Geometry-induced protein reorientation on the spikes of plasmonic gold nanostars.

Functionalized gold nanostars (AuStrs) are remarkable candidates for drug delivery, photothermal therapy and imaging due to their large surface area to volume ratio and plasmonic properties. In this study, we address the challenge of achieving therapeutically controlled dosing using these high aspect ratio nanoparticle vectors by tailoring the nanostar loading area and protein conformation. We synthesized a library of different Au nanostars with varied geometries for potential biomedical applications. The Au nanostars were subsequently coated with different amounts of transferrin (Tf) and a novel depletion method was devised to measure the amount of Tf bound to the surface of the nanostructures. This methodology allowed us to show that coating thickness could be controllably varied and moulded onto the nanoparticle's high index features, whilst simultaneously preserving the key properties of the particle. The orientation of the Tf was measured on nanostars and spheres using transmission electron microscopy by negatively staining the Tf. The Tf was conformal on the nanostars, and protein packing efficiency increased on the AuStrs by 14-fold due to a geometry-induced protein reorientation at the nanoparticle surface. Interestingly, the reorientation of the transferrin observed at the AuStrs spikes did not occur at the AuStrs tips thus highlighting surface energy effects associated with surface curvature.