Enio Lima

Spin disorder and magnetic anisotropy in Fe3O4 nanoparticles

We have studied the magnetic behavior of dextran-coated magnetite (Fe3O4) nanoparticles with median particle size ⟨d⟩=8nm. Magnetization curves and in-field Mossbauer spectroscopy measurements showed that the magnetic moment MS of the particles was much smaller than the bulk material. However, we found no evidence of magnetic irreversibility or nonsaturating behavior at high fields, usually associated to spin canting. The values of magnetic anisotropy Keff from different techniques indicate that surface or shape contributions are negligible. It is proposed that these particles have bulklike ferromagnetic structure with ordered A and B sublattices, but nearly compensated the magnetic moments. The dependence of the blocking temperature with frequency and applied fields, TB(H,ω), suggests that the observed nonmonotonic behavior is governed by the strength of interparticle interactions.

Magnetic Hyperthermia With Fe

We have studied the magnetic and power absorption properties of a series of magnetic nanoparticles (MNPs) of Fe3O4 with average sizes langdrang ranging from 3 to 26 nm. Heating experiments as a function of particle size revealed a strong increase in the specific power absorption (SPA) values for particles with langdrang = 25-30 nm. On the other side saturation magnetization MS values of these MNPs remain essentially constant for particles with langdrang above 10 nm, suggesting that the absorption mechanism is not determined by MS. The largest SPA value obtained was 130 W/g, corresponding to a bimodal particle distribution with average size values of 17 and 26 nm.

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The role of agglomeration and magnetic interparticle interactions in heat generation of magnetic ferrofluids in an ac magnetic field is still unclear, with apparent discrepancy between the results presented in the literature. In this work, we measured the heat generating capability of agglomerated ferrite nanoparticles in a non-invasive ac magnetic field with f = 100 kHz and H0 = 13 kA m −1 . The nanoparticles were morphologically and magnetically characterized, and the specific absorption rate (SAR) for our ac magnetic field presents a clear dependence on the diameter of the nanoparticles, with a maximum SAR = 48 Wg −1 for 15 nm. Our agglomerated nanoparticles have large hydrodynamic diameters, thus the mechanical relaxation can be neglected as a heat generation mechanism. Therefore, we present a model that simulates the SAR dependence of the agglomerated samples on the diameter of the nanoparticles based on the hysteresis losses that is valid for the non-linear region (with H0 comparable to the anisotropy field). Our model takes into account the magnetic interactions among the nanoparticles in the agglomerate. For comparison, we also measured the SAR of non-agglomerated nanoparticles in a similar diameter range, in which N´ eel and Brown relaxations dominate the heat generation. (Some figures may appear in colour only in the online journal)

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We have systematically studied the magnetic properties of ferrite nanoparticles with 3, 7, and 11 nm of diameter with very narrow grain size distributions. Samples were prepared by the thermal decomposition of Fe(acac)3 in the presence of surfactants giving nanoparticles covered by oleic acid. High resolution transmission electron microscopy (HRTEM) images and XRD diffraction patterns confirms that all samples are composed by crystalline nanoparticles with the spinel structure expected for the iron ferrite. ac and dc magnetization measurements, as well in-field Mossbauer spectroscopy, indicate that the magnetic properties of nanoparticles with 11 and 7 nm are close to those expected for a monodomain, presenting large MS (close to the magnetite bulk). Despite the crystalline structure observed in HRTEM images, the nanoparticles with 3 nm are composed by a magnetically ordered region (core) and a surface region that presents a different magnetic order and it contains about 66% of Fe atoms. The high saturati...

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We have investigated the dynamic magnetic properties of dextran-coated magnetite (Fe3O4) nanoparticles in the form of (a) particles suspended in a carrier liquid and (b) concentrated powder obtained from lyophilization. The blocking temperature was found to increase from TB=42(2)to52(2)K (@μ0H=10mT) after lyophilization, showing the effects of dipolar interactions in samples with identical size distributions. The temperature dependence of the hyperfine field Bhyp(T) reveals the effects of collective magnetic excitations at low temperature, and allowed us to obtain the magnetic anisotropy energy Ea=3.6×10−21J for noninteracting particles. The obtained values can be understood assuming only magnetocrystalline anisotropy, without any additional contributions from surface, shape, or exchange origin. Moreover, a magnetocrystalline anisotropy constant value K1=10kJ∕m3 was obtained by assuming the cubic phase with easy magnetic direction [111] of the bulk material above the Verwey transition, supporting the idea...

Nanoparticles: The Influence of Particle Size on Energy Absorption

In this research work, DEXTRAN- and polyethylene glycol (PEG)-coated iron-oxide superparamagnetic nanoparticles were synthetized and their cytotoxicity and biodistribution assessed. Well-crystalline hydrophobic Fe3 O4 SPIONs were formed by a thermal decomposition process with d = 18 nm and σ = 2 nm; finally, the character of SPIONs was changed to hydrophilic by a post-synthesis procedure with the functionalization of the SPIONs with PEG or DEXTRAN. The nanoparticles present high saturation magnetization and superparamagnetic behavior at room temperature, and the hydrodynamic diameters of DEXTRAN- and PEG-coated SPIONs were measured as 170 and 120 nm, respectively. PEG- and DEXTRAN-coated SPIONs have a Specific Power Absorption SPA of 320 and 400 W/g, respectively, in an ac magnetic field with amplitude of 13 kA/m and frequency of 256 kHz. In vitro studies using VERO and MDCK cell lineages were performed to study the cytotoxicity and cell uptake of the SPIONs. For both cell lineages, PEG- and DEXTRAN-coated nanoparticles presented high cell viability for concentrations as high as 200 μg/mL. In vivo studies were conducted using BALB/c mice inoculating the SPIONs intravenously and exposing them to the presence of an external magnet located over the tumour. It was observed that the amount of PEG-coated SPIONs in the tumor increased by up to 160% when using the external permanent magnetic as opposed to those animals that were not exposed to the external magnetic field.

Heat generation in agglomerated ferrite nanoparticles in an alternating magnetic field

Six-line ferrihydrite (FH) nanoparticles have been synthesized in the core of reverse micelles, used as nanoreactors to obtain average particle sizes . The blocking temperatures TBm extracted from magnetization data increased from ≈10 to 20 K for increasing particle size. Low-temperature Mossbauer measurements allowed us to observe the onset of differentiated contributions from the particle core and surface as the particle size increases. The magnetic properties measured in the liquid state of the original emulsion showed that the ferrihydrite phase is not present in the liquid precursor, but precipitates in the micelle cores after the free water is freeze-dried. Systematic susceptibility χac(f,T) measurements showed the dependence of the effective magnetic anisotropy energies Ea with particle volume, and yielded an effective anisotropy value of Keff = 312 ± 10 kJ m−3.

Surface effects in the magnetic properties of crystalline 3 nm ferrite nanoparticles chemically synthesized

The control of the size of bimagnetic nanoparticles represents an important step toward the study of fundamental properties and the design of new nanostructured magnetic materials. We report the synthesis and the structural and magnetic characterization of bimagnetic CoO/CoFe2O4 core/shell nanoparticles. The material was fabricated by a seed-mediated growth high-temperature decomposition method with sizes in the range of 5-11 nm. We show that the core/shell morphology favours the crystallinity of the shell phase, and the reduction of the particle size leads to a remarkable increase of the magnetic hardening. When the size is reduced, the coercive field at 5 K increases from 21.5 kOe to 30.8 kOe, while the blocking temperature decreases from 388 K to 167 K. The size effects on the magnetic behaviour are described through a phenomenological model for strongly ferri-/antiferromagnetic coupled phases.

Interparticle interactions and surface contribution to the effective anisotropy in biocompatible iron oxide nanoparticles used for contrast agents

UNLABELLED Superparamagnetic iron oxide nanoparticles (SPIONS) were synthesized by thermal decomposition of an organometallic precursor at high temperature and coated with a bi-layer composed of oleic acid and methoxy-polyethylene glycol-phospholipid. The formulations were named SPION-PEG350 and SPION-PEG2000. Transmission electron microscopy, X-ray diffraction and magnetic measurements show that the SPIONs are near-spherical, well-crystalline, and have high saturation magnetization and susceptibility. FTIR spectroscopy identifies the presence of oleic acid and of the conjugates mPEG for each sample. In vitro biocompatibility of SPIONS was investigated using three cell lines; up to 100μg/ml SPION-PEG350 showed non-toxicity, while SPION-PEG2000 showed no signal of toxicity even up to 200μg/ml. The uptake of SPIONS was detected using magnetization measurement, confocal and atomic force microscopy. SPION-PEG2000 presented the highest internalization capacity, which should be correlated with the mPEG chain size. The in vivo results suggested that SPION-PEG2000 administration in mice triggered liver and kidney injury. FROM THE CLINICAL EDITOR The potential use of superparamagnetic iron oxide nanoparticles (SPIONS) in the clinical setting have been studied by many researchers. The authors synthesized two types of SPIONS here and investigated the physical properties and biological compatibility. The findings should provide more data on the design of SPIONS for clinical application in the future.

In vitro and in vivo experiments with iron oxide nanoparticles functionalized with DEXTRAN or polyethylene glycol for medical applications: Magnetic targeting

ZnO-core/CoFe2O4-shell nanoparticles of 7.4 nm average size have been synthesized and their magnetic properties have been compared to those of CoO-core/CoFe2O4-shell nanoparticles with similar morphology. The coercive field values are much lower than those for CoO/CoFe2O4 nanoparticles (e.g., at 5 K: Hc = 7.8 kOe for ZnO/CoFe2O4; Hc = 27.8 kOe for CoO/CoFe2O4). The nature of the coercive field values is explained by a phenomenological model for the free energy of a non-magnetic core, or an antiferromagnetic core, encapsulated by a hard ferrimagnetic shell.