Vapor Phase Exchange of Self-Assembled Monolayers for Engineering of Biofunctional Surfaces

We show that 4'-nitro-1,1'-biphenyl-4-thiol self-assembled monolayers (NBPT SAMs) on gold can be exchanged with 11-(mercaptoundecyl)triethylene glycol (C₁₁EG₃OH) SAMs via vapor deposition (VD). The pristine and the exchanged SAMs obtained by VD as well as solution method (SM) were characterized by X-ray photoelectron spectroscopy (XPS) and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). Using surface plasmon resonance (SPR), it is shown that C₁₁EG₃OH SAMs on gold obtained by vapor deposition exchange (VD_Ex) have the same protein resistivity as SAMs obtained by the direct self-assembly process. As expected, the cross-linked NBPT SAM are found to be resistive to both exchange processes, VD_Ex and solution method exchange (SM_Ex). In this way, VD_Ex opens up an elegant and new approach of patterning SAM surfaces in situ at vacuum conditions without using any solvents. By combining electron irradiation-induced chemical lithography of NBPT SAMs with VD_Ex, biofunctional patterned substrates were engineered and used for immobilization of protein arrays.