Ferrimagnetic Oxides Research Articles

Temperature-Dependent Surface Anisotropy in (110) Epitaxial Rare Earth Iron Garnet Films.

Ferrimagnetic oxide thin films are important material platforms for spintronic devices. Films grown on low symmetry orientations such as (110) exhibit complex anisotropy landscapes that can provide insight into novel phenomena such as spin-torque auto-oscillation and spin superfluidity. Using spin-Hall magnetoresistance measurements, the in-plane (IP) and out-of-plane (OOP) uniaxial anisotropy energies are determined for a thickness series (5-50nm) of europium iron garnet (EuIG) and thulium iron garnet (TmIG) films epitaxially grown on a gadolinium gallium substrate with (110) orientation and capped with Pt. Pt/EuIG/GGG exhibits an (001) easy plane of magnetization perpendicular to the substrate, whereas Pt/TmIG/GGG exhibits an (001) hard plane of magnetization perpendicular to the substrate with an IP easy axis. Both IP and OOP surface anisotropy energies comparable in magnitude to the bulk anisotropy are observed. The temperature dependence of the surface anisotropies is consistent with first-order predictions of a simplified Néel surface anisotropy model. By taking advantage of the thickness and temperature dependence demonstrated in these ferrimagnetic oxides grown on the low symmetry (110) orientations, the complex anisotropy landscapes can be tuned to act as a platform to explore rich spin textures and dynamics.

Intracellular Magnetic Hyperthermia Sensitizes Sorafenib to Orthotopic Hepatocellular Carcinoma Via Amplified Ferroptosis.

Sorafenib (SRF) is recognized as the primary treatment for hepatocellular carcinoma (HCC), yet the emergence of SRF resistance in many HCC patients results in unfavorable outcomes. Enhancing the efficacy of SRF in HCC remains a significant challenge. SRF works in inducing ferroptosis, a form of cell death, in cancer cells through the inhibition of glutathione peroxidase 4 (GPX4). The effectiveness of this process is limited by the low levels of cellular iron and reactive oxygen species (ROS). A promising approach to circumvent this limitation is the use of intracellular magnetic hyperthermia (MH) mediated by magnetic iron oxide nanomaterials (MIONs). When MIONs are subjected to an alternating magnetic field (AMF), they heat up, enhancing the Fenton reaction, which in turn significantly increases the production of ROS within cells. In this study, we explore the capability of MH facilitated by high-performance ferrimagnetic vortex-domain iron oxide nanoring (FVIO) to enhance the effectiveness of SRF treatment in HCC. The increased iron uptake facilitated by FVIO significantly enhances the sensitivity of HCC cells to SRF-induced ferroptosis. Moreover, the nanoheat generated by FVIO in response to an AMF further elevates ROS levels and stimulates lipid hydroperoxide (LPO) production and GPX4 inactivation, thereby intensifying ferroptosis. Both in vitro and in vivo animal studies demonstrate that combining FVIO-mediated MH with SRF significantly reduces cell viability and inhibits tumor growth, primarily through enhanced ferroptosis, with minimal side effects. The effectiveness of this combination therapy is affected by the ferroptosis inhibitor ferrostatin-1 (Fer-1) and the iron chelator deferoxamine (DFO). The combination treatment of FVIO-mediated MH and SRF offers a strategy for HCC treatment by promoting accelerated ferroptosis, presenting a different perspective for the development of ferroptosis-based anticancer therapies.

(Invited) Probing Spin Selective Surface Chemistry with Circularly Polarized XUV Light

Controlling spin states of surface reaction intermediates is an important but often overlooked parameter to designing semiconductor photocatalysts to mimic nature’s best photosynthetic complexes. Extreme Ultraviolet Reflection-Absorption (XUV-RA) spectroscopy enables direct observation of surface electron dynamics by combining element, oxidation, and spin state resolution, with surface sensitivity and ultrafast time resolution. While absorption of linearly polarized XUV light can probe the local oxidation and spin states of individual elements, it is insensitive to absolute spin alignment. To enable the study of spin-selective electron dynamics at interfaces, we have recently implemented ultrafast XUV Magnetic Circular Dichroism (XUV-MCD). Employing XUV-MCD in a reflection geometry, we are now studying the ultrafast surface electron dynamics that give rise to spin polarized photocurrents in magnetic and chiral semiconductors. As an example, yttrium iron garnet (Y3Fe5O12, YIG) is a ferrimagnetic oxide with a visible band gap, consisting of two sub-lattices based on octahedrally and tetrahedrally coordinated Fe(III) centers. Ultrafast XUV measurements show that electron-phonon coupling and polaron formation rates differ significantly between octahedral and tetrahedral centers leading to very different charge carrier recombination kinetics. Circular measurements show that this difference in recombination rate gives rise to long-lived, spin-polarized charge accumulation at the YIG surface that drives spin selective water oxidation. This new ability to observe real-time spin polarization at surfaces promises to provide key design parameters for semiconductor photocatalysts capable of spin selective surface chemistry.

Electron holography observation of individual ferrimagnetic lattice planes.

Atomic-scale observations of a specific local area would be considerably beneficial when exploring new fundamental materials and devices. The development of hardware-type aberration correction1,2 in electron microscopy has enabled local structural observations with atomic resolution3-5 as well as chemical and vibration analysis6-8. In magnetic imaging, however, atomic-level spin configurations are analysed by electron energy-loss spectroscopy by placing samples in strong magnetic fields9-11, which destroy the nature of the magnetic ordering in the samples. Although magnetic-field-free observations can visualize the intrinsic magnetic fields of an antiferromagnet by unit-cell averaging12, directly observing the magnetic field of an individual atomic layer of a non-uniform structure is challenging. Here we report that the magnetic fields of an individual lattice plane inside materials with a non-uniform structure can be observed under magnetic-field-free conditions by electron holography with a hardware-type aberration corrector assisted by post-digital aberration correction. The magnetic phases of the net magnetic moments of (111) lattice planes formed by opposite spin orderings between Fe3+ and Mo5+ in a ferrimagnetic double-perovskite oxide (Ba2FeMoO6) were successfully observed. This result opens the door to direct observations of the magnetic lattice in local areas, such as interfaces and grain boundaries, in many materials and devices.

Reprogrammed IDO-Induced Immunosuppressive Microenvironment Synergizes with Immunogenic Magnetothermodynamics for Improved Cancer Therapy.

Indoleamine 2,3-dioxygenase (IDO), highly expressed in hepatocellular carcinoma (HCC), plays a pivotal role in creating an immune-suppressive tumor microenvironment. Inhibiting IDO activity has emerged as a promising immunotherapeutic strategy; however, the delivery of IDO inhibitors to the tumor site is constrained, limiting their therapeutic efficacy. In this study, we developed a magnetic vortex nanodelivery system for the targeted delivery of the IDO inhibitor NLG919, integrated with magnetic hyperthermia therapy to reverse the immune-suppressive microenvironment of liver cancer and inhibit tumor growth. This system comprises thermoresponsive polyethylenimine-coated ferrimagnetic vortex-domain iron oxide nanorings (PI-FVIOs) loaded with NLG919 (NLG919/PI-FVIOs). Under thermal effects, NLG919 can be precisely released from the delivery system, counteracting IDO-mediated immune suppression and synergizing with NLG919/PI-FVIOs-mediated magnetothermodynamic (MTD) therapy-induced immunogenic cell death (ICD), resulting in effective HCC suppression. In vivo studies demonstrate that this combination therapy significantly inhibits tumor growth and metastasis by enhancing the accumulation of cytotoxic T lymphocytes and suppressing regulatory T cells within the tumor. Overall, our findings reveal that NLG919/PI-FVIOs can induce a potent antitumor immune response by disrupting the IDO pathway and activating the ICD, offering a promising therapeutic avenue for HCC treatment.

Influence of magnetic interactions in iron oxide nanoparticle polymer composites on magnetism and induction heating

Induction heating of composite materials is of great interest in fields such as controlled polymer curing or degradation, self-healing or contactless joining. Ferrimagnetic iron oxide nanoparticle (IONPs) are suitable candidates for a powder additive to provide this inductive heating functionality, while being low-cost, abundant and a well-studied material class. Varying IONP size, morphology or doping facilitates fine-tuning of their heating properties. However, the interactions of such IONP additives in material composites are often neglected and can significantly alter the induction heating mechanism. In this work, we systematically vary the IONP interactions in polydimethylsiloxane composite materials by integrating 1.) dispersed IONPs 2.) supraparticles of IONPs (micrometer-assemblies), and 3.) oven-dried hard agglomerated IONPs. Additionally, these three levels of interaction are investigated for three different IONPs types (dodecahedrally and octahedrally shaped, as well as cobalt-doped). In general, dispersed IONPs reveal a broader hysteresis and therefore a faster heating curve. We highlight that not only IONP characteristics (size, morphology, doping), but also excitation field strength and foremost IONP interactions in the composite materials are parameters that are interdependent regarding induction heating and need to be considered as such for optimization in an application-oriented scenario.

Synthesis of 2D-Material(G,GO,rGO,h-BN)-Magnetic(Fe,Fe3O4)Nanocomposites

For the purpose of synthesizing 2D-Material–Magnetic nanocomposites, several new modifications of existing 2D-materials synthesis methods by exfoliation and chemical synthesis from liquid charge are developed. Using them, graphene (G), graphene oxide (GO), reduced graphene oxide (rGO) and hexagonal boron nitride (h-BN) matrix magnetic nanocomposites for the first time are obtained by coating or intercalation their nanoparticles with ferromagnetic iron (Fe) or ferrimagnetic iron oxide – magnetite (Fe3O4). These materials are prospective for variety of high tech applications. In particular, h-BN–Fe3O4 composite nanoparticles can serve for neutron-capturing boron isotope 10B effective delivery agents in BNCT (Boron Neutron Capture Therapy) of cancer as they allow the controlling by an external magnetic field targeting to tumor tissue.

Impact of Nanoheater Subcellular Localization on the Antitumor Immune Efficacy of Magnetic Hyperthermia

Magnetic nanoparticles (MNPs)-mediated magnetic hyperthermia therapy is garnering attention as a promising modality for tumor remission. This therapy combines localized nano-scale heating and reactive oxygen species-related immunologic effects. A critical aspect in optimizing this therapy involves understanding how nanoheaters’ subcellular localizations influence the therapeutic efficacy and immunological effects of magnetic hyperthermia. Herein, we investigate these effects by focusing on the strategic localization of ferrimagnetic vortex-domain iron oxide (FVIO) nanorings within lysosomes and the cytoplasm of hepatocellular carcinoma (HCC) cells. The comparative analysis revealed that lysosomal-localized magnetic hyperthermia markedly increased apoptosis in Hepa1–6 cells and effectively induced immunogenic cell death (ICD). Mechanistically, lysosomal-localized magnetic hyperthermia led to Bid-associated apoptosis and caspase-1-dependent interleukin-1β (IL-1β) secretion, likely due to enhanced lysosomal membrane permeabilization. Moreover, it reduced calreticulin degradation and increased its presence at the cell membrane, thereby boosting ICD efficiency. In contrast, cytoplasmic-localized magnetic hyperthermia showed comparatively lesser impact than its lysosomal-localized counterpart. In vivo experiments reinforced the exceptional efficacy of lysosomal-localized magnetic hyperthermia, which notably enhanced dendritic cells activation and T cells infiltration in both tumors and lymph nodes, thereby triggering a robust antitumor immune response. Additionally, lysosomal-localized magnetic hyperthermia improved tumor vaccine efficacy and demonstrated the potential for sustaining long-term immune responses in antitumor treatments. This study highlights the crucial role of subcellular positioning of magnetic nanoheaters in determining the efficacy of antitumor immunological responses in magnetic hyperthermia therapy, offering valuable insights for future cancer treatment strategies.

Magnetic anisotropy, magnetization reversal and switching in Ni4Nb2O9 single crystals

Ni4Nb2O9 is an insulating compensated ferrimagnet with TN = 77 K and T comp= 33 K. We report here the study of the magnetic anisotropy using millimeter-size crystals grown in an image furnace. The magnetization measurements, vs temperature, performed with H aligned along the three main crystallographic axes, show similar Curie–Weiss temperatures (Θp ≈ 190 K) and rather similar effective paramagnetic moments (from 3.5 μ B to 3.6 μ B). This suggests that the strongest magnetic interaction is the antiferromagnetic one, coupling the ferromagnetic distorted honeycomb layers and zigzag ribbons via face sharing NiO6 octahedra. This strong antiferromagnetic coupling is supported by DFT calculations that do not evidence any inter site ferromagnetic interaction, leading to total compensation between magnetic moments of both Ni2+ sites. Measurements vs magnetic field below TN reveal an anisotropic behaviour, with square magnetization loops for H in the ab plane, whereas linear M(H) curves without hysteresis are observed for H‖c. This anisotropy between ab plane and c axis occurs also in the magnetization reversal (MR), which is observed in the ab plane only. Starting from M(H) virgin curves collected just below T comp= 33 K with H‖a or H‖b, the memory-like effect was tested through magnetization switching induced by H or T alternating changes. Below T comp, smaller H is needed to switch M symmetrically for H along b than along a, and, for T switching (2 K interval, constant H), a larger M change is obtained along a than along b. The comparison with ferrimagnetic oxides which exhibit MR, like spinels or rare earth orthoferrites, shows that Ni4Nb2O9 is unique since only one magnetic cation over two sites in octahedral coordination is at play, thus providing a unique platform to study M switching but also a challenge for theoretical interpretation.

Intracellular Magnetic Hyperthermia Enables Concurrent Down-Regulation of CD47 and SIRPα To Potentiate Antitumor Immunity.

Harnessing the potential of tumor-associated macrophages (TAMs) to engulf tumor cells offers promising avenues for cancer therapy. Targeting phagocytosis checkpoints, particularly the CD47-signal regulatory protein α (SIRPα) axis, is crucial for modulating TAM activity. However, single checkpoint inhibition has shown a limited efficacy. In this study, we demonstrate that ferrimagnetic vortex-domain iron oxide (FVIO) nanoring-mediated magnetic hyperthermia effectively suppresses the expression of CD47 protein on Hepa1-6 tumor cells and SIRPα receptor on macrophages, which disrupts CD47-SIRPα interaction. FVIO-mediated magnetic hyperthermia also induces immunogenic cell death and polarizes TAMs toward M1 phenotype. These changes collectively bolster the phagocytic ability of macrophages to eliminate tumor cells. Furthermore, FVIO-mediated magnetic hyperthermia concurrently escalates cytotoxic T lymphocyte levels and diminishes regulatory T cell levels. Our findings reveal that magnetic hyperthermia offers a novel approach for dual down-regulation of CD47 and SIRPα, reshaping the tumor microenvironment to stimulate immune responses, culminating in significant antitumor activity.

Studies on electromagnetic properties of lithium based ferrimagnetic spinel oxides prepared with different additives and microwave sintering

Soft ferrimagnetic spinel lithium based oxides were prepared with additives like V2O5 and Na2SiO3 and sintered with the efficient microwave sintering technique. Tetravalent metal ions substituents like Mn+4, Ti+4 were used to enhance the important properties like D. C. resistivity, saturation magnetization, permeability, hysteresis and dielectric behavior. The ferrites were sintered at different sintering temperatures viz., 900, 950 and 1000 °C for 10 min by microwave technique and by conventional technique at 1050 °C for 4h. X-ray diffraction (XRD) studied the structural behavior which confirmed the spinel characteristics, Scanning electron microscopy (SEM) and EDAX revealed the microstructural and elemental compositions respectively of the ferrites. The use of additives and the microwave sintering significantly influencing the microstructural behavior and subsequently on the electromagnetic properties could be observed. Studies of initial permeability and initial permeability loss found to remain nearly constant with change in frequency until at certain frequency they showed resonance behavior. The resonance frequency’s dependence on the microstructures of the ferrites could be observed. Temperature dependence behavior of the dielectric parameters and the B-H loop traced from torroidal samples of the ferrites were studied.

Re/Ir@Os-doping induced insulator-to-metal transition in Mott-insulator Ca2FeOsO6: octahedral distortion effects.

Regardless of several investigations to elucidate the ground state of the strongly correlated electron systems in doped Mott-insulators (MIs), the origin of the doping-induced insulator-to-metal transition (IMT) remains a crucial and debatable subject in solid-state physics. Herein, we explore the consequences of Re/Ir-doping at the Os-site (Re/Ir@Os), on the physical properties of the MI ferrimagnetic (FiM) Ca2FeOsO6 double perovskite oxides using density functional theory calculations. The doped structures' solidity is analyzed by computing the defect formation energies in terms of the dopant-rich situation, which confirms their growth credibility at ambient conditions along with mechanical and dynamical stabilities. Various FiM spin-ordering is taken into account in the doped structures to analyze the magnetic ground state, which is FiM-I/FiM-II in the Re/Ir@Os-doped system. Remarkably, an IMT is predicted in the Re/Ir@Os-doped structures, which is due to the admixture of the partially occupied 5d orbitals of these ions. The calculated partial spin magnetic moments (ms) of +4.12, -1.58, -0.75 and +0.88μB on the Fe, Os, Re, and Ir ions, endorse the +3, +5, +5, and +4 states having electronic configurations of t32g↑t02g↓e2g↑e0g↓, t32g↑t02g↓e0g↑e0g↓, t22g↑t02g↓e0g↑e0g↓, t32g↑t22g↓e0g↑e0g↓, respectively. The "+" and "-" signs on the ions ms values, lead the systems into various FiM magnetic ordering. Moreover, the estimated Curie temperature (TC) using the Heisenberg model in the pristine structure is 334 K, which is close to the experimentally observed value of 320 K along with a colossal uniaxial magneto crystalline anisotropy energy constant (K) of 2.95 × 107 erg cm-3 having the easy magnetic axis of the ac-plane ([101]). It is established that TC/K reduces and enhances to 298 K/1.33 × 107 erg cm-3 and 365 K/4.71 × 107 erg cm-3 for the Re@Os and Ir@Os-doped motif due to an increase and decrease in the octahedral distortions compared to that of the pristine system, respectively.

Tunable Spin-Polarized States in Graphene on a Ferrimagnetic Oxide Insulator.

Spin-polarized two-dimensional (2D) materials with large and tunable spin-splitting energy promise the field of 2D spintronics. While graphene has been a canonical 2D material, its spin properties and tunability are limited. Here, this work demonstrates the emergence of robust spin-polarization in graphene with large and tunable spin-splitting energy of up to 132 meV at zero applied magnetic fields. The spin polarization is induced through a magnetic exchange interaction between graphene and the underlying ferrimagnetic oxide insulating layer, Tm3 Fe5 O12 , as confirmed by its X-ray magnetic circular dichroism (XMCD). The spin-splitting energies are directly measured and visualized by the shift in their Landau-fan diagram mapped by analyzing the measured Shubnikov-de-Haas (SdH) oscillations as a function of applied electric fields, showing consistent fit with the first-principles and machine learning calculations. Further, the observed spin-splitting energies can be tuned over a broad range between 98 and 166 meV by field cooling. The methods and results are applicable to other 2D (magnetic) materials and heterostructures, and offer great potential for developing next-generation spin logic and memory devices.

Single-cell transcriptomics reveals ferrimagnetic vortex iron oxide nanoring-mediated mild magnetic hyperthermia exerts antitumor effects by alleviating macrophage suppression in breast cancer

The potential of Ferrimagnetic vortex iron oxide nanoring-mediated mild magnetic hyperthermia (FVIO-MHT) in solid tumor therapy has been demonstrated. However, the impact of FVIO-MHT on the tumor microenvironment (TME) remains unclear. This study utilized single-cell transcriptome sequencing to examine the alterations in the TME in response to FVIO-MHT in breast cancer. The results revealed the cellular composition within the tumor microenvironment (TME) was primarily modified due to a decrease in tumor cells and an increased infiltration of myeloid cells. Subsequently, an enhancement in active oxygen (ROS) metabolism was observed, indicating oxidative damage to tumor cells. Interestingly, FVIO-MHT reprogrammed the macrophages’ phenotypes, as evidenced by alterations in the transcriptome characteristics associated with both classic and alternative activated phenotypes. And an elevated level of ROS generation and oxidative phosphorylation suggested that activated phagocytosis and inflammation occurred in macrophages. Additionally, cell–cell communication analysis revealed that FVIO-MHT attenuated the suppression between tumor cells and macrophages by inhibiting phagocytic checkpoint and macrophage migration inhibitory factor signaling pathways. Inhibition of B2m, an anti-phagocytosis checkpoint, could promote macrophage-mediated phagocytosis and significantly inhibit tumor growth. These data emphasize FVIO-MHT may promote the antitumor capabilities of macrophages by alleviating the suppression between tumor cells and macrophages.

Amino-grafted water-soluble ferrimagnetic iron oxide nanoparticles with ultra-high relaxivity for dual-modal magnetic resonance imaging

Highly stable dispersion is an important precondition for functionalized magnetic nanoparticles used as a contrast agent. Amino-grafted ferromagnetic γ-Fe2O3 nanoparticles are synthesized by deep-eutectic-solvent electrolysis for magnetic resonance imaging. The statistical naked scale of the particle is 8.2 nm with a magnetization of 71.9 emu g−1. An ultra-high Zeta potential of + 50 mV boosts the dispersion stable for more than 600 days, which is unprecedented. The 26.4 nm hydrated nanoparticles exhibit high biocompatibility after being efficiently ingested by cells in vitro. Both longitudinal relaxation efficiency of 179.7 mM−1 s−1 and transverse relaxivity of 497.8 mM−1 s−1 are among the highest demonstrated in recent years. Whether in vitro or in vivo, the imaging mode changes from T1 to T2 with the increase of iron equivalent. At doses 0.12 and 0.91 mg Fe per kg living body, the nanoparticles are capable of prominently weighted imaging of T1 and T2 of the liver, respectively. The nanocrystals can significantly distinguish between normal tissue and the tumor site of the liver as well. Findings demonstrate that the highly stable dispersion of amino-grafted ferrimagnetic nanoparticles is capable of dual-modal magnetic resonance imaging with high relaxation efficiency and significant resolution.

Microstructure and physical properties of Sr2CrHfO6 ferrimagnetic double‐perovskite oxides

AbstractHalf‐metallic ferromagnets (HMFs) are highly desirable materials for applications in spintronics because of their semiconducting behavior for one spin projection and metallic nature for the other. To operate spintronic devices at room temperature (RT), HMFs should simultaneously have a large saturation magnetization (MS), high magnetic Curie temperature (TC), and a wide half‐metallic gap. However, HMFs that simultaneously fulfill these three criteria are rare. In this work, we report for the first time on the ferrimagnetic double perovskite oxides of Sr2CrHfO6 (SCHO) with a magnetic TC up to 545 K due to the strong Cr3+(↑)Cr4+(↓) antiferromagnetic spin interactions. The combined experimental results confirmed that the SCHO powders crystallized in an orthogonal crystal structure with Pnma symmetry. The SEM images demonstrate that the powders exhibit a spherical morphology with particle sizes between 150 and 250 nm. XPS spectra verified the presence of Sr2+, Cr 3+/Cr4+, and Hf4+/Hfx+ (x < 4) ions in the SCHO powder. Oxygen was present as lattice oxygen and adsorbed oxygen species. At 2 K, the SCHO powder exhibited ferrimagnetic behavior with MS of 0.11 μB/f. u and a magnetic coercive field of 290 Oe. The SCHO ceramics displayed a normal butterfly‐like magnetoresistance‐magnetic field (MR‐H) curve at 2 K due to the intergranular tunneling effect, and the MR (2 K, 7 T) value was −2.05%. The temperature dependence of the resistivity of the SCHO ceramics revealed their semiconducting nature, and the electrical transport data in the temperature range 2−800 K were well fitted by the Mott's variable‐range hopping model, thermal activation model, and small polaron hopping model. Optical measurements demonstrate that the SCHO powders have a direct optical bandgap of 2.25 eV in the visible light window. Having both high TC and a direct optical bandgap (2.25 eV) makes SCHO oxides attractive for use in advanced spintronic devices and solar cells.

Mineral magnetic properties of urban forest soils tailored to soil quality indicator

Ecosystem surveys reveal the benefits to society, provided by the natural environment, which in turn is chiefly regulated by the geodiversity. Thus, physico-chemical processes regulating the solid rock/sediment response to environmental changes comprise an important part in the assessment of natural ecosystems. Environmental magnetism provides a wide set of field and laboratory data able to discover natural and anthropogenic processes affecting different environmental compartments. Despite this, geosciences and environmental magnetism in particular, are under-represented in ecosystem assessment tools due to the lack of unified and clearly articulated application template. In this study, we propose a new mineral magnetic indicator of soil’s quality, based on detailed appraisal of field- and laboratory mineral magnetic characteristics of a collection of 453 urban topsoil samples. Field magnetic susceptibility (Kfield) and laboratory measurements of magnetic parameters revealed that soil magnetism reflects sensitively soils affected by vehicle traffic and park’s alleys foot load from semi-natural soil. Geochemical analyses of the content of Potentially Toxic Elements (PTEs) on a sub-set of samples was used for magnetic data validation. Correlation analysis showed strong positive link between magnetic parameters and the main PTEs, the strongest being obtained between magnetic susceptibility and the complex pollution load index (PLI). Factor analysis suggested that three factors account for the 74% of data variability. They were assigned to: 1) traffic emissions, 2) pedogenic contribution and 3) lithogenic input plus anthropogenic organic waste additions. Novel mineral magnetic Indicator (MAG) was defined, combining information on composition, concentration and grain size of ferrimagnetic iron oxides, using scored contributions from five magnetic parameters and grain size sensitive ratios. Evaluation of the spatial MAG map showed its suitability as a complex indicator of soils’ contamination with PTEs. Kfield reflected sensitively overall anthropogenic load not necessarily related to PTEs contamination but also to foot trampling and application of fertilizers.

Spin-Selective Oxygen Evolution Reaction in Chiral Iron Oxide Nanoparticles: Synergistic Impact of Inherent Magnetic Moment and Chirality.

Electron spin polarization is identified as a promising avenue for enhancing the oxygen evolution reaction (OER), which is the bottleneck that limits the energy efficiency of water-splitting. Here, we report that both ferrimagnetic (f-Fe3O4) and superparamagnetic iron oxide (s-Fe3O4) catalysts can exhibit external magnetic field (Hext)-induced OER enhancement, and the activity is proportional to their intrinsic magnetic moment. Additionally, the chirality-induced spin selectivity (CISS) effect was utilized in synergy with Hext to get a maximum enhancement of up to 89% improvement in current density (at 1.8 V vs RHE) with a low onset potential of 270 mV in s-Fe3O4 catalysts. Spin polarization and the resultant spin selectivity suppress the production of H2O2 and promote the formation of ground state triplet O2 during the OER. Furthermore, the design of chiral s-Fe3O4 with synergistic spin potential effect demonstrates a high spin polarization of ∼42%, as measured using conductive atomic force microscopy (c-AFM).

Reversal of HMGA1-Mediated Immunosuppression Synergizes with Immunogenic Magnetothermodynamic for Improved Hepatocellular Carcinoma Therapy.

Magnetothermodynamic (MTD) therapy can activate antitumor immune responses by inducing potent immunogenic tumor cell death. However, tumor development is often accompanied by multifarious immunosuppressive mechanisms that can counter the efficacy of immunogenic MTD therapy. High-mobility group protein A1 (HMGA1) is overexpressed within hepatocellular carcinoma tissues and plays a crucial function in the generation of immunosuppressive effects. The reversal of HMGA1-mediated immunosuppression could enhance immunogenic tumor cell death-induced immune responses. A ferrimagnetic vortex-domain iron oxide (FVIO) nanoring-based nanovehicle was developed, which is capable of efficiently mediating an alternating magnetic field for immunogenic tumor cell death induction, while concurrently delivering HMGA1 small interfering (si)RNA (siHMGA1) to the cytoplasm of hepatocellular carcinoma Hepa 1-6 cells for HMGA1 pathway interference. Using siHMGA1-FVIO-mediated MTD therapy, the proliferation of hepatocellular carcinoma Hepa 1-6 tumors was inhibited, and the survival of a mouse model was improved. We also demonstrated that siHMGA1-FVIO-mediated MTD achieved synergistic antitumor effects in a subcutaneous hepatocellular carcinoma Hepa 1-6 and H22 tumor model by promoting dendritic cell maturation, enhancing antigen-presenting molecule expression (both major histocompatibility complexes I and II), improving tumor-infiltrating T lymphocyte numbers, and decreasing immunosuppressive myeloid-derived suppressor cells, interleukin-10, and transforming growth factor-β expression. The nanoparticle system outlined in this paper has the potential to target HMGA1 and, in combination with MTD-induced immunotherapy, is a promising approach for hepatocellular carcinoma treatment.

Acquisition of natural remanence in the basaltic laterites of Deccan volcanic province (India): Implications to palaeomagnetic studies in laterites

Lateritization in the Deccan basalt province (India) represents a large spectrum of chemical weathering with up to 99% CIA values and complete ferri- to antiferromagnetic transformations. We combined rock magnetic, palaeomagnetic, XRD, and XRF analyses to investigate the mineralogical transformations and its relationship to the acquisition of natural remanent magnetization (NRM) by sampling a 25 m thick Deccan lateritic profile from the West Coast of India. Significant amount of amorphous hematite (ha), crystalline hematite (hc), goethite and their Al- substituted forms were detected along with gibbsite and kaolinite. The domain size association of ‘SP + SD and ‘SP + SD + MD’ in the ferri- as well as antiferromagnetic forms; and the combination of ha and hc yield strong NRMs amongst these laterites. Low field demagnetization (<5mT) allows removal of haNRM; and the secondary components due to ferrimagnetic oxides can be removed at < 25 mT. Thereafter, the hcNRM continued to decay up to > 150 mT. Palaeomagnetic tests (Koenigsberger ratio, MDF, intensity decay and Zijderveld diagrams) indicate stable Characteristic remanent magnetizations (ChRM) due to hc; and the Al-substitutions does not affect the ChRM stability, depicting these laterites as excellent palaeomagnetic recorders. The stable ChRMs due to Chemical/Crystallization RMs due to ‘hc’ also benchmarks the degree of maturity within the process of lateritization.