Structure of polymer-capped gold nanorods binding to model phospholipid monolayers

Abstract We report an experimental study of the structure of polymer-capped gold nanorods (AuNRs) binding to model phospholipid monolayers to elucidate the mechanism that drives the insertion of the AuNRs into phospholipid membranes. The experimental system consists of four different cases of AuNRs interacting with lipid monolayers: cationic and anionic polymer-capped AuNRs suspended in the pure water subphase of Langmuir monolayers of zwitterionic and anionic phospholipids, separately. Liquid surface x-ray reflectivity was used to measure in situ the structure of the lipids and AuNRs at the air-water interface with sub-nanometer resolution, yielding quantitatively the amount, orientation, as well as depth of AuNR insertion into the monolayer. In the case of a zwitterionic monolayer composed of 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine, cationic Poly-diallyldimethylammonium chloride (PDC) capped AuNRs (PDC-AuNRs) adsorbed peripherally at the water-lipid interface whereas the anionic Poly-sodium 4-styrenesulfonate (PSS) capped AuNRs (PSS-AuNRs) penetrated deeply into the lipid monolayer. In the case of an anionic monolayer composed of 1-stearoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (SOPG), PDC-AuNRs inserted into the monolayer whereas PSS-AuNRs were not even attracted to the monolayer. The results suggest that the adsorption process of AuNRs to model membranes may proceed through different mechanisms. In the presence of a charged membrane, electrostatic interactions drove the AuNRs to or away from the membrane depending on the nature of the charge of the lipid film and the AuNRs, while in the presence of a zwitterionic membrane, both electrostatic interactions and hydrophobic interactions mediated the insertion of the AuNRs into the membrane.