We report on the suitability of core/shell nanoparticles (NPs) for magnetic fluid hyperthermia in a selfregulated and theranostic approach. Aqueous magnetic colloids based on core/shell ZnxMnyFezO4@γ-Fe2O3 and ZnxCoyFe-zO4@γ-Fe2O3 NPs were produced by a three-step chemical synthesis. Systematic deviations from stoichiometry was observed with increasing Zn substitution for both series of samples. We investigated how the chemical composition affects saturation magnetization, magnetic anisotropy and thermomagnetic properties of these core/shell NPs. The heating efficiency through specific power absorption (SPA) was analyzed in the framework of the linear response theory. SPA values obtained for NPs presenting different contrast of anisotropy between the core and shell materials indicate no evidence of enhanced exchange coupling contribution to the heating efficiency.

The heat produced by magnetic nanoparticles, when they are submitted to a time-varying magnetic field, has been used in many auspicious biotechnological applications. In the search for better performance in terms of the specific power absorption (SPA) index, researchers have studied the influence of the chemical composition, size and dispersion, shape, and exchange stiffness in morphochemical structures. Monodisperse assemblies of magnetic nanoparticles have been produced using elaborate synthetic procedures, where the product is generally dispersed in organic solvents. However, the colloidal stability of these rough dispersions has not received much attention in these studies, hampering experimental determination of the SPA. To investigate the influence of colloidal stability on the heating response of ferrofluids, we produced bimagnetic core@shell NPs chemically composed of a ZnMn mixed ferrite core covered by a maghemite shell. Aqueous ferrofluids were prepared with these samples using the electric double layer (EDL) as a strategy to maintain colloidal stability. By starting from a proper sample, ultrastable concentrated ferrofluids were achieved by both tuning the ion/counterion ratio and controlling the water content. As the colloidal stability mainly depends on the ion configuration on the surface of the magnetic nanoparticles, different levels of nanoparticle clustering are achieved by changing the ionic force and pH of the medium. Thus, the samples were submitted to two procedures of EDL destabilization, which involved dilution with an alkaline solution and a neutral pH viscous medium. The SPA results of all prepared ferrofluid samples show a reduction of up to half the efficiency of the standard sample when the ferrofluids are in a neutral pH or concentrated regime. Such results are explained in terms of magnetic dipolar interactions. Our results point to the importance of ferrofluid colloidal stability in a more reliable experimental determination of the NP heat generation performance.

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In this work, the crystalline structure, chemical composition, size, and morphology of core@shell nanoparticles based on Zn-Mn ferrite nanocrystals were investigated. These materials have been proposed as promising candidates for multifunctional applications in biomedicine, catalysis, environmental remediation, among others. Those properties were probed by using several experimental techniques such as Synchrotron X-Ray Diffraction, Energy-Dispersive X-ray Spectroscopy, Transmission Electron Microscopy and Selected Area Electron Diffraction. Results show that all synthesized nanoparticles present a single crystalline spinel phase without the appearance of undesirable byproducts. The nanoparticles present a non-stoichiometric Zn-Mn ferrite core, due to a Fe enrichment and a Zn loss with respect to the synthesis medium. The surface treatment of the nanoparticles induces a greater iron enrichment, which occurs at the nanoparticles surface without changing the crystalline structure. Finally, modifications in lattice parameters and strain suggest a contribution of the Mn 2+ cations, mainly related to their easy oxidation in the synthesis route, which increases the structural vacancies of Mn-richer ferrites.

RESUMOA estrutura, a morfologia e o tamanho de nanopartículas de ferrita mista de Zn-Mn obtidas durante o processo de síntese de fluidos magnéticos foram investigadas utilizando as técnicas de