The Influence of Alkanethiols on the Production of Hydrophobic Gold Nanoparticles via Pulsed Laser Ablation in Liquids

The ability to suspend plasmonic metal nanoparticles in apolar environments is an important feat towards harnessing their optical properties for use in amphiphilic biological environments. Pulsed laser Ablation in Liquids (PLAL) is a well-established method for the production of gold nanoparticles (AuNPs) in aqueous environments; however, ablation in organic liquids for the synthesis of hydrophobic AuNPs still has many unknowns, such as the relationship between colloidal stability and the ligand shell. In this study, hydrophobic AuNPs were produced by PLAL of gold in a 1-alkanethiol/n-decane solution and treated with laser fragmentation. Results demonstrate that longer chain length ATs produced particles with a smaller average size; however, there was no strong correlation between alkanethiol (AT) concentration and particle size. Stability was investigated by monitoring the temporal evolution of the extinction spectra which revealed that lower concentrations of AT stabilize the colloids while higher concentrations tend to result in quicker particle aggregation. Furthermore, longer chain length ATs demonstrated improved stability. Additionally, vibrational spectroscopy was employed to examine the AuNP surface chemistry, which pointed to the presence of oxidized carbon species and graphitic carbon.