How size, shape and assembly of magnetic nanoparticles give rise to different hyperthermia scenarios.

The use of magnetic nanoparticles (MNPs) to locally increase the temperature at the nanoscale under the remote application of alternating magnetic fields (magnetic particle hyperthermia, MHT) has become an important subject of nanomedicine multidisciplinary research, focusing among other topics on the optimization of the heating performance of MNPs and their assemblies under the effect of the magnetic field. We report experimental data of heat released by MNPs using a wide range of anisometric shapes and their assemblies in different media. We outline a basic theoretical investigation, which assists the interpretation of the experimental data, including the effect of the size, shape and assembly of MNPs on the MNPs' hysteresis loops and the maximum heat delivered. We report heat release data of anisometric MNPs, including nanodisks, spindles (elongated nanoparticles) and nanocubes, analysing, for a given shape, the size dependence. We study the MNPs either acting as individuals or assembled through a magnetic-field-assisted method. Thus, the physical geometrical arrangement of these anisometric particles, the magnetization switching and the heat release (by means of the determination of the specific adsorption rate, SAR values) under the application of AC fields have been analysed and compared in aqueous suspensions and after immobilization in agar matrix mimicking the tumour environment. The different nano-systems were analysed when dispersed at random or in assembled configurations. We report a systematic fall in the SAR for all anisometric MNPs randomly embedded in a viscous environment. However, certain anisometric shapes will have a less marked, an almost total preservation or even an increase in SAR when embedded in a viscous environment with certain orientation, in contrast to the measurements in water solution. Discrepancies between theoretical and experimental values reflect the complexity of the systems due to the interplay of different factors such as size, shape and nanoparticle assembly due to magnetic interactions. We demonstrate that magnetic assembly holds great potential for producing materials with high functional and structural diversity, as we transform our nanoscale building blocks (anisometric MNPs) into a material displaying enhanced SAR properties.

Magnetic nanoparticles: An indicator of health risks related to anthropogenic airborne particulate matter.

Due to their small dimensions, airborne particles are able to penetrate through inhalation into many human organs, from the lungs to the cardiovascular system and the brain, which can threaten our health. This work establishes a novel approach of collecting quantitative data regarding the fraction, the composition and the size distribution of combustion-emitted particulate matter through the magnetic characterization and analysis of samples received by common air pollution monitoring. To this end, SQUID magnetometry measurements were carried out for samples from urban and suburban areas in Thessaloniki, the second largest city of Greece, taking into consideration the seasonal and weekly variation of airborne particles levels as determined by occurring traffic and meteorological conditions. The level of estimated magnetically-responding atmospheric particulate matter was at least 0.5 % wt. of the collected samples, mostly being present in the form of ultrafine particles with nuclei sizes of approximately 14 nm and their aggregates. The estimated quantities of magnetic particulate matter show maximum values during autumn months (0.8 % wt.) when increased commuting takes place, appearing higher in the city center by up to 50% than those in suburban areas. In combination with high-resolution transmission electron imaging and elemental analysis, it was found that Fe3O4 and similar ferrites, some of them attached to heavy metals (Co, Cr), are the dominant magnetic contributors arising from anthropogenic high-temperature processes, e.g. due to traffic emissions. Importantly, nasal cytologic samples collected from residents of both central and suburban areas showed same pattern in what concerns magnetic behavior, thus verifying the critical role of nanosized magnetic particles in the assessment of air pollution threats. Despite the inherent statistical limitations of our study, such findings also indicate the potential transmission of infectious pathogens by means of pollution-derived nanoparticles into the respiratory system of the human body.

Controlling Magnetization Reversal and Hyperthermia Efficiency in Core-Shell Iron-Iron Oxide Magnetic Nanoparticles by Tuning the Interphase Coupling.

Magnetic particle hyperthermia, in which colloidal nanostructures are exposed to an alternating magnetic field, is a promising approach to cancer therapy. Unfortunately, the clinical efficacy of hyperthermia has not yet been optimized. Consequently, routes to improve magnetic particle hyperthermia, such as designing hybrid structures comprised of different phase materials, are actively pursued. Here, we demonstrate enhanced hyperthermia efficiency in relatively large spherical Fe/Fe-oxide core-shell nanoparticles through the manipulation of interactions between the core and shell phases. Experimental results on representative samples with diameters in the range 30-80 nm indicate a direct correlation of hysteresis losses to the observed heating with a maximum efficiency of around 0.9 kW/g. The absolute particle size, the core-shell ratio, and the interposition of a thin wüstite interlayer are shown to have powerful effects on the specific absorption rate. By comparing our measurements to micromagnetic calculations, we have unveiled the occurrence of topologically nontrivial magnetization reversal modes under which interparticle interactions become negligible, aggregates formation is minimized and the energy that is converted into heat is increased. This information has been overlooked until date and is in stark contrast to the existing knowledge on homogeneous particles.

Isothermal anisotropic magnetoresistance in antiferromagnetic metallic IrMn.

Antiferromagnetic spintronics is an emerging field; antiferromagnets can improve the functionalities of ferromagnets with higher response times, and having the information shielded against external magnetic field. Moreover, a large list of aniferromagnetic semiconductors and metals with Néel temperatures above room temperature exists. In the present manuscript, we persevere in the quest for the limits of how large can anisotropic magnetoresistance be in antiferromagnetic materials with very large spin-orbit coupling. We selected IrMn as a prime example of first-class moment (Mn) and spin-orbit (Ir) combination. Isothermal magnetotransport measurements in an antiferromagnetic-metal(IrMn)/ferromagnetic-insulator thin film bilayer have been performed. The metal/insulator structure with magnetic coupling between both layers allows the measurement of the modulation of the transport properties exclusively in the antiferromagnetic layer. Anisotropic magnetoresistance as large as 0.15% has been found, which is much larger than that for a bare IrMn layer. Interestingly, it has been observed that anisotropic magnetoresistance is strongly influenced by the field cooling conditions, signaling the dependence of the found response on the formation of domains at the magnetic ordering temperature.

Intrinsic antiferromagnetic/insulating phase at manganite surfaces and interfaces.

In this work we investigate interfacial effects in bilayer systems integrated by La(2/3)Sr(1/3)MnO(3) (LSMO) thin films and different capping layers by means of surface-sensitive synchrotron radiation techniques and transport measurements. Our data reveal a complex scenario with a capping-dependent variation of the Mn oxidation state by the interface. However, irrespective of the capping material, an antiferromagnetic/insulating phase is also detected at the interface, which is likely to originate from a preferential occupancy of Mn 3d 3z(2)-r(2) e(g) orbitals. This phase, which extends approximately to two unit cells, is also observed in uncapped LSMO reference samples, thus pointing to an intrinsic interfacial phase separation phenomenon, probably promoted by the structural disruption and inversion symmetry breaking at the LSMO free surface/interface. These experimental observations strongly suggest that the structural disruption, with its intrinsic inversion symmetry breaking at the LSMO interfaces, plays a major role in the observed depressed magnetotransport properties in manganite-based magnetic tunneling junctions and explains the origin of the so-called dead layer.

Self-assembled pit arrays as templates for the integration of Au nanocrystals in oxide surfaces.

We report on the fabrication of long-range ordered arrays of Au nanocrystals (sub-50 nm range) on top of manganite (La(2/3)Sr(1/3)MnO(3)) thin films achieving area densities around 2 × 10(10) gold nanocrystals per cm(2), well above the densities achievable by using conventional nanofabrication techniques. The gold-manganite interface exhibits excellent conduction properties. Long-range order is achieved by a guided self-assembling process of Au nanocrystals on self-organized pit-arrays acting as a template for the nucleation of gold nanocrystals. Self-organization of pits on the manganite film surface promoted by the underlying stepped SrTiO(3) substrate is achieved by a fine tuning of the growth kinetic pathway, taking advantage of the unusual misfit strain relaxation behaviour of manganite films.

Kinetic versus strain formation of self-organized nanoholes in manganite thin films.

We report on the formation of self-organized rows of pits in highly epitaxial La(2/3)Sr(1/3)MnO(3) thin films on top of substrates having different structural misfits by rf magnetron sputtering. The best-defined pits form in coherently grown films at a low misfit irrespective of its nature (tensile or compressive stress). It is also found that the pit rows align along the step edges, which indicates in-phase growth instability with the step edges, irrespective of the misfit. However, out-of-phase pit rows are also found when the terrace width increases due to a decrease of the miscut angle. Pit's volume scales inversely with the lattice mismatch suggesting that structural strain alone does not favor the formation of pits. The formation of pits is analyzed within a thermodynamic model.

The effects of exchange bias on Fe-Co/MgO magnetic nanoparticles with core/shell morphology.

The effects of exchange bias on core/shell structured nanoparticles are analyzed. Nanoparticles are integrated with high moment Fe-Co crystallites covered epitaxially with MgO shells. It is observed that the coercive field H(C)(FeCo)>H(C)(Co)>H(C)(Fe); however, the exchange bias field H(E) of the Co sample is higher than that of the FeCo one, while H(E)=0 for the Fe sample. It is suggested that the exchange bias is induced by the formation of a (Co, Mg)O solid solution. In fact, we show that it is possible to modify the exchange bias properties by manipulating the level of Mg dusting at the interface, as recently reported for thin films.

Material damage induced by nanofabrication processes in manganite thin films.

We investigated the use of the focused ion-beam (FIB) technique as a nanofabrication tool for the implementation of oxide-based magnetic and magnetoelectronic functional devices. In particular, we studied the effect of using FIB lithography for the patterning of La(2/3)Ca(1/3)MnO(3) magnetic oxide thin films. Results obtained show that the transport properties of patterned areas were strongly degraded after the patterning process. In contrast, no degradation was detected when the patterning was performed using a less aggressive technique. The origin of this degradation correlates with Ga(+) ion implantation, as indicated by Auger spectroscopy analysis of the patterned films.