Rare earth based nanostructures constitute a type of functional materials widely used and studied in the recent literature. The purpose of this review is to provide a general and comprehensive overview of the current state of the art, with special focus on the commonly employed synthesis methods and functionalization strategies of rare earth based nanoparticles and on their different bioimaging and biosensing applications. The luminescent (including downconversion, upconversion and permanent luminescence) and magnetic properties of rare earth based nanoparticles, as well as their ability to absorb X‐rays, will also be explained and connected with their luminescent, magnetic resonance and X‐ray computed tomography bioimaging applications, respectively. This review is not only restricted to nanoparticles, and recent advances reported for in other nanostructures containing rare earths, such as metal organic frameworks and lanthanide complexes conjugated with biological structures, will also be commented on.

A facile solvothermal route has been developed for the preparation of europium doped gadolinium orthovanadate nanoparticles (∼70 nm) with tetragonal structure, based on a homogenous precipitation reaction at 120 °C from rare earth precursors (yttrium nitrate and europium nitrate) and sodium orthovanadate solutions using an ethylene glycol–water mixture as the solvent. The effects of the doping level on the luminescence properties were evaluated in order to find the optimum nanophosphors. These nanocrystals were successfully functionalized with amino (two step process) and carboxylate (one-pot process) groups provided by amino-dextran polymers (AMD) and polyacrylic acid (PAA), respectively. It was found that while the luminescent properties of both kinds of functionalized systems were similar, the colloidal stability of the PAA-modified sample was higher, because of which, it was selected to study their cytotoxicity and magnetic properties (relaxivity and phantom analyses) to assess their potentiality as multifunctional probes for both “in vitro” optical biolabels and negative contrast agents for magnetic resonance imaging.

Why is the Eu ³⁺ :CaMoO ₄ unit cell bigger than that of CaMoO ₄ ? Does Na ⁺ co-doping improve the quantum yield of Eu ³⁺ :CaMoO ₄ phosphors?

Near-ultraviolet and visible excitable Eu- and Bi-doped NPs based on rare earth vanadates (REVO₄, RE = Y, Gd) have been synthesized by a facile route from appropriate RE precursors, europium and bismuth nitrate, and sodium orthovanadate, by homogeneous precipitation in an ethylene glycol/water mixture at 120 °C. The NPs can be functionalized either by a one-pot synthesis with polyacrylic acid (PAA) or by a Layer-by-Layer approach with poly(allylamine hydrochloride) (PAH) and PAA. In the first case, the particle size can also be tuned by adjusting the amount of PAA. The Eu- Bi-doped REVO₄ based nanophosphors show the typical red luminescence of Eu(III), which can be excited through an energy transfer process from the vanadate anions, resulting in a much higher luminescence intensity in comparison to the direct excitation of the europium cations. The incorporation of Bi into the REVO₄ structure shifts the original absorption band of the vanadate anions towards longer wavelengths, giving rise to nanophosphors with an excitation maximum at 342 nm, which can also be excited in the visible range. The suitability of such nanophosphors for bioimaging and biosensing applications, as well as their colloidal stability in different buffer media of biological interest, their cytotoxicity, their degradability at low pH, and their uptake by HeLa cells have been evaluated. Their suitability for bioimaging and biosensing applications is also demonstrated.