Versatile Route toward Hydrophobically Polymer-Grafted Gold Nanoparticles from Aqueous Dispersions

Stabilization of gold nanoparticles in organic solvents is a key challenge in making them available for a wider range of material applications. Polymers are often used as stabilizing ligands because they also allow for the introduction of new properties and functionalities. Many of the established synthesis protocols for gold nanoparticles are water-based. However, the insolubility of many synthetic polymers in water renders the direct functionalization of aqueous particle dispersions with these ligands difficult. Here, we report on an approach for the functionalization of gold nanoparticles, which were prepared by aqueous synthesis, with hydrophobic polymer ligands and their characterization in nonpolar, organic dispersions. Our method employs an auxiliary ligand to first transfer gold nanoparticles from an aqueous to an organic medium. In the organic phase, the auxiliary ligand is then displaced by thiolated polystyrene ligands to form a dense polymer brush on the particle surface. We characterize the structure of the ligand shell using electron microscopy, scattering techniques, and ultracentrifugation and analyze the influence of the molecular weight of the polystyrene ligands on the structure of the polymer brush. We further investigate the colloidal stability of polystyrene-functionalized gold nanoparticles in various organic solvents. Finally, we extend the use of our protocol from small, spherical gold nanoparticles to larger gold nanorods and nanocubes.