalline polymethylenes. Temperature-programmed infrared spectroscopy in ultrahigh vacuum reveals a significantly improved thermal stability of the SAM under investigation, as compared to two analogous OEG derivatives without the extended alkyl chain. Our study points out the advantages of adopting a "modular approach" in designing novel SAM-forming compounds with precisely positioned in plane stabilizing groups. We demonstrate also the potential of using the above set of compounds in the fabrication of "hydrogel-like" arrays with controlled wetting properties for application in the ever-growing fields of protein and cell analysis, as well as for bioanalytical applications.