Structure and thermodynamics of supported lipid membranes on hydrophobic van der Waals surfaces

Understanding the adsorption and physical characteristics of supported lipid membranes is crucial for their effective use as model cell membranes. Their morphological and thermodynamic properties at the nanoscale have traditionally been studied on hydrophilic substrates, such as mica and silicon oxide, which have proved to facilitate the reconstruction of biomembranes. However, in more recent years, with the advent of the van der Waals crystals technology, two-dimensional crystals such as graphene have been proposed as potential substrates in biosensing devices. Membranes formed on these crystals are expected to behave differently owing to their intrinsic hydrophobicity, however thus far knowledge of their morphological and thermodynamic properties is lacking. Here we present a comprehensive nanoscale analysis of the adsorption of phosphatidylcholine lipid monolayers on two of the most commonly used van der Waals crystals, graphite and hexagonal boron nitride. Both morphological and thermodynamic properties of the lipid membranes were investigated using temperature-controlled atomic force microscopy. Our experiments show that the lipids adsorb onto the crystals, forming monolayers with their orientation dependent upon their concentration. Furthermore, we found that the hydrophobicity of van der Waals crystals determines a strong increase in the transition temperature of the lipid monolayer compared to that observed on hydrophilic substrates. These results are important for understanding the properties of lipid membranes at solid surfaces and extending their use to novel drug delivery and biosensing devices made of van der Waals crystals.