Hydrophilic metal nanoparticles functionalized by 2-Diethylaminoethanethiol: a close look at the metal-ligand interaction and interface chemical structure

Hydrophilic gold and silver nanoparticles stabilized with 2-diethylaminoethanethiol hydrochloride (DEA) have been prepared and characterized. AuNPs-DEA and AgNPs-DEA with mean diameter below 10 nm have been characterized by means of dynamic light scattering and field-emission scanning electron microscopy techniques. Nuclear magnetic resonance (NMR) studies allowed to assess translational mobility, aggregation equilibrium in function of pH variations and presence of chemisorbed and physisorbed thiol molecules; in particular ethyl groups on DEA ligands are free to rotate, suggesting a rather loose packing of the thiols on the nanoparticle surface. NMR results were compared with X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure, and X-ray absorption spectroscopy. The complementary information acquired allowed to obtain information on the interaction at the interface between the organic thiol ligand and metal nanoparticles (NPs) at atomic level as well as on the molecular structure. The influence of the thickness of the functionalizing layer on the stability of NPs has been studied and opened new insight on the local structure surrounding the NPs.