Horacio E. Troiani

Magnetic dead layer in ferromagnetic manganite nanoparticles

We present experimental evidence on the physical origin of a magnetic dead layer (MDL) in manganite nanoparticles. The studied nanoparticles constitute the wall of La0.67Sr0.33MnO3 and La0.67Ca0.33MnO3 manganite nanotubes. Magnetic properties analysis and high resolution transmission electron microscopy show a shell of approximately 2 nm thickness with different properties from the core. In this shell the atoms are in a noncrystalline array that perfectly explains the 50% reduction of the magnetization compared to the bulk. Moreover, we present experimental evidence that the internal magnetic structure of the MDL is constituted by small ferromagnetic clusters in a frustrated configuration.

Nanotubes of rare-earth manganese oxide

We report the synthesis of rare-earth manganese-oxide-based nanotubes. The pore wetting technique was used to obtain structures of nominal composition La0.325Pr0.300Ca0.375MnO3 with 800 nm external diameter, 4000 nm length, and wall thickness below 100 nm exhibiting magnetic and magnetoresistive behavior below 200 K, including nonvolatile memory. Walls are found to be formed by small crystals of approximately 20 nm. Structures obtained using different diameter of pores, as small as 100 nm, have a similar aspect ratio. Results show the realization of nanotubes of manganites exhibiting intrinsic phase separation.

Room-temperature ferromagnetism in La2∕3Sr1∕3MnO3 nanoparticle assembled nanotubes

We present magnetic and transmission electron microscopy experiments on the double-exchange compound La2∕3Sr1∕3MnO3, nanostructured to form tubes with 700 nm of external diameter. Microscopy reveals that their walls are formed by a compact agglomerate of grains, whose sizes are around 20 nm. The study of magnetic properties of randomly oriented nanotubes shows that the transition from the ferromagnetic to paramagnetic state is at TC=320K, close to the bulk sample value. They exhibit hysteresis in magnetic field loops. The coercive field at 90 K is around 130 Oe, and estimated single-domain size is around 20 nm.

Heat generation in agglomerated ferrite nanoparticles in an alternating magnetic field

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)

Preparation of iron oxide nanoparticles stabilized with biomolecules: experimental and mechanistic issues.

Nanoparticles (NPs) with magnetic properties based on magnetite (Fe(3)O(4), MAG) modified with oleic acid (OA), chitosan (CS) and bovine serum albumin (BSA) have been prepared. A versatile method of synthesis was employed, involving two steps: (i) co-precipitation of MAG; and (ii) nanoprecipitation of macromolecules on as-formed MAG NPs. Experimental variables have been explored to determine the set of conditions that ensure suitable properties of NPs in terms of their size, functionality and magnetic properties. It was found that the presence of OA in Fe(+2)/Fe(+3) solutions yields MAG NPs with lower aggregation levels, while increasing initial amounts of OA may change the capability of NPs to disperse in aqueous or organic media by modifying the stabilization mechanism. Incorporation of CS was verified through Fourier transform IR spectroscopy. This biopolymer stabilizes NPs by electrostatic repulsions leading to stable ferrofluids and minimal fraction of recoverable solid NPs. BSA was successfully added to NP formulations, increasing their functionality and probably their biocompatibility. In this case too stable ferrofluids were obtained, where BSA acts as a polyelectrolyte. From the proposed methodology it is possible to achieve a wide range of NPs magnetically active intended for several applications. The required properties may be obtained by varying experimental conditions.

Silver Nanoparticle-Mesoporous Oxide Nanocomposite Thin Films: A Platform for Spatially Homogeneous SERS-Active Substrates with Enhanced Stability

We introduce a nanoparticle-mesoporous oxide thin film composite (NP-MOTF) as low-cost and straightforward sensing platforms for surface-enhanced Raman Spectroscopy (SERS). Titania, zirconia, and silica mesoporous matrices templated with Pluronics F-127 were synthesized via evaporation-induced self-assembly and loaded with homogeneously dispersed Ag nanoparticles by soft reduction or photoreduction. Both methods give rise to uniform and reproducible Raman signals using 4-mercaptopyridine as a probe molecule. Details on stability and reproducibility of the Raman enhancement are discussed. Extensions in the design of these composite structures were explored including detection of nonthiolated molecules, such as rhodamine 6-G or salicylic acid, patterning techniques for locating the enhancement regions and bilayered mesoporous structures to provide additional control on the environment, and potential size-selective filtration. These inorganic oxide-metal composites stand as extremely simple, reproducible, and versatile platforms for Raman spectroscopy analysis.

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

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.

Size effects in bimagnetic CoO/CoFe2O4 core/shell nanoparticles

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.

Evolution of the magnetic anisotropy with particle size in antiferromagnetic Cr2O3 nanoparticles

We report the magnetic properties of antiferromagnetic Cr2O3 from bulk material down to 6 nm nanoparticles. We have found a decrease in the lattice parameters and the cell volume when the size diminishes. On the contrary, the magnetic anisotropy constant, Keff, shows a nonmonotonic behavior. The Keff decreases from its bulk value, shows a minimum near ϕ∼30 nm and displays an important increase for smaller sizes. We analyzed the size dependence of Keff in terms of the magnetocrystalline and surface contributions, and we fitted the Keff size evolution on the basis of a phenomenological model taking into account the magnetically ordered core and the surface contribution.

Superparamagnetic iron-oxide nanoparticles mPEG350– and mPEG2000-coated: cell uptake and biocompatibility evaluation

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.