Adsorption of Lipid-Functionalized Poly(ethylene glycol) to Gold Surfaces as a Cushion for Polymer-Supported Lipid Bilayers

Inclusion of a polymer cushion between a lipid bilayer membrane and a solid surface has been suggested as a means to provide a soft, deformable layer that will allow for transmembrane protein insertion and mobility. In this study, the properties of a heterofunctional, telechelic PEG lipopolymer (1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-poly(ethylene glycol)-2000-N- [3-(2-(pyridyldithio)propionate]) (DSPE-PEG-PDP) adsorbed from ethanol and water solutions onto gold surfaces were studied using a variety of surface-sensitive techniques. X-ray photoelectron spectroscopy showed that the PEG molecules are tethered to the gold surface via thiolate bonds. When adsorbed from water, ethanol, or their mixtures, reflection-absorption infrared spectroscopy showed that amorphous PEG layers with disordered DSPE alkyl chains were formed, independent of adsorption time or solution concentration. On the basis of advancing and receding water and hexadecane contact angles on the lipopolymer films, the DSPE lipid groups appear to segregate from the PEG layer and become exposed at the surface of the polymer films. Swelling observed in surface plasmon resonance experiments and the large contact angle hysteresis observed indicate that highly swellable, mobile films capable of molecular rearrangements are formed. The self-assembling and amorphous properties of these PEG layers make them ideal candidates as polymer cushions for polymer-supported lipid bilayers. The DSPE surface concentration can be controlled, to a limited degree, by varying the adsorption time of DSPE-PEG-PDP from ethanol. A more effective strategy is to coadsorb DSPE-PEG-PDP with a non-lipid-functionalized PEG-PDP from an ethanol/water mixture, which allows the PEG thickness and density to remain constant while decreasing the density of DSPE groups.