Molecular Dynamics Simulations of Nanostructures Formed by Hydrophobins and Oil in Seawater

Classical molecular dynamics simulations using the Martini coarse-grained force field were performed to study oil nanodroplets surrounded by fungal hydrophobin (HP) proteins in seawater. The class I EAS and the class II HFBII HPs were studied along with two model oils, namely, benzene and n-decane. Both HPs exhibit free energy minima at the oil-seawater interface, which is deeper in benzene compared to the n-decane systems. Larger constraint forces are required to keep both HPs within the n-decane phase compared to inside benzene, with HFBII being more affine to benzene compared to EAS. Smaller surface tensions are observed at benzene-seawater interfaces coated with HPs compared to their n-decane counterparts. In the latter the surface tension remains unchanged upon increases in the concentration of HPs, whereas in benzene systems adding more HPs lead to decreases in surface tension. EAS has a larger tendency to cluster together in the interface compared to HFBII, with both HPs having larger coordination numbers when surrounding benzene droplets compared to when they are around n-decane nanoblobs. The HP-oil nanostructures in seawater examined have radii of gyration ranging between 2 and 12 nm, where the n-decane structures are larger and have more irregular shapes compared to the benzene systems. The n-decane molecules within the nanostructures form a compact spherical core, with the HPs partially covering its surface and clustering together, conferring irregular shapes to the nanostructures. The EAS with n-decane structures are larger and have more irregular shapes compared to their HFBII counterparts. In contrast, in the HP-benzene structures both HPs tend to penetrate the oil part of the droplet. The HFBII-benzene structures having the larger oil/HP ratios examined tend to be more compact and spherical compared to their EAS counterparts; however, some of the HFBII-benzene systems that have smaller oil/HP ratios have a more elongated structure compared to their EAS counterparts. This simulation study provides insights into HP-oil nanostructures that are smaller than the oil droplets and gas bubbles recently studied in experiments and, thus, might be challenging to examine with experimental techniques.