Air and Water Free Solid-Phase Synthesis of Thiol Stabilized Au Nanoparticles with Anchored, Recyclable Dendrimer Templates

Solid-phase synthetic templates for Au nanoparticles were developed using Merrifield resins and polyamidoamine (PAMAM) dendrimers. This synthetic scheme affords the opportunity to prepare metal nanoparticles in the absence of air and water, and it does not necessitate phase transfer agents that can be difficult to remove in subsequent steps. Amine-terminated generation 5 PAMAM (G5NH<sub>2</sub>) dendrimers were grafted to anhydride functionalized polystyrene resin beads and alkylated with 1,2-epoxydodecane to produce G5C12<sub>anch</sub>. The anchored dendrimers bound both Co<sup>II</sup> and Au<sup>III</sup> salts from toluene solutions at ratios comparable to those of solution phase alkyl-terminated PAMAM dendrimers. The encapsulated Au<sup>III</sup> salts could be reduced with NaBH<sub>4</sub> to produce anchored dendrimer encapsulated nanoparticles (DENs). Treatment of the anchored DENs with decanethiol in toluene extracted the Au nanoparticles from the dendrimers as monolayer protected clusters (MPCs). After a brief NaCN etch, the anchored dendrimers were readily recycled and a subsequent synthesis of decanethiol Au MPCs was performed with comparable MPC yield and particle size distribution.