Tuning Properties of Cerium Dioxide Nanoparticles by Surface Modification with Catecholate-type of Ligands

Cerium dioxide (CeO₂) finds applications in areas such as corrosion protection, solar cells, or catalysis, finding increasing applications in biomedicine. This work reports on surface-modified CeO₂ particles in order to tune their applicability in the biomedical field. Stable aqueous CeO₂ sol, consisting of 3-4 nm in size crystallites, was synthesized using forced hydrolysis. The coordination of catecholate-type of ligands (catechol, caffeic acid, tiron, and dopamine) to the surface-Ce atoms is followed with the appearance of absorption in the visible spectral range as a consequence of interfacial charge-transfer complex formation. The spectroscopic observations are complemented with the density functional theory calculations using a cluster model. The synthesized samples were characterized by X-ray diffraction analysis, transmission electron microscopy, and nitrogen adsorption-desorption isotherms. The ζ-potential measurements indicated that the stability of CeO₂ sol is preserved upon surface modification. The pristine CeO₂ nanoparticles (NPs) are nontoxic against pre-osteoblast cells in the entire studied concentration range (up to 1.5 mM). Hybrid CeO₂ NPs, capped with dopamine or caffeic acid, display toxic behavior for concentrations ≥0.17 and 1.5 mM, respectively. On the other hand, surface-modified CeO₂ NPs with catechol and tiron promote the proliferation of pre-osteoblast cells.