Gold-Supported Lipid Membranes Formed by Redox-Triggered Vesicle Fusion on Binary Self-Assembled Monolayers: Ion-Pairing Association and Surface Hydrophilicity

The assembly of biomimetic, planar supported lipid bilayers (SLBs) by the popular vesicle fusion method, which relies on the spontaneous adsorption and rupture of small unilamellar vesicles from aqueous solution on a solid surface, typically works with a limited range of support materials and lipid systems. We previously reported a conceptual advance in the formation of SLBs from vesicles in the gel or fluid phase using the interfacial ion-pairing association of charged phospholipid headgroups with electrochemically generated cationic ferroceniums bound to a self-assembled monolayer (SAM) chemisorbed to gold. This redox-driven approach lays down a single bilayer membrane on the SAM-modified gold surface at room temperature within minutes and is compatible with both anionic and zwitterionic phospholipids. The present work explores the effects of the surface ferrocene concentration and hydrophobicity/hydrophilicity on the formation of continuous SLBs of dialkyl phosphatidylserine, dialkyl phosphatidylglycerol, and dialkyl phosphatidylcholine using binary SAMs of ferrocenylundecanethiolate (FcC 11 S) and dodecanethiolate (CH 3 C 11 S) or hydroxylundecanethiolate (HOC 11 S) comprising different surface mole fractions of ferrocene (χ Fc surf ). An increase in the surface hydrophilicity and surface free energy of the FcC 11 S/HOC 11 S SAM mitigates the decrease in the attractive ion-pairing interactions resulting from a reduced χ Fc surf . SLBs of ≳80% area coverage form on the FcC 11 S/HOC 11 S SAM for all the phospholipid types down to χ Fc surf of at least 0.2, composition yielding a water contact angle (θ W ) of 44 ± 4°. By contrast, a greater number of ion-pairing interactions is required on the hydrophobic FcC 11 S/CH 3 C 11 S surface to drive the vesicle fusion process; bilayers or bilayer patches form at χ Fc surf ≳ 0.6 (θ W = 97 ± 3°). These findings will aid in tailoring the surface chemistry of redox-active modified surfaces to widen the conditions that yield supported lipid membranes.