PEG-Neridronate-Modified NaYF₄:Gd³⁺,Yb³⁺,Tm³⁺/NaGdF₄ Core-Shell Upconverting Nanoparticles for Bimodal Magnetic...

Upconverting nanoparticles are attracting extensive interest as a multimodal imaging tool. In this work, we report on the synthesis and characterization of gadolinium-enriched upconverting nanoparticles for bimodal magnetic resonance and optical luminescence imaging. NaYF₄:Gd³⁺,Yb³⁺,Tm³⁺ core upconverting nanoparticles were obtained by a thermal coprecipitation of lanthanide oleate precursors in the presence of oleic acid as a stabilizer. With the aim of improving the upconversion emission and increasing the amount of Gd³⁺ ions on the nanoparticle surface, a 2.5 nm NaGdF₄ shell was grown by the epitaxial layer-by-layer strategy, resulting in the 26 nm core-shell nanoparticles. Both core and core-shell nanoparticles were coated with poly(ethylene glycol) (PEG)-neridronate (PEG-Ner) to have stable and well-dispersed upconverting nanoparticles in a biological medium. FTIR spectroscopy and thermogravimetric analysis indicated the presence of ∼20 wt % of PEG-Ner on the nanoparticle surface. The addition of inert NaGdF₄ shell resulted in a total 26-fold enhancement of the emission under 980 nm excitation and also affected the T ₁ and T ₂ relaxation times. Both r ₁ and r ₂ relaxivities of PEG-Ner-modified nanoparticles were much higher compared to those of non-PEGylated particles, thus manifesting their potential as a diagnostic tool for magnetic resonance imaging. Together with the enhanced luminescence efficiency, upconverting nanoparticles might represent an efficient probe for bimodal in vitro and in vivo imaging of cells in regenerative medicine, drug delivery, and/or photodynamic therapy.