The nature of the axial ligand coordinated to the Yb3+ ion in [Yb­(DOTAM)]3+ has profound consequences in the magnetic anisotropy and optical properties of the complex, as evidenced by 1H NMR and UV–vis spectroscopies. The pseudocontact shifts of 1H nuclei and the 2F5/2 ← 2F7/2 absorption band were found to be very sensitive to the nature of the axial ligand (MeOH, H2O, MeOH, or F–). The energy levels of the 2F5/2 and 2F7/2 manifolds in [Yb­(DOTAM)­(X)]3+ (X = MeOH, H2O, or dimethyl sulfoxide (DMSO)) and [Yb­(DOTAM)­F]2+ complexes were assigned from the analysis of the optical spectra and ab initio calculations based on CASSCF wave functions that considered dynamic correlation through perturbation theory (NEVPT2) and spin–orbit coupling effects. The magnetic anisotropies obtained with ab initio calculations are in good agreement with the experimental values derived from 1H NMR spectral data, though for the [Yb­(DOTAM)­(H2O)]3+ and [Yb­(DOTAM)­F]2+ complexes, the explicit inclusion of a few second-sphere water molecules is required to improve the calculated data. Crystal-field calculations show that the observed pseudocontact shifts do not correlate well with the crystal-field parameter B 2 0, as predicted by Bleaney’s theory. The change in the sign of the magnetic anisotropy from prolate (X = MeOH, H2O, or DMSO) to oblate in [Yb­(DOTAM)­F]2+ is related to the relative energies of the 4f z 3 orbital and the 4f x 3/4f y 3 pair, which are affected by the coordination ability of the axial ligand.

Nanotechnology offers the possibility of operating on the same scale length at which biological processes occur, allowing to interfere, manipulate or study cellular events in disease or healthy conditions. The development of hybrid nanostructured materials with a high degree of chemical control and complex engineered surface including biological targeting moieties, allows to specifically bind to a single type of molecule for specific detection, signaling or inactivation processes. Magnetite nanostructures with designed composition and properties are the ones that gather most of the designs as theragnostic agents for their versatility, biocompatibility, facile production and good magnetic performance for remote in vitro and in vivo for biomedical applications. Their superparamagnetic behavior below a critical size of 30 nm has allowed the development of magnetic resonance imaging contrast agents or magnetic hyperthermia nanoprobes approved for clinical uses, establishing an inflection point in the field of magnetite based theragnostic agents.

Challenging magnetic hyperthermia (MH) applications of immobilized magnetic nanoparticles require detailed knowledge of the effective anisotropy constant (K eff ) to maximize heat release. Designing optimal MH experiments entails the precise determination of magnetic properties, which are, however, affected by the unavoidable concurrence of magnetic interactions in common experimental conditions. In this work, a mean-field energy barrier model (𝚫E), accounting for anisotropy (E A ) and magnetic dipolar (E D ) energy, is proposed and used in combination with AC measurements to a specifically developed model system of spherical magnetic nanoparticles with well-controlled silica shells, acting as a spacer between the magnetic cores. This approach makes it possible to experimentally demonstrate the mean field dipolar interaction energy prediction with the interparticle distance, d ij , E D ≈ 1/d ij 3 and obtain the E A as the asymptotic limit for very large d ij . In doing so, K eff uncoupled from interaction contributions is obtained for the model system (iron oxide cores with average sizes of 8.1, 10.2, and 15.3 nm) revealing to be 48, 23, and 11 kJ m −3 , respectively, close to bulk magnetite/maghemite values and independent from the specific spacing shell thicknesses selected for the study.

Iron oxide magnetic nanoparticles (MNPs) have been widely studied due to their versatility for diagnosis, tracking (magnetic resonance imaging (MRI)) and therapeutic (magnetic hyperthermia and drug delivery) applications. In this work, iron oxide MNPs with different single-core (8–40 nm) and multi-core (140–200 nm) structures were synthesized and functionalized by organic and inorganic coating materials, highlighting their ability as magnetic nanotools to boost cell biotechnological procedures. Single core Fe3O4@PDA, Fe3O4@SiO2-FITC-SiO2 and Fe3O4@SiO2-RITC-SiO2 MNPs were functionalized with fluorescent components with emission at different wavelengths, 424 nm (polydopamine), 515 (fluorescein) and 583 nm (rhodamine), and their ability as transfection and imaging agents was explored with HeLa cells. Moreover, different multi-core iron oxide MNPs (Fe3O4@CS, Fe3O4@SiO2 and Fe3O4@Citrate) coated with organic (citrate and chitosan, CS) and inorganic (silica, SiO2) shells were tested as efficient nanoheaters for magnetic hyperthermia applications for mild thermal heating procedures as an alternative to simple structures based on single-core MNPs. This work highlights the multiple abilities offered by the synergy of the use of external magnetic fields applied on MNPs and their application in different biomedical approaches.

Magnetic nanoparticles are versatile materials that have boosted the development of different biomedical applications, being superparamagnetic magnetite nanoparticles a milestone in the field, after achieving clinical approval as contrast agents in magnetic resonance imaging (Feridex®), magnetic hyperthermia agents for oncological treatments (NanoTherm®), or iron deficiency supplement (Feraheme®). However, its potential as theragnostic agent could be further expanded by its encapsulation within a biodegradable hydrogel, capable of enhancing the biocompatibility and loading abilities, to simultaneously carry drugs, radiotracers, or biomolecules. Gelatin, is a natural biopolymer with optimal in vivo feature and gelling capacity that has been extensively used for decades in pharmaceuticals. In this work, we have addressed the preparation of gelatin nanoparticles, bare and loaded with magnetite nanoparticles, with controlled size to be used as contrast agents in magnetic resonance imaging. The main formulation parameters influencing the preparation of gelatin nanoparticles with controlled size by single-step desolvation method, were studied and optimized, to produce small gelatin nanoparticles (97nm) and highly loaded (38% w/w) Fe3O4@citrate gelatin nanoparticles (150 nm) with high magnetic response (65emus/g). The viability assays of the magnetic gelatin nanoparticles, tested with mesenchymal stem cells, showed negligible toxicity and in vitro magnetic resonance imaging tests, performed in agar phantoms, revealed a good contrast for T2 weighting MRI, r2 = 265.5(mM−1 s−1), superior to commercial products, such as Resovist or Endorem.