Sulfate-Mediated End-to-End Assembly of Gold Nanorods

There is interest in the controlled aggregation of gold nanorods (GNRs) for the production of extended nanoassemblies. Prior studies have relied upon chemical modification of the GNR surface to achieve a desired final aggregate structure. Herein we illustrate that control of electrolyte composition can facilitate end-to-end assembly of cetyltrimethylammonium-bromide-coated (CTAB) GNRs. By adjusting either the sulfate anion concentration or the exposure time it is possible to connect GNRs in chain-like assemblies. In contrast, end-to-end assembly was not observed in control experiments using monovalent chloride salts. We attribute the end-to-end assembly to the localized association of sulfate with exposed quaternary ammonium head groups of CTAB at the nanorod tip. To quantify the assembly kinetics, visible-near-infrared extinction spectra were collected over a predetermined time period, and the colloidal behavior of the GNR suspensions was interpreted using plasmon band analysis. Transmission electron microscopy and atomic force microscopy results support the conclusions reached via plasmon band analysis, and the colloidal behavior is consistent with Derjaguin-Landau-Verwey-Overbeek theory.