Synthesis and organic surface modification of luminescent, lanthanide-doped core/shell nanomaterials (LnF3@SiO2@NH2@organic acid) for potential bioapplications: spectroscopic, structural, and in vitro cytotoxicity evaluation.

A facile coprecipitation reaction between Ce(3+), Gd(3+), Tb(3+), and F(-) ions, in the presence of glycerine as a capping agent, led to the formation of ultrafine, nanocrystalline CeF3:Tb(3+) 5%, Gd(3+) 5% (LnF3). The as-prepared fluoride nanoparticles were successfully coated with an amine modified silica shell. Subsequently, the obtained LnF3@SiO2@NH2 nanostructures were conjugated with 4-ethoxybenzoic acid in order to prove the possibility of organic modification and obtain a new functional nanomaterial. All of the nanophosphors synthesized exhibited intense green luminescence under UV light irradiation. Based on TEM (transmission electron microscopy) measurements, the diameters of the cores (≈12 nm) and core/shell particles (≈50 nm) were determined. To evaluate the cytotoxic activity of the nanomaterials obtained, their effect on human erythrocytes was investigated. LnF3 nanoparticles were bound to the erythrocyte membrane, without inducing any cytotoxic effects. After coating with silica, the nanoparticles revealed significant cytotoxicity. However, further functionalization of the nanomaterial with -NH2 groups as well as conjugation with 4-ethoxybenzoic acid entailed a decrease in cytotoxicity of the core/shell nanoparticles.