The interplay between single particle anisotropy and interparticle interactions in ensembles of magnetic nanoparticles.

This paper aims to analyze the competition of single particle anisotropy and interparticle interactions in nanoparticle ensembles using a random anisotropy model. The model is first applied to ideal systems of non-interacting and strongly dipolar interacting ensembles of maghemite nanoparticles. The investigation is then extended to more complex systems of pure cobalt ferrite CoFe2O4 (CFO) and mixed cobalt-nickel ferrite (Co,Ni)Fe2O4 (CNFO) nanoparticles. Both samples were synthetized by the polyol process and exhibit the same particle size (DTEM ≈ 5 nm), but with different interparticle interaction strengths and single particle anisotropy. The implementation of the random anisotropy model allows investigation of the influence of single particle anisotropy and interparticle interactions, and sheds light on their complex interplay as well as on their individual contribution. This analysis is of fundamental importance in order to understand the physics of these systems and to develop technological applications based on concentrated magnetic nanoparticles, where single and collective behaviors coexist.

Studying the effect of Zn-substitution on the magnetic and hyperthermic properties of cobalt ferrite nanoparticles.

The possibility to finely control nanostructured cubic ferrites (M(II)Fe2O4) paves the way to design materials with the desired magnetic properties for specific applications. However, the strict and complex interrelation among the chemical composition, size, polydispersity, shape and surface coating renders their correlation with the magnetic properties not trivial to predict. In this context, this work aims to discuss the magnetic properties and the heating abilities of Zn-substituted cobalt ferrite nanoparticles with different zinc contents (ZnxCo1-xFe2O4 with 0 < x < 0.6), specifically prepared with similar particle sizes (∼7 nm) and size distributions having the crystallite size (∼6 nm) and capping agent amount of 15%. All samples have high saturation magnetisation (Ms) values at 5 K (>100 emu g(-1)). The increase in the zinc content up to x = 0.46 in the structure has resulted in an increase of the saturation magnetisation (Ms) at 5 K. High Ms values have also been revealed at room temperature (∼90 emu g(-1)) for both CoFe2O4 and Zn0.30Co0.70Fe2O4 samples and their heating ability has been tested. Despite a similar saturation magnetisation, the specific absorption rate value for the cobalt ferrite is three times higher than the Zn-substituted one. DC magnetometry results were not sufficient to justify these data, the experimental conditions of SAR and static measurements being quite different. The synergic combination of DC with AC magnetometry and (57)Fe Mössbauer spectroscopy represents a powerful tool to get new insights into the design of suitable heat mediators for magnetic fluid hyperthermia.

Evolution of the magnetic structure with chemical composition in spinel iron oxide nanoparticles.

Magnetic properties of iron oxide nanoparticles with spinel structure are strictly related to a complex interplay between cationic distribution and the presence of a non-collinear spin structure (spin canting). With the aim to gain better insight into the effect of the magnetic structure on magnetic properties, in this paper we investigated a family of small crystalline ferrite nanoparticles of the formula CoxNi1-xFe2O4 (0 ≤x≤ 1) having equal size (≈4.5 nm) and spherical-like shape. The field dependence of magnetization at low temperatures indicated a clear increase of magnetocrystalline anisotropy and saturation magnetization (higher than the bulk value for CoFe2O4: ∼130 A m(2) kg(-1)) with the increase of cobalt content. The magnetic structure of nanoparticles has been investigated by Mössbauer spectroscopy under an intense magnetic field (8 T) at a low temperature (10 K). The magnetic properties have been explained in terms of an evolution of the magnetic structure with the increase of cobalt content. In addition a direct correlation between cationic distribution and spin canting has been proposed, explaining the presence of a noncollinear spin structure in terms of superexchange interaction energy produced by the average cationic distribution and vacancies in the spinel structure.

Gold-assisted E' centres formation on the silica surface of Au/SBA-15 catalysts for low temperature CO oxidation.

SH-functionalized SBA-15 was synthesized and gold nanoclusters were grafted inside its channels. Different portions of such gold-containing material were subjected to a variety of thermal treatments, including calcination in the 300-560 °C temperature range and further treatments under a hydrogen atmosphere at diverse temperatures (up to 600 °C). The resulting materials were thoroughly characterized by CHS elemental analysis, X-ray diffraction, transmission electron microscopy, N2 physisorption and H2 chemisorption, as well as by Raman, NMR, FTIR and EPR spectroscopies, in order to investigate the influence of the temperature and atmosphere of the pretreatment on the gold particle size and oxidation state, the formation of defective E' centres on the silica support and their ability to induce the formation of reactive O2(-) surface species. Catalytic testing for the CO oxidation reaction was carried out in the 40-150 °C temperature range. Significant differences in catalytic behaviour were observed among the catalysts, which are discussed in the light of the characterization results. A mechanism for the "activation" of the non-reducible ("inert") SBA-15 support involving Au(0)→ Au(+) transformation is proposed, where gold metal plays an essential twofold role: it induces the formation of atomic hydrogen by dissociatively adsorbing H2 and triggers the formation of E' centres by transferring an electron to positively charged silicon species.

Cationic distribution and spin canting in CoFe2O4 nanoparticles.

CoFe(2)O(4) nanoparticles (D(NPD) ~6 nm), prepared by a thermal decomposition technique, have been investigated through the combined use of dc magnetization measurements, neutron diffraction, and (57)Fe Mössbauer spectrometry under high applied magnetic field. Despite the small particle size, the value of saturation magnetization at 300 K (M(s) Í = 70 A m(2) kg(-1)) and at 5 K (M(s) Í = 100 A m(2) kg(-1)) are rather close to the bulk values, making the samples prepared with this method attractive for biomedical applications. Neutron diffraction measurements indicate the typical ferrimagnetic structure of the ferrites, showing an inversion degree (γ(NPD) = 0.74) that is in very good agreement with cationic distribution established from low temperature (10 K) Mössbauer measurements in high magnetic field (γ(moss) = 0.76). In addition, the in-field Mössbauer spectrum shows the presence of a non-collinear spin structure in both A and B sublattices. The results allow us to explain the high value of saturation magnetization and provide a better insight into the complex interplay between cationic distribution and magnetic disorder in ferrimagnetic nanoparticles.

Thermal hysteresis of Morin transition in hematite particles.

Rhombohedral shaped, single crystal hematite particles with narrow size distribution (D(TEM) = 93 +/- 2 nm) were prepared by hydrolysis of iron chloride and polymerisation in water. The results of field dependent magnetization measurements at different warming-cooling rates and ac susceptibility measurements at varying frequencies are reported and discussed. Thermal hysteresis (DeltaT(M)) associated with the Morin transition and field dependence of the Morin temperature (T(M)) are observed in warming-cooling cycles (DeltaT(M) = 25 and 13 K for H = 0.1 and 3 T, respectively) due to the first order phase transition. A frequency dependence of ac susceptibility is observed above T(M), as a result of the relaxation of the magnetic moment of hematite particles in the weak-ferromagnetic phase.

Spin-glass-like freezing and enhanced magnetization in ultra-small CoFe2O4 nanoparticles.

The magnetic properties of ultra-small (3 nm) CoFe(2)O(4) nanoparticles have been investigated by DC magnetization measurements as a function of temperature and magnetic field. The main features of the magnetic behaviour are blocking of non-interacting particle moments (zero-field-cooled magnetization T(max) approximately 40 K), a rapid increase of saturation magnetization (up to values higher than for the bulk material) at low T and an increase in anisotropy below 30 K due to the appearance of exchange bias. The low temperature behaviour is determined by a random freezing of surface spins. Localized spin-canting and cation distribution between the two sublattices of the spinel structure account quantitatively for the observed increase in saturation magnetization.

Spin-canting and magnetic anisotropy in ultrasmall CoFe2O4 nanoparticles.

The magnetic properties of cobalt ferrite nanoparticles dispersed in a silica matrix in samples with different concentrations (5 and 10 wt% CoFe2O 4) and same particle size (3 nm) were studied by magnetization, DC and AC susceptibility, and Mossbauer spectroscopy measurements. The results indicate that the particles are very weakly interacting. The magnetic properties (saturation magnetization, anisotropy constant, and spin-canting) are discussed in relation to the cation distribution.

Magnetic properties of cobalt ferrite-silica nanocomposites prepared by a sol-gel autocombustion technique.

The magnetic properties of cobalt ferrite-silica nanocomposites with different concentrations (15, 30, and 50 wt %) and sizes (7, 16, and 28 nm) of ferrite particles have been studied by static magnetization measurements and Mossbauer spectroscopy. The results indicate a superparamagnetic behavior of the nanoparticles, with weak interactions slightly increasing with the cobalt ferrite content and with the particle size. From high-field Mossbauer spectra at low temperatures, the cationic distribution and the degree of spin canting have been estimated and both parameters are only slightly dependent on the particle size. The magnetic anisotropy constant increases with decreasing particle size, but in contrast to many other systems, the cobalt ferrite nanoparticles are found to have an anisotropy constant that is smaller than the bulk value. This can be explained by the distribution of the cations. The weak dependence of spin canting degree on particle size indicates that the spin canting is not simply a surface phenomenon but also occurs in the interiors of the particles.

[Propofol and fentanyl in Sanfilippo disease. Surgical intervention with adenotonsillectomy]. / Propofol e fentanyl nella malattia di Sanfilippo. Intervento chirurgico di adenotonsillectomia.

An intravenous anesthesia with propofol and fentanyl was used for adenotonsillectomy in a child affected by mucopolysaccharidosis. This technique proved to be safe and convenient without peri- and postoperative complications.