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Understanding interactions between functional nanoparticles and lipid bilayers is important to many emerging biomedical and bioanalytical applications. In this paper, we report incorporation of hydrophobic cadmium sulphide quantum dots (CdS QDs) into mixed 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) liposomes, and into their supported bilayers (SLBs). The QDs were found embedded in the hydrophobic regions of the liposomes and the supported bilayers, which retained the QD fluorescent properties. In particular, we studied the effect of the QD size (2.7-5.4 nm in diameter) on the formation kinetics and structure of the supported POPC/POPE bilayers, monitored in situ using quartz crystal microbalance with dissipation monitoring (QCM-D), as the liposomes ruptured onto the substrate. The morphology of the obtained QD-lipid hybrid bilayers was studied using atomic force microscopy (AFM), and their structure by synchrotron X-ray reflectivity (XRR). It was shown that the incorporation of hydrophobic QDs promoted bilayer formation on the PEI cushion, evident from the rupture and fusion of the QD-endowed liposomes at a lower surface coverage compared to the liposomes without QDs. Furthermore, the degree of disruption in the supported bilayer structure caused by the QDs was found to be correlated with the QD size. Our results provide mechanistic insights into the kinetics of the rupturing and formation process of QD-endowed supported lipid bilayers via liposome fusion on polymer cushions.

The formation of complete supported lipid bilayers by vesicle adsorption and rupture was studied in relation to deposition conditions of vesicles and underlying cushion formed from various polyelectrolytes. Lipid vesicles were formed from zwitterionic 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and negatively charged 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) in phosphate buffer of various pH with or without NaCl addition. Polyelectrolyte multilayer films (PEM) were constructed by sequential adsorption of alternately charged polyelectrolytes from their solutions-layer-by-layer deposition (LBL). The mechanism of the formation of supported lipid bilayer on polyelectrolyte films was studied by quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). QCM-D allowed following the adsorption kinetics while AFM measurements verified the morphology of lipid vesicles and isolated bilayer patches on the PEM cushions providing local topological images in terms of lateral organization. Additionally, polyelectrolyte cushions were characterized with ellipsometry to find thickness and swelling properties, and their roughness was determined using AFM. It has been demonstrated that the pH value and an addition of NaCl in the buffer solution as well as the type of the polyelectrolyte cushion influence the kinetics of bilayer formation and the quality of formed bilayer patches.

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The surface properties of polyelectrolyte multilayers (PEMs) obtained via sequential adsorption of oppositely charged polyions from their solutions and used as cushions for supported lipid bilayers were investigated. Five types of polyelectrolytes were used: cationic polyethyleneimine (PEI), poly(diallyldimethylammonium)chloride (PDADMAC), and poly-l-lysine hydrobromide (PLL); and anionic polysodium 4-styrenesulfonate (PSS) and poly-l-glutamic acid sodium (PGA). The wettability and surface free energy of the PEMs were determined by contact angle measurements using sessile drop analysis. Electrokinetic characterisation of the studied films was performed by streaming potential measurements of selected multilayers and the structure of the polyelectrolyte multilayer was characterized by synchrotron X-ray reflectometry. The examined physicochemical properties of the PEMs were correlated with the kinetics of the formation of supported lipid bilayers atop the PEM cushion.

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