Oxidation State of Capping Agent Affects Spatial Reactivity on Gold Nanorods

Despite enormous progress toward controlling the shapes and surface chemistry of colloidal nanoparticles, spatial control of nanoparticle surface chemistry remains a major challenge. In recent years, there have been tantalizing reports demonstrating anisotropic silica coating of gold nanorods in which silica is deposited only on the sides by functionalizing the nanorods with poly(ethylene glycol) methyl ether thiol (PEG-thiol) prior to silica coating, but such results have been difficult to reproduce. We report that the oxidation state of PEG-thiol is key to anisotropic silica coating, with the disulfide, not the thiol, leading to side silica coating. PEG-disulfide appears to selectively functionalize the ends of gold nanorods, and robust methods are developed to reliably deposit side silica shells on PEG-disulfide functionalized gold nanorods.