Polarization Controlled Assembly of Ultrathin Thiorphan Nanostructures on ZnO Surface Facets.

Despite the importance of thiorphan as a small molecule with vital biological roles, its interactions with zinc oxide (ZnO) nanomaterials that are prospective in drug delivery and theranostic applications have not yet been sufficiently explored. Here the impact of surface polarity of different ZnO facets on thiorphan adsorption is studied both experimentally by atomic force microscopy (AFM) and angle resolved X-ray photoelectron spectroscopy (XPS) and theoretically by force field molecular dynamics (FFMD) and density functional tight binding simulations (DFTB). Polar ZnO surfaces cause the formation of thiorphan nanodots, where the size of the nanodots depends on the direction of dipoles: small (4 nm) nanodots are formed on Zn-face ZnO, while large (25 nm) nanodots are formed on O-face ZnO. Nonpolar ZnO surfaces cause self-assembly into layered nanoislands with characteristic 4 nm layer thickness, which subsequently merge into rigid nanolayers. The self-assembly is shown to be controlled solely by the effect of surface dipole electric field orientation and magnitude, whereas effects of surface chemistry or solution are negligible. The results thus also show a way for controlling the assembly of thiorphan and other molecular nanomaterials for diverse applications.