Gram-Scale Synthesis of Isolated Monodisperse Gold Nanorods

Abstract

Although gold nanorods (AuNRs) have strong potential applications in nanotechnology, plasmonics, and sensing, the scale-up synthesis of isolated AuNRs in gram quantities remains a challenge. Nearly all previously reported methods produce aqueous solutions of cetyltrimethylammonium bromide (CTAB)-coated AuNRs in milligram quantities with yields of approximately 20-30 % in terms of Au^I to Au⁰ conversion. In addition, it is difficult to remove the CTAB bilayer from the surface of AuNRs and yet make them soluble and functionalized for further processing and chemical modification. This report describes the synthesis of monodisperse functionalized AuNRs (standard deviation, σ≈5 %) in gram quantities. Our approach involved increasing the concentration of HAuCl₄ ⋅3 H₂ O in the growth solution to produce larger quantities of starting AuNRs and further reducing the remaining Au^I ions onto the surface of AuNRs. The slow and controlled addition of ascorbic acid as a reducing agent continued the conversion of Au^I into Au⁰ (through a disproportionation reaction) onto the surface of the nanorods, which maintained their uniform morphology without creating any unwanted impurities of various shapes. In addition, this approach significantly narrowed the size distribution owing to continuous growth of the partially grown AuNRs during the initial stage of the synthesis. To isolate a 1 g quantity of the AuNRs and to make them functionalized for further chemical reactions, a ligand-exchange approach was utilized, in which the CTAB surfactant was replaced with 4-mercaptophenol. The thiol group from 4-mercaptophenol formed a covalent bond with the surface of the AuNRs, leaving free functional OH groups available for further chemical coupling reactions. For the ligand-exchange process, a concentrated solution of 4-mercaptophenol in tetrahydrofuran solution was introduced into the AuNRs solution. Pure AuNRs functionalized with 4-mercaptophenol were isolated by dispersion and rinsing with an excess amount of THF, followed by centrifugation.

Keywords: amplification; gold; monodisperse; nanostructures; surface functionalization.