Facile ligand-exchange with polyvinylpyrrolidone and subsequent silica coating of hydrophobic upconverting β-NaYF4:Yb3+/Er3+nanoparticles

Abstract

A facile ligand-exchange strategy with a water-soluble polymer, i.e. polyvinylpyrrolidone (PVP), to replace the surface passivating oleate ligands on the β-NaYF₄ nanoparticle surface is reported. Highly monodisperse oleate-stabilized β-NaYF₄ nanoparticles were synthesized and the oleates were exchanged with a commercially available PVP allowing the phase transfer of these nanoparticles. The exchanged nanoparticles are readily dispersible in water and other polar solvents. To show the effectiveness of the exchange reaction we used the affinity of the PVP chains to silica and coated the nanoparticles with a uniform, thin silica shell. The PVP exchanged and silica-coated nanoparticles show longer colloidal stability and no surfactant related problems as compared to the reverse microemulsion-based silica-coated nanoparticles, which show a high tendency to aggregate, when removed from the microemulsion. The optical properties of the ligand-exchanged nanoparticles dispersed in water were compared with that of the oleate-stabilized nanoparticles in organic solvents. A decrease in the upconversion emission intensity and a different relative ratio of the green and red upconverted light were observed for the particles dispersed in water after ligand-exchange. PVP is a highly biocompatible polymer and is reported to have a longer blood circulation time and very low accumulation in vital organs, two highly desired properties for in vivo studies. This ligand-exchange strategy opens a new pathway to study the use of β-NaYF₄ for biological applications in vivo.