Gold-decorated magnetic nanoparticles design for hyperthermia applications and as a potential platform for their surface-functionalization.

The integration of noble metal and magnetic nanoparticles with controlled structures that can couple various specific effects to the different nanocomposite in multifunctional nanosystems have been found interesting in the field of medicine. In this work, we show synthesis route to prepare small Au nanoparticles of sizes = 3.9 ± 0.2 nm attached to Fe3O4 nanoparticle cores ( = 49.2 ± 3.5 nm) in aqueous medium for potential application as a nano-heater. Remarkably, the resulted Au decorated PEI-Fe3O4 (Au@PEI-Fe3O4) nanoparticles are able to retain bulk magnetic moment MS = 82-84 Am2/kgFe3O4, with the Verwey transition observed at TV = 98 K. In addition, the in vitro cytotoxicity analysis of the nanosystem microglial BV2 cells showed high viability (>97.5%) to concentrate up to 100 µg/mL in comparison to the control samples. In vitro heating experiments on microglial BV2 cells under an ac magnetic field (H0 = 23.87 kA/m; f = 571 kHz) yielded specific power absorption (SPA) values of SPA = 43 ± 3 and 49 ± 1 µW/cell for PEI-Fe3O4 and Au@PEI-Fe3O4 NPs, respectively. These similar intracellular SPA values imply that functionalization of the magnetic particles with Au did not change the heating efficiency, providing at the same time a more flexible platform for multifunctional functionalization.

55Mn NMR observation of colossal magnetoresistance effect in Sm0.55Sr0.45MnO3.

Temperature dependent 55Mn NMR study of Sm0.55Sr0.45MnO3 is reported. Previous bulk magnetization measurements have shown that below T C ~ 125 K the sample is ferromagnetic metallic (FMM) and above TC it is charge ordered and insulating. In present report, we show that from zero-field NMR a single line double-exchange (DE) signal is observed at temperatures up to 139 K, which is due to a presence of FMM clusters also above T C. The intensity of the DE line follows the temperature dependence of the magnetization measured at 0.01 T. When a magnetic field up to 2 T is applied at 139 K (i.e. 14 K above T C), a strong increase in NMR intensity of the DE line is observed indicating that content of FMM regions increases. This reveals that metallicity is induced in the material by the applied magnetic field and explains the observed colossal magnetoresistance (CMR) effect at the microscopic level. The observation agrees with previous results, which confirm that the percolation of the FMM clusters is responsible for the CMR effect. The shift of the resonant frequency in the applied field is three times smaller compared to decrease expected from gyromagnetic ratio, which indicates an antiferromagnetic coupling between the FMM clusters.

High-resolution imaging of remanent state and magnetization reversal of superdomain structures in high-density cobalt antidot arrays.

Remanent state and magnetization reversal processes of a series of cobalt antidot arrays with a fixed hole diameter (d ≈ 55 nm) and an array periodicity (p) ranging between 95 and 524 nm were studied by in situ Lorentz microscopy (LM) as a function of the magnetic field. At remanence, defocused LM images showed the periodicity dependence of the magnetic states inside the lattice. A remarkable transition was observed in the type of domain structures as a function of p: for the large periodicities (p > 300 nm), conventional 90° and 180° domain walls were formed, whereas in small-period antidot arrays (p â‰¦ 160 nm) magnetic superdomain walls (SDWs) were nucleated to separate regions with different average magnetization direction, the so-called magnetic superdomains. In the SDW regime, a low-frequency Fourier filtering method was implemented to allow a quantitative analysis of the LM images by the transport of intensity equation method. In situ LM experiments under applied magnetic fields were performed to study the reversal magnetization process in a particular array (p = 160 nm), and clear differences were observed as a function of the magnetic field orientation. The switching process under magnetic fields parallel to the horizontal antidot rows occurs in two stages: the system first nucleates and propagates horizontal SDWs, parallel to the field. Then, at higher magnetic fields, vertical SDWs, perpendicular to the field, appear before saturation. When the magnetic field is applied at 45° with respect to the antidot rows, both horizontal and vertical SDWs are nucleated and propagated simultaneously. All the experiments were successfully correlated with micromagnetic simulations. The current study sheds new light on the magnetization reversal processes of antidot arrays and opens new possibilities of exploiting the potential of high-resolution in situ LM and new data analysis procedures to probe magnetization processes in nanomagnetism, particularly in periodic arrays of nanomagnets.

Improvement of domain wall conduit properties in cobalt nanowires by global gallium irradiation.

Applications based on the movement of domain walls (DWs) in magnetic nanowires (NWs) require a good DW conduit behavior, i.e. a significant difference between DW nucleation and propagation fields. In this work, we have systematically studied how this property evolves in cobalt NWs grown by focused electron beam induced deposition (FEBID) as a function of global gallium irradiation, for irradiation doses up to 1.24 × 10(17) ions cm(-2). Whereas for high doses the DW conduit is lost, below 6.42 × 10(15) ions cm(-2) the difference between the two fields increases with irradiation, becoming up to ∼9 times larger than for non-irradiated wires, due to a strong increase in the nucleation field, while the propagation field remains approximately constant. This behavior stems from two effects. The first effect is a decrease in the magnetic volume of the parasitic halo around the NW, typically present in FEBID nanostructures, leading to the disappearance of weak nucleation centers. The second effect is the formation of a 20 nm outer shell with Co crystals about twice the size of those forming the NW core, causing a net increase of the local magnetocrystalline anisotropy. The results presented here are important for the potential use of magnetic NWs grown by FEBID in DW-based devices, and might also be of interest for magnetic NWs fabricated by other techniques.

Quantitative in situ magnetization reversal studies in Lorentz microscopy and electron holography.

A generalized procedure for the in situ application of magnetic fields by means of the excitation of the objective lens for magnetic imaging experiments in Lorentz microscopy and electron holography is quantitatively described. A protocol for applying magnetic fields with arbitrary in-plane magnitude and orientation is presented, and a freeware script for Digital Micrograph(™) is provided to assist the operation of the microscope. Moreover, a method to accurately reconstruct hysteresis loops is detailed. We show that the out-of-plane component of the magnetic field cannot be always neglected when performing quantitative measurements of the local magnetization. Several examples are shown to demonstrate the accuracy and functionality of the methods.

Induced cell toxicity originates dendritic cell death following magnetic hyperthermia treatment.

Magnetic hyperthermia (MH) is based on the use of magnetic nanoparticles (MNPs) to selectively increase the temperature of MNP-loaded target tissues when applying an alternating magnetic field (AMF) in the range of radiofrequency. To date, all MH research has focused on heat generation in an attempt to elucidate the mechanisms for the death of MNP-loaded cells submitted to AMF. However, recent in vitro studies have demonstrated the feasibility of inducing dramatic cell death without increasing the macroscopic temperature during AMF exposure. Here, we show that the cell death observed following AMF exposure, specifically that of MNP-loaded dendritic cells (DCs) in culture, was caused by the release of toxic agents into the cell culture supernatants and not due to a macroscopic temperature increase. We performed MH in vitro experiments to demonstrate that the supernatant of the cell culture following AMF exposure was highly toxic when added to control unloaded DCs, as this treatment led to nearly 100% cell death. Therefore, our results demonstrate that heat is not the only agent responsible for triggering cell death following MH treatment. This finding offers new perspectives for the use of DCs as the proverbial Trojan horse to vectorise MNPs to the target tumour area and these results further support the use of DCs as therapeutic agents against cancer when submitted to AMF. Furthermore, this discovery may help in understanding the mechanism of cell death mediated by exposure to AMF.

Magnetic field-induced dissipation-free state in superconducting nanostructures.

A superconductor in a magnetic field acquires a finite electrical resistance caused by vortex motion. A quest to immobilize vortices and recover zero resistance at high fields made intense studies of vortex pinning one of the mainstreams of superconducting research. Yet, the decades of efforts resulted in a realization that even promising nanostructures, utilizing vortex matching, cannot withstand high vortex density at large magnetic fields. Here, we report a giant reentrance of vortex pinning induced by increasing magnetic field in a W-based nanowire and a TiN-perforated film densely populated with vortices. We find an extended range of zero resistance with vortex motion arrested by self-induced collective traps. The latter emerge due to order parameter suppression by vortices confined in narrow constrictions by surface superconductivity. Our findings show that geometric restrictions can radically change magnetic properties of superconductors and reverse detrimental effects of magnetic field.

Application of magnetically induced hyperthermia in the model protozoan Crithidia fasciculata as a potential therapy against parasitic infections.

BACKGROUND: Magnetic hyperthermia is currently a clinical therapy approved in the European Union for treatment of tumor cells, and uses magnetic nanoparticles (MNPs) under time-varying magnetic fields (TVMFs). The same basic principle seems promising against trypanosomatids causing Chagas disease and sleeping sickness, given that the therapeutic drugs available have severe side effects and that there are drug-resistant strains. However, no applications of this strategy against protozoan-induced diseases have been reported so far. In the present study, Crithidia fasciculata, a widely used model for therapeutic strategies against pathogenic trypanosomatids, was targeted with Fe(3)O(4) MNPs in order to provoke cell death remotely using TVMFs. METHODS: Iron oxide MNPs with average diameters of approximately 30 nm were synthesized by precipitation of FeSO(4) in basic medium. The MNPs were added to C. fasciculata choanomastigotes in the exponential phase and incubated overnight, removing excess MNPs using a DEAE-cellulose resin column. The amount of MNPs uploaded per cell was determined by magnetic measurement. The cells bearing MNPs were submitted to TVMFs using a homemade AC field applicator (f = 249 kHz, H = 13 kA/m), and the temperature variation during the experiments was measured. Scanning electron microscopy was used to assess morphological changes after the TVMF experiments. Cell viability was analyzed using an MTT colorimetric assay and flow cytometry. RESULTS: MNPs were incorporated into the cells, with no noticeable cytotoxicity. When a TVMF was applied to cells bearing MNPs, massive cell death was induced via a nonapoptotic mechanism. No effects were observed by applying TVMF to control cells not loaded with MNPs. No macroscopic rise in temperature was observed in the extracellular medium during the experiments. CONCLUSION: As a proof of principle, these data indicate that intracellular hyperthermia is a suitable technology to induce death of protozoan parasites bearing MNPs. These findings expand the possibilities for new therapeutic strategies combating parasitic infection.

Magnetic properties of epitaxial discontinuous Fe/MgO multilayers.

We report magnetic, dynamic and transport properties of discontinuous metal-insulator multilayers Fe/MgO grown on amorphous Corning glass and single-crystalline MgO (001) substrates. The films of structure Substrate/MgO (3 nm)/[Fe (0.6 nm)/MgO (3.0 nm)] x 10 were prepared in ultra-high vacuum conditions using Pulsed Laser Deposition. It was shown that conditions of epitaxial growth are favorable for MgO substrates. As a result a substantial increase of tunneling magnetoresistance caused by spin-filtering effect was observed and reasonably theoretically explained. The value of TMR - 9.2% at room temperature in 18 kOe magnetic field is three times higher comparing to that for the samples grown on Corning glass substrates.

Quantitative biomolecular sensing station based on magnetoresistive patterned arrays.

The combination of magnetoresistive sensors and magnetic labeling of bioanalytes, which are selectively captured by their complementary antibody in the proximity of the sensor is a powerful method in order to attain truly quantitative immunological assays. In this paper we present a technical solution to exploit the existing spin valve technology to readout magnetic signals of bio-functionalized magnetic nanoparticles. The method is simple and reliable, and it is based on a discrete scan of lateral flow strips with a precise control of the contact force between sensor and sample. It is shown that the signal of the sensor is proportional to the local magnetization produced by the nanoparticles in a wide range of concentrations, and the sensitivity thresholds in both calibration samples and real immunorecognition assays of human chorionic gonadotropin hormone are well below the visual inspection limit (5.5 ng/ml). Furthermore the sample scanning approach and the reduced dimensions of the sensors provide unprecedented spatial resolution of the nanoparticle distribution across the supporting nitrocellulose strip, therefore enabling on-stick control references and multi-analyte capability.

Correlation between the magnetic imaging of cobalt nanoconstrictions and their magnetoresistance response.

Scanning transmission x-ray microscopy (STXM) and magnetoresistance (MR) measurements are used to investigate the magnetic behavior of a nanoconstriction joining two micrometric electrodes (a pad and a wire). The reversal of the magnetization under variable external static magnetic fields is imaged. By means of a detailed analysis of the STXM images at the nanocontact area, the MR is calculated, based on diffusive anisotropic-MR. This MR agrees well with that obtained from electrical transport measurements, allowing a direct correlation between the MR signal and the magnetic reversal of the system. The magnetization behavior depends on the sample thickness and constriction dimensions. In 40 nm-thick samples, with 20 × 175 nm(2) contact areas, the magnetization at the two sides of the constriction forms a net angle of 90°, with a progressive evolution of the magnetization structure between the electrodes during switching. The MR in those cases has a more peaked shape than with 20 nm-thick electrodes and 10 × 80 nm(2) contact areas, where the magnetization forms 180° between them, with a wide domain wall pinned at the constriction. As a consequence of this configuration, a plateau in the MR is observed for about 20 Oe.

Controlled cell death by magnetic hyperthermia: effects of exposure time, field amplitude, and nanoparticle concentration.

PURPOSE: To investigate the effects of alternating magnetic fields (AMF) on the death rate of dendritic cells (DCs) loaded with magnetic nanoparticles (MNPs) as heating agents. AMF exposure time and amplitude as well as the MNPs concentration were screened to assess the best conditions for a controlled field-induced cell death. METHODS: Human-monocyte-derived DCs were co-incubated with dextran-coated MNPs. The cells were exposed to AMF (f = 260 kHz; 0 < H(0) < 12.7 kA/m) for intervals from 5 to 15 min. Morphology changes were assessed by scanning electron microscopy. Cell viability was measured by Trypan blue and fluorescence-activated cell sorting (FACS) using Annexin-propidium iodide markers. RESULTS: We were able to control the DCs viability by a proper choice AMF amplitude and exposure time, depending on the amount of MNPs uploaded. About 20% of cells showed Annexin-negative/PI-positive staining after 5-10 min of AMF exposure. CONCLUSIONS: Controlled cell death of MNP-loaded DCs can be obtained by adequate tuning of the physical AMF parameters and MNPs concentration. Necrotic-like populations were observed after exposure times as short as 10 min, suggesting a fast underlying mechanism for cell death. Power absorption by the MNPs might locally disrupt endosomic membranes, thus provoking irreversible cell damage.

Designing novel hybrid materials by one-pot co-condensation: from hydrophobic mesoporous silica nanoparticles to superamphiphobic cotton textiles.

This work reports the synthesis and characterization of mesoporous silica nanoparticles (MSNs) functionalized with tridecafluorooctyltriethoxysilane (F13) and their in situ incorporation onto cotton textiles. The hybrid MSNs and the functional textiles were prepared by a one-pot co-condensation methodology between tetraethylorthosilicate (TEOS) and F13, with hexadecyltrimethylammonium chloride (CTAC) as the template and triethanolamine as the base. The influence of the F13 to TEOS molar ratio (1:10, 1:5 and 1:3) on the nanoparticle morphology, porosity, degree of functionalization, and hydro/oleophobic properties is discussed. The hybrid nanosilicas presented high colloidal stability and were spherical and monodispersed with average particle size of ∼45 nm. They also showed high surface areas, large pore volumes, and a wormhole-type mesoporous structure. The increase in the organosilane proportion during the co-condensation process led to a more radially branched wormhole-like mesoporosity, a decrease in the surface area, pore volume, and amount of surface silanol groups, and an enrichment of the surface with fluorocarbon moieties. These changes imparted hydrophobic and oleophobic properties to the materials, especially to that containing the highest F13 loading. Cotton textiles were coated with the F13-MSNs through an efficient and less time-consuming route. The combination between surface roughness and mesoporosity imparted by the MSNs, and the low surface energy provided by the organosilane resulted in superhydrophobic functional textiles. Moreover, the textile with the highest loading of fluorocarbon groups was superamphiphobic.

Focused electron beam induced etching of titanium with XeF2.

Titanium is a relevant technological material due to its extraordinary mechanical and biocompatible properties, its nanopatterning being an increasingly important requirement in many applications. We report the successful nanopatterning of titanium by means of focused electron beam induced etching using XeF(2) as a precursor gas. Etch rates up to 1.25 × 10(-3) µm(3) s(-1) and minimum pattern sizes of 80 nm were obtained. Different etching parameters such as beam current, beam energy, dwell time and pixel spacing are systematically investigated, the etching process being optimized by decreasing both the beam current and the beam energy. The etching mechanism is investigated by transmission electron microscopy. Potential applications in nanotechnology are discussed.

Direct observation of stress accumulation and relaxation in small bundles of superconducting vortices in tungsten thin films.

We study the behavior of bundles of superconducting vortices when increasing the magnetic field using scanning tunneling microscopy and spectroscopy at 100 mK. Pinning centers are given by features on the surface corrugation. We find strong net vortex motion in a bundle towards a well-defined direction. We observe continuous changes of the vortex arrangements, and identify small displacements, which stress and deform the vortex bundle, separated by larger rearrangements or avalanches, which release accumulated stress.

Cell death induced by the application of alternating magnetic fields to nanoparticle-loaded dendritic cells.

In this work, the capability of primary, monocyte-derived dendritic cells (DCs) to uptake iron oxide magnetic nanoparticles (MNPs) is assessed and a strategy to induce selective cell death in these MNP-loaded DCs using external alternating magnetic fields (AMFs) is reported. No significant decrease in the cell viability of MNP-loaded DCs, compared to the control samples, was observed after five days of culture. The number of MNPs incorporated into the cytoplasm was measured by magnetometry, which confirmed that 1-5 pg of the particles were uploaded per cell. The intracellular distribution of these MNPs, assessed by transmission electron microscopy, was found to be primarily inside the endosomic structures. These cells were then subjected to an AMF for 30 min and the viability of the blank DCs (i.e. without MNPs), which were used as control samples, remained essentially unaffected. However, a remarkable decrease of viability from approximately 90% to 2-5% of DCs previously loaded with MNPs was observed after the same 30 min exposure to an AMF. The same results were obtained using MNPs having either positive (NH(2)(+)) or negative (COOH(-)) surface functional groups. In spite of the massive cell death induced by application of AMF to MNP-loaded DCs, the number of incorporated magnetic particles did not raise the temperature of the cell culture. Clear morphological changes at the cell structure after magnetic field application were observed using scanning electron microscopy. Therefore, local damage produced by the MNPs could be the main mechanism for the selective cell death of MNP-loaded DCs under an AMF. Based on the ability of these cells to evade the reticuloendothelial system, these complexes combined with an AMF should be considered as a potentially powerful tool for tumour therapy.

Fe:O:C grown by focused-electron-beam-induced deposition: magnetic and electric properties.

We systematically study the effect of oxygen content on the magneto-transport and microstructure of Fe:O:C nanowires deposited by focused-electron-beam-induced (FEBID) deposition. The Fe/O ratio can be varied with an Fe content varying between ∼ 50 and 80 at.% with overall low C content (≈16 ± 3 at.%) by adding H(2)O during the deposition while keeping the beam parameters constant as measured by energy dispersive x-ray (EDX) spectroscopy. The room-temperature magnetic properties for deposits with an Fe content of 66-71 at.% are investigated using the magneto-optical Kerr effect (MOKE) and electric magneto-transport measurements. The nanostructure of the deposits is investigated through cross-sectional high-resolution transmission electron microscopy (HRTEM) imaging, allowing us to link the observed magneto-resistance and resistivity to the transport mechanism in the deposits. These results demonstrate that functional magnetic nanostructures can be created, paving the way for new magnetic or even spintronics devices.

Magnetic hydrogels derived from polysaccharides with improved specific power absorption: potential devices for remotely triggered drug delivery.

We report on novel ferrogels derived from polysaccharides (sodium alginate and chitosan) with embedded iron oxide nanoparticles synthesized in situ and their combination with thermally responsive poly(N-isopropylacrylamide) for externally driven drug release using AC magnetic fields. Samples were characterized by Raman spectroscopy, transmission electron microscopy, and magnetic measurements. The obtained nanoparticles were found to be of ∼10 nm average size, showing magnetic properties very close to those of the bulk material. The thermal response was measured by power absorption experiments, finding specific power absorption values between 100 and 300 W/g, which was enough for attaining the lower critical solution temperature of the polymeric matrix within few minutes. This fast response makes these materials good candidates for externally controlled drug release.

Determination of the percolation threshold in Fe/MgO magnetic granular multilayers.

The evolution of the morphology, magnetic and transport properties of Fe(t nm)/MgO(3.0 nm) multilayers with respect to the nominal metallic layer thickness was investigated. A comparison with existing experimental data on discontinuous metal-insulator multilayers, ultrathin epitaxial Fe films on MgO substrates and granular cermet films is made. It is confirmed that the deposition conditions and the material composition play a crucial role in the percolation process. Nominal thicknesses of Fe layers at which an infinite metallic cluster is formed and the conditions for continuous Fe coverage were determined. Different methods of percolation threshold detection were analysed. We show that investigation of the temperature dependence of resistance in nanostructures could lead to an overestimation of the percolation threshold value, while magnetic measurements alone could lead to its underestimation.

Magnetization reversal in individual cobalt micro- and nanowires grown by focused-electron-beam-induced-deposition.

We systematically study individual micro- and nanometric polycrystalline cobalt wires grown by focused-electron-beam-induced-deposition. The deposits were grown in a range of aspect ratios varying from 1 up to 26. The minimum lateral dimension of the nanowires was 150 nm, for a thickness of 40 nm. Atomic force microscopy images show beam-current-dependent profiles, associated with different regimes of deposition. The magnetization reversal of individual nanowires is studied by means of the spatially resolved magneto-optical Kerr effect. Abrupt switching is observed, with a systematic dependence on the wire's dimensions. This dependence of the coercive field is understood in magnetostatic terms, and agrees well with previous results on cobalt wires grown with different techniques. The influence of compositional gradients along the structural profile on the magnetic reversal is studied by using micromagnetic simulations. This work demonstrates the feasibility of using this technique to fabricate highly pure magnetic nanostructures, and highlights the advantages and disadvantages of the technique with respect to more conventional ones.