A detailed investigation of the onion structure of exchanged coupled magnetic Fe3-dO4@CoFe2O4@Fe3-dO4 nanoparticles

Nanoparticles that combine several magnetic phases offer wide perspectives for cutting edge applications because of the high modularity of their magnetic properties. Besides the addition of the magnetic characteristics intrinsic to each phase, the interface that results from core-shell and, further, from onion structures leads to synergistic properties such as magnetic exchange coupling. Such a phenomenon is of high interest to overcome the superparamagnetic limit of iron oxide nanoparticles which hampers potential applications such as data storage or sensors. In this manuscript, we report on the design of nanoparticles with an onion-like structure which has been scarcely reported yet. These nanoparticles consist of a Fe3-dO4 core covered by a first shell of CoFe2O4 and a second shell of Fe3-dO4, e.g., a Fe3-dO4@CoFe2O4@Fe3-dO4 onion-like structure. They were synthesized through a multistep seed-mediated growth approach which consists consists in performing three successive thermal decomposition of metal complexes in a high-boiling-point solvent (about 300 °C). Although TEM micrographs clearly show the growth of each shell from the iron oxide core, core sizes and shell thicknesses markedly differ from what is suggested by the size increasing. We investigated very precisely the structure of nanoparticles in performing high resolution (scanning) TEM imaging and geometrical phase analysis (GPA). The chemical composition and spatial distribution of atoms were studied by electron energy loss spectroscopy (EELS) mapping and spectroscopy. The chemical environment and oxidation state of cations were investigated by 57Fe Mössbauer spectrometry, soft X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The combination of these techniques allowed us to estimate the increase of Fe2+ content in the iron oxide core of the core@shell structure and the increase of the cobalt ferrite shell thickness in the core@shell@shell one, whereas the iron oxide shell appears to be much thinner than expected. Thus, the modification of the chemical composition as well as the size of the Fe3-dO4 core and the thickness of the cobalt ferrite shell have a high impact on the magnetic properties. Furthermore, the growth of the iron oxide shell also markedly modifies the magnetic properties of the core-shell nanoparticles, thus demonstrating the high potential of onion-like nanoparticles to accurately tune the magnetic properties of nanoparticles according to the desired applications. © 2021 American Chemical Society

Unveiling the role of surface, size, shape and defects of iron oxide nanoparticles for theranostic applications

Iron oxide nanoparticles (IONPs) are well-known contrast agents for MRI for a wide range of sizes and shapes. Their use as theranostic agents requires a better understanding of their magnetic hyperthermia properties and also the design of a biocompatible coating ensuring their stealth and a good biodistribution to allow targeting of specific diseases. Here, biocompatible IONPs of two different shapes (spherical and octopod) were designed and tested in vitro and in vivo to evaluate their abilities as high-end theranostic agents. IONPs featured a dendron coating that was shown to provide anti-fouling properties and a small hydrodynamic size favoring an in vivo circulation of the dendronized IONPs. While dendronized nanospheres of about 22 nm size revealed good combined theranostic properties (r2 = 303 mM s−1, SAR = 395 W gFe−1), octopods with a mean size of 18 nm displayed unprecedented characteristics to simultaneously act as MRI contrast agents and magnetic hyperthermia agents (r2 = 405 mM s−1, SAR = 950 W gFe−1). The extensive structural and magnetic characterization of the two dendronized IONPs reveals clear shape, surface and defect effects explaining their high performance. The octopods seem to induce unusual surface effects evidenced by different characterization techniques while the nanospheres show high internal defects favoring Néel relaxation for magnetic hyperthermia. The study of octopods with different sizes showed that Néel relaxation dominates at sizes below 20 nm while the Brownian one occurs at higher sizes. In vitro experiments demonstrated that the magnetic heating capability of octopods occurs especially at low frequencies. The coupling of a small amount of glucose on dendronized octopods succeeded in internalizing them and showing an effect of MH on tumor growth. All measurements evidenced a particular signature of octopods, which is attributed to higher anisotropy, surface effects and/or magnetic field inhomogeneity induced by tips. This approach aiming at an analysis of the structure–property relationships is important to design efficient theranostic nanoparticles.The Region Alsace, France, and the Labex Chimie des Systemes Complexes, University of Strasbourg, France are gratefully acknowledged for the doctoral fellowship to Geoffrey Cotin. This research project was also co-funded by Labex CSC, Alsace contre le cancer, INCA (project PRTK14, THERAMAG 2014-225) and the INTERREG project NANOTRANSMED. The “NANOTRANSMED” project is co-funded by the European Regional Development Fund (ERDF) and by the Swiss Confederation and the Swiss cantons of Aargau, Basel-Landschaft and Basel-Stadt, in the framework of the INTERREG V Upper Rhine program (“Transcending borders with every project”). The authors thank Morgane Rabineau for epifluorescence imaging and Nadia Messaddeq for TEM imaging of cells. The authors thank the Center for Microscopy and Molecular Imaging (CMMI, supported by the European Regional Development Fund and the Walloon Region). This work was supported by the Fond National de la Recherche Scientifique (FNRS), UIAP VII, ARC Programs of the French Community of Belgium and the Walloon region (Gadolymph and Holocancer programs). All the authors acknowledge the COST action TD1402 “RADIOMAG”. D. Ortega and F. J. Teran acknowledge support from the ‘Severo Ochoa’ Programme for Centres of Excellence in R&D (MINECO, Grant SEV-2016-0686), the Spanish Ministry of Economy and Competitiveness for the NANOLICO project (MAT2017-85617-R), the Spanish Ministry of Science through the NaNoCAR grant PID2020-117544RB-I00, the Ramón y Cajal grant RYC2018-025253-I and Research Networks grant RED2018-102626-T, the HEATOOLS project (BIO2017-84246-C2-1-R), the Comunidad de Madrid for grant NANOMAGCOST (P2018/NMT-4321), DGA for public funding from Fondo Social (grupos DGA), and the European Commission for the funding received through the H2020 “NoCanTher” project (GA No. 685795).Peer reviewe

INHOMOGENEOUS PROPERTIES OF IONIC SEMI-SPIN-GLASSES STUDIED BY MÖSSBAUER SPECTROSCOPY

We have analysed in terms of static hyperfine field distributions the Mössbauer spectra of mixed Zn-Mg ferrites. Typical features of semi-spin glasses are observed both in average and locally : in each sample, the relevant data are smeared out in a way which reveals the behavior of the series

Microstructural and magnetic properties of Fe/Cr-substituted ferrite composites

Composites made of iron and Cr doped magnetite are obtained by precipitation from the metallic chlorides salts into a KOH solution heated under reflux. A KOH concentration of 14 mol l−1 is required. The composition of the samples is determined by X-ray diffraction, TG measurements, chemical analysis and Mössbauer spectrometry. The higher the chromium content, the smaller the lattice parameter and the lower the metal ratio. For Cr/Fe ≤ 0.1, the chemical formula of the composites can be written FeA/(Fe$^{\nu+}_{x}$Cr$^{3+}_{y}\square_{3-(x+y)}$O$_{4})_{1-{\rm A}}$, $0\le y\le0.23$. We show that only in-field Mössbauer spectrometry at low temperature is suitable to estimate unambiguously both the proportions of octahedral and tetrahedral iron sites in spinel and the valence of delocalised iron state, if any. A peculiar A-site occupation by either vacancies or Cr3+ ions is observed. This is probably due to the low temperature synthesis. The two phases, metal and spinel are found to be intimately mixed within the nanometer sized particles. For Cr/Fe ratios higher than 0.1, hydroxide phase is also present

Unconventional magnetic behavior of iron-oxide nanoparticles in polymeric matrices

We report the results of magnetization and 57Fe Mössbauer spectroscopy measurements performed in the temperature range 5-300 K on composites containing iron¿oxide nanoparticles encased in polystyrene type resins. After carrying out a suitable field treatment in order to decouple the particles from the matrix, a fraction of the particles freely rotate in response to an applied magnetic fiel

Magnetism of nanocrystalline Finemet alloy: experiment and simulation

Mössbauer spectrometry and magnetic measurements are employed to experimentally investigate the magnetic behavior of nanocrystalline Fe 73.5 Cu 1Nb 3Si 13.5 B9 ribbons obtained by appropriate annealing of the amorphous precursor. A detailed analysis of the correlation between the microstructure of annealed samples and their magnetic properties is provided. Thermomagnetic data allow the Curie temperatures of both amorphous residual matrix and nanocrystalline phase to be estimated. The differences between Curie temperatures of amorphous residual matrix and amorphous precursor are investigated and explained in terms of magnetic polarization of the matrix by exchange fields arising from the nanocrystalline grains. Theoretical systems of spins consisting of a single ferromagnetic nanocrystalline grain immersed in weakly ferromagnetic environment, quite similar to our real samples, are considered and their magnetic behavior is investigated by Monte Carlo simulation of low temperature spin ordering, with emphasize on the matrix-nanocrystalline grain interface which is shown to exhibit peculiar magnetic behavior. The magnetic features of the matrix-nanocrystalline grain interface are studied, as depending on matrix-nanocrystalline grain exchange coupling as well as crystalline fraction of the nanocrystalline systems. Copyright Springer-Verlag Berlin/Heidelberg 2003

Towards the reactivity of MIL-53 or FeIII(OH)0.8F0.2[O2C-C6H4-CO2]versus lithium

We demonstrate here the reversible electrochemical insertion of lithium into the hybrid porous solid FeIII(OH)0.8F0.2[O2C-C6H4-CO2]. Used as an electrode in Li-half cell, this material shows a reversible redox process around 3.0V vs. Li+/Li° exchanging 0.6Li per formula unit with interesting capacity retention and rate capability. Moreover, it reveals an interesting feature for MOFs with large tunnels: the uptake of electrolyte molecules within their channels, which facilitates ionic transport in MOFs. Mixed valence in MOFs opens new opportunities for the elaboration of materials with tuneable properties for various applications. © 2007 Elsevier B.V. All rights reserved