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Zhizhi Sun,1 Matthew Worden,2 Yaroslav Wroczynskyj,3 Vinith Yathindranath,4 Johan van Lierop,3 Torsten Hegmann,1,2,4,5 Donald W Miller1 1Department of Pharmacology and Therapeutics, University of Manitoba, Winnipeg, Manitoba, Canada; 2Department of Chemistry and Biochemistry, Kent State University, Kent, OH, USA; 3Department of Physics and Astronomy, 4Department of Chemistry, University of Manitoba, Winnipeg, Manitoba, Canada; 5Chemical Physics Interdisciplinary Program, Liquid Crystal Institute, Kent State University, Kent, OH, USA Purpose: The present study examines the use of an external magnetic field in combination with the disruption of tight junctions to enhance the permeability of iron oxide nanoparticles (IONPs) across an in vitro model of the blood–brain barrier (BBB). The feasibility of such an approach, termed magnetic field enhanced convective diffusion (MFECD), along with the effect of IONP surface charge on permeability, was examined. Methods: The effect of magnetic field on the permeability of positively (aminosilane-coated [AmS]-IONPs) and negatively (N-(trimethoxysilylpropyl)ethylenediaminetriacetate [EDT]-IONPs) charged IONPs was evaluated in confluent monolayers of mouse brain endothelial cells under normal and osmotically disrupted conditions. Results: Neither IONP formulation was permeable across an intact cell monolayer. However, when tight junctions were disrupted using D-mannitol, flux of EDT-IONPs across the bEnd.3 monolayers was 28%, increasing to 44% when a magnetic field was present. In contrast, the permeability of AmS-IONPs after osmotic disruption was less than 5%. The cellular uptake profile of both IONPs was not altered by the presence of mannitol. Conclusions: MFECD improved the permeability of EDT-IONPs through the paracellular route. The MFECD approach favors negatively charged IONPs that have low affinity for the brain endothelial cells and high colloidal stability. This suggests that MFECD may improve IONP-based drug delivery to the brain. Keywords: drug delivery, iron oxide nanoparticles, permeability, blood–brain barrier, magnetic targeting

The magnetic and magnetotransport properties of Ni80Fe20/La0.7Sr0.3MnO3 (NiFe/LSMO) bilayers were investigated after bombarding the LSMO surface with low-energy Ar+ or O2+/Ar+ ion beams before the growth of the top NiFe layer. A variety of magnetic properties are revealed, including an asymmetric two-stepped hysteresis loop with an exchange bias loop shift, and alternatively, a symmetric two-stepped hysteresis loop with an enhanced coercivity. Polarized neutron reflectometry measurements provide details of the magnetic depth profile and interface layer magnetism at different temperatures. The LSMO surface modifications determine a complex magnetic and electric NiFe/LSMO interface having a strong effect on the magnetoresistance of the bilayer. Surface engineering based on ion beam bombardment is presented as a promising technique for optimizing the electronic and magnetic properties of NiFe/LSMO junctions for future device applications. [ABSTRACT FROM AUTHOR]

Significant efforts towards understanding bi-magnetic core-shell nanoparticles are underway currently as they provide a pathway towards properties unavailable with single-phased systems. Recently, we have demonstrated that the magnetism of c-Fe2O3/CoO core-shell nanoparticles, in particular, at high temperatures, originates essentially from an interfacial doped iron-oxide layer that is formed by the migration of Co2+ from the CoO shell into the surface layers of the γ-Fe2O3 core [Skoropata et al., Phys. Rev. B 89, 024410 (2014)]. To examine directly the nature of the intermixed layer, we have used high-resolution transmission electron microscopy (HRTEM) and first-principles calculations to examine the impact of the core-shell intermixing at the atomic level. By analyzing the HRTEM images and energy dispersive spectra, the level and nature of intermixing was confirmed, mainly as doping of Co into the octahedral site vacancies of γ-Fe2O3. The average Co doping depths for different processing temperatures (150 °C and 235 °C) were 0.56 nm and 0.78 nm (determined to within 5% through simulation), respectively, establishing that the amount of core-shell intermixing can be altered purposefully with an appropriate change in synthesis conditions. Through first-principles calculations, we find that the intermixing phase of γ-Fe2O3 with Co doping is ferromagnetic, with even higher magnetization as compared to that of pure γ-Fe2O3. In addition, we show that Co doping into different octahedral sites can cause different magnetizations. This was reflected in a change in overall nanoparticle magnetization, where we observed a 25% reduction in magnetization for the 235 °C versus the 150 °C sample, despite a thicker intermixed layer. [ABSTRACT FROM AUTHOR]

We use a novel solution-based disassociation synthesis scheme of the ionic complex Fe(LiBH4)2 to form Fe nanoparticles. The complex was formed initially using a gentle mechanochemical process, and the Fe nanoparticles emerged after 4 h of ball milling in an air-free environment. Rietveld refinement of x-ray diffraction measurements in an air-free sample holder identified a Im3m α-Fe phase. A room temperature Mössbauer spectrum of the sample presented a six-line spectrum unique to Fe0 metal, and the Fe nanoparticles were extremely well crystallized. Magnetometry results presented a reduced saturation magnetization (e.g., Ms ∼ 85 emu/g at 50 K) that had a Bloch-like T2 temperature dependence, consistent with a gap in the magnon fluctuation spectrum due to finitesize effects. The Fe nanoparticles were magnetically soft, with a coercivity ranging from ∼10 to 20mT with decreasing temperature from 350 K. [ABSTRACT FROM AUTHOR]

A series of core/shell Fe-oxide/SiO2 nanoparticles were produced to form Fe-oxide (1:1 Fe3O4 and c-Fe2O3) cores with diameters of approximately 4.6 nm and shell thicknesses ranging from 3.6 to 5.4 nm. Hot press sintering of core/shell nanoparticles created a nanocomposite of Fe-oxide nanoparticles in a SiO2 matrix. The presence of an iron-orthosilicate at the core-shell interface defines the intrinsic magnetic properties of the nanoparticle systems, resulting in an increase in magnetic anisotropy with thicker SiO2 shell. We find that dipole-dipole interactions are mediated by the overall SiO2 shell, and that these interactions are coupling neighbouring particles' magnetization with increasing correlation lengths. When the nanoparticles from a composite material, packing significantly increases the interaction strengths, altering the overall magnetization of the system so that the iron-oxide cores present an approximate 25% increase in (saturation) magnetization to a bulk-like (∼80 emu/g) value. [ABSTRACT FROM AUTHOR]

We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell. [ABSTRACT FROM AUTHOR]

We have examined the effects of core-shell intermixing on the dynamical magnetism of γ-Fe2O3/ MnO nanoparticles. The core and shell phases were identified using x-ray diffraction, and x-ray absorption spectroscopy identified Mn ions in both octahedral and tetrahedral sites, consistent with a significant amount of substitution at the core-shell interface to form an Fe/Mn-ferrite. The dynamical response was probed by Mössbauer spectroscopy, which decouples surface and core spins, and suggested a change in the relaxation behaviour among the spin populations within γ-Fe2O3/MnO relative to the γ-Fe2O3 seed particles. Interestingly, the magnetic relaxation effects at the atomic scale, measured via Möossbauer spectroscopy, were enhanced, indicating that the addition of an MnO shell and intermixing affected the dynamical freezing process which altered the surface magnetism of the γ-Fe2O3 core. Our results show that both the MnO shell and the interfacial intermixed layer are important in determining the core-shell nanoparticle magnetism. [ABSTRACT FROM AUTHOR]

We have fabricated thin films of iron nanocrystallites embedded in a copper matrix using a dual ion beam assisted deposition technique. A secondary End-Hall ion beam bombarded the iron atoms during deposition altering significantly the morphology of the films and allowing for control of the intermixing between iron and copper components. Cross-sectional transmission electron microscopy and x-ray reflectometry experiments indicated that the morphology of the films was that of iron nanocrystallites embedded in a copper matrix. Rietveld refinements of the diffraction pattern identified fcc-copper and amorphous iron. An increased amount of disorder was observed with a reduction in the amount of deposited iron from a 1:1 Fe:Cu ratio to 0.25:0.75 Fe:Cu ratio. Interfacial copper-iron alloys were identified by DC susceptibility experiments through their reduced TC,Alloy (370, 310, and 280 K) compared with that of bulk iron (~1000 K). Element specific x-ray absorption and x-ray magnetic circular dichroism experiments were performed to identify the contributions to the magnetism from the iron and the copper-iron alloy. [ABSTRACT FROM AUTHOR]

Ni3Fe/(Ni, Fe)O thin films with bilayer and nanocrystallite dispersion morphologies are prepared with a dual ion beam deposition technique permitting precise control of nanocrystallite growth, composition, and admixtures. A bilayer morphology provides a Ni3Fe-to-NiO interface, while the dispersion films have different mixtures of Ni3Fe, NiO, and FeO nanocrystallites. Using detailed analyses of high resolution transmission electron microscopy images with Multislice simulations, the nanocrystallites' structures and phases are determined, and the intermixing between the Ni3Fe, NiO, and FeO interfaces is quantified. From field-cooled hysteresis loops, the exchange bias loop shift from spin interactions at the interfaces are determined. With similar interfacial molar ratios of FM-to-AF, we find the exchange bias field essentially unchanged. However, when the interfacial ratio of FM to AF was FM rich, the exchange bias field increases. Since the FM/AF interface 'contact' areas in the nanocrystallite dispersion films are larger than that of the bilayer film, and the nanocrystallite dispersions exhibit larger FM-to-AF interfacial contributions to the magnetism, we attribute the changes in the exchange bias to be from increases in the interfacial segments that suffer defects (such as vacancies and bond distortions), that also affects the coercive fields. [ABSTRACT FROM AUTHOR]

The strength, polarity, and temperature dependence of the exchange bias field in ferromagnet/antiferromagnet thin film systems depend critically on the nature of the interfacial microstructure. Using ion bombardment during film deposition, we have found a way to modulate the interface microstructure, providing unique control over the exchange bias magnetism. We demonstrate interfacial microstructure modulation in Ni80Fe20/(Ni,Fe)O thin films, where different ion bombardment energies alter the exchange coupling between the (Ni,Fe)O and Ni80Fe20 interfaces. One interface configuration provides positive or negative exchange coupling depending on whether the film was cooled with or without an external magnetic field, while another interface configuration results in the more typical negative exchange coupling independent of the field cooling. [ABSTRACT FROM AUTHOR]

The exchange bias field dependence on the Mn-oxide and its microstructure in NiFe/Mn-oxide bilayers was investigated. Transmission electron microscopy results have shown that the bilayer bottom consisted of either α-Mn, rocksalt MnO, or a composite of tetragonal Mn3O4+MnO, depending on the ratio of O2/Ar used during dual ion-beam deposition. Magnetometry results at 5 K indicate that the exchange bias field (Hex∼-300 Oe) is largest in a NiFe/Mn (0%O2/Ar) bilayer. The MnO formation by in situ Mn oxidation results in a decrease in Hex in a NiFe/Mn-oxide (21%O2/Ar) bilayer. In contrast, a further increase in the O2/Ar ratio during deposition results in larger Hex and Hc. This is attributed to the oxidation of MnO into a harder ferrimagnet, Mn3O4. Our results indicate that the antiferromagnetic Mn enabled stronger coupling with NiFe than MnO. In addition, we find that the MnO–Mn3O4 coupling dominates the exchange bias effects at high oxygen concentrations. [ABSTRACT FROM AUTHOR]

Muon spin relaxation has been used to study transverse spin freezing in a-Fe[sub x]Zr[sub 100-x] and a-Fe[sub 90-x]Ru[sub x]Zr[sub 10]. The derived phase diagrams, while generally consistent with model calculations, exhibit some significant differences. Comparison between zero-field and applied field measurements shows that T[sub xy] is strongly affected by a field and falls as B[sup -1], contrary to mean field predictions. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]