Chemical heterogeneities in nanometric titanomagnetites prepared by soft chemistry and studied ex situ : evidence for fe-segregation and oxidation kinetics

Nanocrystalline Fe-based spinels with composition Fe3-xTixO4 are synthesized using soft chemistry. Two steps are involved:  precipitation in an aqueous solution followed by thermal annealing under a reducing mixture of N2/H2/H2O gases. Fe-segregation is found inside stoichiometric particles when the powders are studied ex situ; they exhibit a strong surface iron enrichment. This heterogeneity is related to kinetic effects linked to the difference of mobility between Fe2+ and Ti4+ cations during the partial oxidation of cations occurring ex situ. Stresses in the grains induced by oxidation govern the oxidation kinetics and lead to an abrupt compositional variation inside each particle. These…

Apparent magic numbers in embedded Ti-O clusters

Stable clusters constituted of four ${\mathrm{TiO}}_{2}$ entities have been evidenced in nanometer-sized spinel oxides by a combination of diffraction and x-ray-absorption experiments. Contrary to free clusters, the size of the embedded clusters is strongly determined by the constraints imposed by the surrounding matrix so that the magic number of four is in fact specific to the matrix and only then apparent.

Phénomènes de ségrégation dans les ferrites de titane nanométriques : apports complémentaires de différentes techniques expérimentales (DRX, XPS, EXAFS ...)

Grâce a la complementarite de diverses techniques deux phenomenes de segregation ont ete mis en evidence dans les ferrites de titane nanostructures: une segregation cinetique (dite dynamique) et une segregation thermodynamique. Par des techniques d'analyse locales (MET, XPS) et statistiques (DRX...), des heterogeneites au sein des grains de poudre contenant des cations Fe 2+ ont ete mises en evidence lors de leur etude a l'air. Leur origine est cinetique et decoule d'une oxydation incomplete des cations Fe 2+ . Des affinement de Rietveld de diagrammes de diffraction des rayons X et diffraction de neutrons ont permis de montrer quant a eux que le titane ainsi que toutes les lacunes creees lo…

A top-down synthesis route to ultrasmall multifunctional Gd-based Silica nanoparticles for theranostic applications

International audience; New, ultrasmall nanoparticles with sizes below 5 nm have been obtained. These small rigid platforms (SRP) are composed of a polysiloxane matrix with DOTAGA (1,4,7,10-tetraazacyclododecane-1-glutaric anhydride-4,7,10-triacetic acid)-Gd3+ chelates on their surface. They have been synthesised by an original top-down process: 1) formation of a gadolinium oxide Gd2O3 core, 2) encapsulation in a polysiloxane shell grafted with DOTAGA ligands, 3) dissolution of the gadolinium oxide core due to chelation of Gd3+ by DOTAGA ligands and 4) polysiloxane fragmentation. These nanoparticles have been fully characterised using photon correlation spectroscopy (PCS), transmission elec…

Cation Distribution in a Titanium Ferrite Fe2.75Ti0.25O4Measured byin-SituAnomalous Powder Diffraction Using Rietveld Refinement

Many ferrites contain different cations with various valence states and location in the spinel structure. In compounds such as these, only a combination of different techniques such as Mussbauer spectroscopy, IR analysis, and thermogravimetry allows the distribution of cations to be obtained. For very complicated distributions, the mathematical decomposition of derivative thermogravimetric curves (DTG) leading to quantitative distribution is uncertain. In this paper, we present an alternative technique based on resonant diffraction. The anomalous scattering of each cation in the crystalline material is used to determine its amount and position by Rietveld refinement. Since the energy for su…

Sintering of copper nanopowders under hydrogen: an in situ X-ray diffraction analysis.

Abstract The reduction by hydrogen gas of the cuprite layer on copper nanocrystals and the subsequent sintering of the nano-particles were studied using in-situ X-ray diffraction and dilatometry. Spherical nanocrystals produced by evaporation and condensation have an average size of 35 nm, exhibiting a large surface curvature. Each nanoparticle is coated with a 3.5 nm layer of Cu 2 O, which is rough and disordered, as revealed by high-resolution electron microscopy. Reduction by hydrogen of this curved cuprite layer occurs at 363 K, which is ≈65 K lower than is observed on a layer supported by micrometer-sized or bulk copper with a flat surface. The reduction process and its effect on the s…

Minor changes in the macrocyclic ligands but major consequences on the efficiency of gold nanoparticles designed for radiosensitization

International audience; Many studies have been devoted to adapting the design of gold nanoparticles to efficiently exploit their promising capability to enhance the effects of radiotherapy. In particular, the addition of magnetic resonance imaging modality constitutes an attractive strategy for enhancing the selectivity of radiotherapy since it allows the determination of the most suited delay between the injection of nanoparticles and irradiation. This requires the functionalization of the gold core by an organic shell composed of thiolated gadolinium chelates. The risk of nephrogenic systemic fibrosis induced by the release of gadolinium ions should encourage the use of macrocyclic chelat…

Experimental set up for determining the temperature-oxygen partial pressure conditions during synthesis of spinel oxide nanoparticles

Abstract Nanometric spinel oxide powders, Fe 3− x M x O 4 , where M is a transition element, have been synthetized by soft chemistry. This method generally leads to a non-stoichiometric phase, Fe 3− x M x O 4+δ where δ is the deviation from stoichiometry so that further annealing at low temperatures around 450°C and low oxygen partial pressure around 10 −25 Pa given by N 2 /H 2 /H 2 O gas mixtures is required: this enables a stoichiometric compound to be obtained and a nanometric size to be maintained. The complete set up consisting of a gas mixer, a thermogravimetric apparatus and a preparative furnace is described. Some results concerning the conditions of temperature and oxygen partial p…

The use of theranostic gadolinium-based nanoprobes to improve radiotherapy efficacy

International audience; A new efficient type of gadolinium-based theranostic agent (AGuIX) has recently been developed for magnetic resonance imaging (MRI)-guided radiotherapy. These new particles consist of a polysiloxane network surrounded by a number of gadolinium chelates, usually 10. Due to their small size (<5 nm), AGuIX typically exhibit biodistributions that are almost ideal for diagnostic and therapeutic purposes. For example, while a significant proportion of these particles accumulate in tumours, the remainder is rapidly eliminated by the renal route. In addition, these particles present no evidence of toxicity, in the absence of irradiation with up to 10 times the planned dose f…

Cation Distribution in Ferrites with Spinel Structure Measured by Anomalous Powder Diffraction

Ultrasmall Rigid Particles as Multimodal Probes for Medical Applications

International audience; Ultrasmall but multifunctional: Rigid imaging particles that are smaller than 5 nm in size can be obtained in a top-down process starting from a core–shell structure (core=gadolinium oxide; shell=polysiloxane). They represent the first multifunctional silica-based particles that are sufficiently small to escape hepatic clearance and enable animal imaging by four complementary techniques.

Utilisation de la diffraction résonnante pour déterminer la distribution cationique d'un ferrite de titane nanométrique

Les proprietes magnetiques des ferrites de structure spinelle dependent, entre autres, de la distribution cationique dans la maille. La connaissance de cette repartition a pu etre obtenue dans le cas d'un ferrite substitue au titane en utilisant la diffraction anomale de poudre couplee avec un affinement structural de type Rietveld, methode qui est le fruit des dernieres avancees effectuees autour du rayonnement synchrotron.

Réactivité vis-à-vis de l'oxygène de spinelles de fer-vanadium de taille nanométrique et distribution cationique

Resume L'etat de division des spinelles de fer-vanadium nanometriques V x Fe 3− x O 4 (0 ⩽ x ⩽ 2 ) permet d'oxyder au sein-meme de la structure spinelle les ions du fer et du vanadium. Les analyses calorimetriques et thermogravimetriques, ainsi que la spectroscopie infrarouge, montrent que les ions Fe B 2+ ,V B 3+ et Fe A 2+ sont oxydes successivement en ions Fe 3+ et V 5+ a des temperatures inferieures a 450 °C. Les spinelles lacunaires a valence mixte qui en resultent, ont un taux en lacunes croissant avec x, qui peut etre superieur a ceux determines jusqu'alors pour ce type d'oxydes.

Correlation between oxidation states of transition metal ions and variation of the coercivity in mixed-valence defect spinel ferrites

Abstract Due to the very high dispersion of mixed-valence spinel ferrites prepared by ‘soft chemistry’ it becomes possible to oxidize in the spinel lattice, not only ferrous ions but also different transition metal ions (Cr 3+ , Mn 2+ , Mn 3+ , Mo 3+ , Mo 4+ V 2+ , V 3+ , Cu + ), by ‘soft’ oxidation between 150 and 500°C, under formation of non-stoichiometric spinels cation vacancies. The oxidation state with the coordination and the oxidation temperature of the cations have been determined in coppermanganese ferrites by derivative thermogravimetry (DTG), based on the specific solid-state reactivity of cations in the redox reaction. For Co-modified non-stoichiometric spinels, which present…

Mechanical activation conditions of the Fe2O3 and V2O3 mixture powders in order to obtain a nanometric vanadium spinel ferrite

Abstract Co-milling of iron and vanadium oxides allows to obtain an intimate oxides mixture at a nanoscale, similar to a coprecipitate elaborated by soft chemistry. Reduction of such a mixture in the same temperature and oxygen partial pressure conditions (500°C and 10−25 Pa) as the soft chemistry products leads to a nanometric vanadium ferrite with the only spinel phase. The characterization of the powders is achieved by X-ray diffraction (XRD), scanning electron microscopy, infrared (IR) spectrometry, thermogravimetry and calorimetry. Homogeneity of grain size and chemical composition is reached if the initial oxides have similar grain size.

XPS and EELS investigations of chemical homogeneity in nanometer scaled Ti-ferrites obtained by soft chemistry

Abstract Nanocrystalline Ti-ferrites with composition Fe 3− x Ti x O 4 with 0≤ x ≤1 are synthesized using the soft chemistry route. Heterogeneities in precipitate and annealed powders are investigated by a combination of XPS and EELS techniques. As-prepared powder consists in particles with spinel structure and grain size of about 15 nm. Due to high reactivity towards oxygen of nanoparticules, a significant amount of Fe 2+ cations oxidize during precipitation, so that precipitated powders present large deviation from oxygen-metal stoichiometry. Moreover precipitated particles are evidenced to exhibit a strong surface titanium enrichment and an iron richer core. Observation of such cation se…

Evidence for the verwey transition in highly nonstoichiometric nanometric fe-based ferrites

The nanometric scale allows an investigation of the Verwey transition: the impact of varying degree of oxidation of Fe cations on this transition was studied by means of zero-field-cooled superconducting quantum interference device measurements in nanometric highly nonstoichiometric particles of pure and Ti-substituted magnetite synthesized using soft chemistry route. It is clearly shown that (i) there is a shift of the transition towards higher temperatures for nanometer scaled compounds and (ii) the amplitude, the temperature, and the order of the transition are only depending on the number of ${\mathrm{Fe}}^{2+}{/\mathrm{F}\mathrm{e}}^{3+}$ pairs in octahedral coordination.

New Ceramics for the Information Storage: Nanoparticles of Titanium Ferrites. Influence of Oxidation and Reduction Reactions upon the Coercivity

Synthèse de poudres nanométriques de titanate de strontium par émulsion stabilisée mécaniquement: maîtrise et prédiction de la taille des particules

Resume La synthese de poudres nanometriques de titanate de strontium a partir d'une emulsion eau dans alcool stabilisee par agitation mecanique a ete etudiee avec l'objectif de maitriser a la lois la taille et la stœchiometrie des poudres obtenues. La taille des particules a ete ajustee par l'intermediaire de deux parametres du milieu reactionnel: la fraction volumique de la phase aqueuse et la concentration en precurseurs. Une relation entre la taille des gouttelettes de l'emulsion et la taille des particules des poudres de SrTiO3 obtenues apres precipitation a ainsi ete mise en evidence. Elle s'explique a partir d'un modele qui implique, entre autres hypotheses, que la vitesse de germinat…

Ultrasmall particles for Gd-MRI and68Ga-PET dual imaging

Nanoparticles made of a polysiloxane matrix and surrounded by 1,4,7,10-tetraazacyclododecane-1-glutaric anhydride-4,7,10-triacetic acid (DOTAGA)[Gd(3+) ] and 2,2'-(7-(1-carboxy-4-((2,5-dioxopyrrolidin-1-yl)oxy)-4-oxobutyl)-1,4,7-triazonane-1,4-diyl)diacetic acid) NODAGA[(68) Ga(3+) ] have been synthesized for positron emission tomography/magnetic resonance (PET/MRI) dual imaging. Characterizations were carried out in order to determine the nature of the ligands available for radiolabelling and to quantify them. High radiolabelling purity (>95%) after (68) Ga labelling was obtained. The MR and PET images demonstrate the possibility of using the nanoparticles for a combined PET/MR imaging sca…