Chemical engineering of cationic distribution in spinel ferrite nanoparticles: the effect on the magnetic properties.

A set of ∼9 nm CoFe2O4 nanoparticles substituted with Zn2+ and Ni2+ was prepared by thermal decomposition of metallic acetylacetonate precursors to correlate the effects of replacement of Co2+ with the resulting magnetic properties. Due to the distinct selectivity of these cations for the spinel ferrite crystal sites, we show that it is possible to tailor the magnetic anisotropy, saturation magnetization, and interparticle interactions of the nanoparticles during the synthesis stage. This approach unlocks new possibilities for enhancing the performance of spinel ferrite nanoparticles in specific applications. Particularly, our study shows that the replacement of Co2+ by 48% of Zn2+ ions led to an increase in saturation magnetization of approximately 40% from ∼103 A m2 kg-1 to ∼143 A m2 kg-1, whereas the addition of Ni2+ at a similar percentage led to an ∼30% decrease in saturation magnetization to 68-72 A m2 kg-1. The results of calculations based on the two-sublattice Néel model of magnetization match the experimental findings, demonstrating the model's effectiveness in the strategic design of spinel ferrite nanoparticles with targeted magnetic properties through doping/inversion degree engineering.

Iron Oxide Nanoparticle-Assisted Delamination of Ti3C2Tx MXenes: A New Approach to Produce Magnetic MXene-Based Composites.

Ti3C2Tx MXene is one of the most comprehensively studied 2D materials in terms of its adsorptive, transport, and catalytic properties, cytotoxic performance, etc. Still, conventional MXene synthesis approaches provide low single-flake MXene yield and frequently uncontrollable properties, demanding further post-processing. The MXene family also lacks magnetism, which is helpful for producing effective nanoadsorbents as their magnetic decantation is the cheapest and most convenient way to remove the spent adsorbent from water. Composite materials consisting of magnetic nanoparticles grown on top of MXene flakes are commonly used to provide magnetic properties to the resulting nanocomposite. In this paper, we study the possibility to delaminate multilayer Ti3C2Tx MXene sheets directly by growing iron oxide magnetic nanoparticles inside their interlayer spacing. We find out that, with a mass fraction of particles comparable or exceeding that of MXenes, their growth is accompanied by an effective enhancement of single-layer MXene yield and suitable magnetic properties of the resulting composite. The developed approach can be further used for simplifying synthesis protocols to obtain magnetic MXene-based nanoadsorbents with tunable properties.

Effect of Piezoelectric BaTiO3 Filler on Mechanical and Magnetoelectric Properties of Zn0.25Co0.75Fe2O4/PVDF-TrFE Composites.

Polymer-based multiferroics, combining magnetic and piezoelectric properties, are studied experimentally-from synthesis to multi-parameter characterization-in view of their prospects for fabricating biocompatible scaffolds. The main advantage of these systems is facile generation of mechanical deformations and electric signals in response to external magnetic fields. Herein, we address the composites based on PVDF-TrFE polymer matrices filled with a combination of piezoelectric (BaTiO3, BTO) and/or ferrimagnetic (Zn0.25Co0.75Fe2O4, ZCFO) particles. It is shown that the presence of BTO micron-size particles favors stripe-type structuring of the ZCFO filler and enhances the magnetoelectric response of the sample up to 18.6 mV/(cm∙Oe). Besides that, the admixing of BTO particles is crucial because the mechanical properties of the composite filled with only ZCFO is much less efficient in transforming magnetic excitations into the mechanical and electric responses. Attention is focused on the local surfacial mechanical properties since those, to a great extent, determine the fate of stem cells cultivated on these surfaces. The nano-indentation tests are accomplished with the aid of scanning probe microscopy technique. With their proven suitable mechanical properties, a high level of magnetoelectric conversion and also biocompatibility, the composites of the considered type are enticing as the materials for multiferroic-based polymer scaffolds.

Star-Shaped Magnetic-Plasmonic Au@Fe3O4 Nano-Heterostructures for Photothermal Therapy.

Here, we synthesize a Au@Fe3O4 core@shell system with a highly uniform unprecedented star-like shell morphology with combined plasmonic and magnetic properties. An advanced electron microscopy characterization allows assessing the multifaceted nature of the Au core and its role in the growth of the peculiar epitaxial star-like shell with excellent crystallinity and homogeneity. Magnetometry and magneto-optical spectroscopy revealed a pure magnetite shell, with a superior saturation magnetization compared to similar Au@Fe3O4 heterostructures reported in the literature, which is ascribed to the star-like morphology, as well as to the large thickness of the shell. Of note, Au@Fe3O4 nanostar-loaded cancer cells displayed magneto-mechanical stress under a low frequency external alternating magnetic field (few tens of Hz). On the other hand, such a uniform, homogeneous, and thick magnetite shell enables the shift of the plasmonic resonance of the Au core to 640 nm, which is the largest red shift achievable in Au@Fe3O4 homogeneous core@shell systems, prompting application in photothermal therapy and optical imaging in the first biologically transparent window. Preliminary experiments performing irradiation of a stable water suspension of the nanostar and Au@Fe3O4-loaded cancer cell culture suspension at 658 nm confirmed their optical response and their suitability for photothermal therapy. The outstanding features of the prepared system can be thus potentially exploited as a multifunctional platform for magnetic-plasmonic applications.

Spatial Manipulation of Particles and Cells at Micro- and Nanoscale via Magnetic Forces.

The importance of magnetic micro- and nanoparticles for applications in biomedical technology is widely recognised. Many of these applications, including tissue engineering, cell sorting, biosensors, drug delivery, and lab-on-chip devices, require remote manipulation of magnetic objects. High-gradient magnetic fields generated by micromagnets in the range of 103-105 T/m are sufficient for magnetic forces to overcome other forces caused by viscosity, gravity, and thermal fluctuations. In this paper, various magnetic systems capable of generating magnetic fields with required spatial gradients are analysed. Starting from simple systems of individual magnets and methods of field computation, more advanced magnetic microarrays obtained by lithography patterning of permanent magnets are introduced. More flexible field configurations can be formed with the use of soft magnetic materials magnetised by an external field, which allows control over both temporal and spatial field distributions. As an example, soft magnetic microwires are considered. A very attractive method of field generation is utilising tuneable domain configurations. In this review, we discuss the force requirements and constraints for different areas of application, emphasising the current challenges and how to overcome them.

Boosting Magnetoelectric Effect in Polymer-Based Nanocomposites.

Polymer-based magnetoelectric composite materials have attracted a lot of attention due to their high potential in various types of applications as magnetic field sensors, energy harvesting, and biomedical devices. Current researches are focused on the increase in the efficiency of magnetoelectric transformation. In this work, a new strategy of arrangement of clusters of magnetic nanoparticles by an external magnetic field in PVDF and PFVD-TrFE matrixes is proposed to increase the voltage coefficient (αME) of the magnetoelectric effect. Another strategy is the use of 3-component composites through the inclusion of piezoelectric BaTiO3 particles. Developed strategies allow us to increase the αME value from ~5 mV/cm·Oe for the composite of randomly distributed CoFe2O4 nanoparticles in PVDF matrix to ~18.5 mV/cm·Oe for a composite of magnetic particles in PVDF-TrFE matrix with 5%wt of piezoelectric particles. The applicability of such materials as bioactive surface is demonstrated on neural crest stem cell cultures.

Multiferroic Coupling of Ferromagnetic and Ferroelectric Particles through Elastic Polymers.

Multiferroics are materials that electrically polarize when subjected to a magnetic field and magnetize under the action of an electric field. In composites, the multiferroic effect is achieved by mixing of ferromagnetic (FM) and ferroelectric (FE) particles. The FM particles are prone to magnetostriction (field-induced deformation), whereas the FE particles display piezoelectricity (electrically polarize under mechanical stress). In solid composites, where the FM and FE grains are in tight contact, the combination of these effects directly leads to multiferroic behavior. In the present work, we considered the FM/FE composites with soft polymer bases, where the particles of alternative kinds are remote from one another. In these systems, the multiferroic coupling is different and more complicated in comparison with the solid ones as it is essentially mediated by an electromagnetically neutral matrix. When either of the fields, magnetic or electric, acts on the 'akin' particles (FM or FE) it causes their displacement and by that perturbs the particle elastic environments. The induced mechanical stresses spread over the matrix and inevitably affect the particles of an alternative kind. Therefore, magnetization causes an electric response (due to the piezoeffect in FE) whereas electric polarization might entail a magnetic response (due to the magnetostriction effect in FM). A numerical model accounting for the multiferroic behavior of a polymer composite of the above-described type is proposed and confirmed experimentally on a polymer-based dispersion of iron and lead zirconate micron-size particles.

Green Synthesis of Co-Zn Spinel Ferrite Nanoparticles: Magnetic and Intrinsic Antimicrobial Properties.

Spinel ferrite magnetic nanoparticles have attracted considerable attention because of their high and flexible magnetic properties and biocompatibility. In this work, a set of magnetic nanoparticles of cobalt ferrite doped with zinc was synthesized via the eco-friendly sol-gel auto-combustion method. Obtained particles displayed a room-temperature ferromagnetic behavior with tuned by chemical composition values of saturation magnetization and coercivity. The maximal values of saturation magnetization ~74 Am2/kg were found in cobalt ferrite nanoparticles with a 15-35% molar fraction of cobalt replaced by zinc ions. At the same time, the coercivity exhibited a gradually diminishing trend from ~140 to ~5 mT whereas the concentration of zinc was increased from 0 to 100%. Consequently, nanoparticles produced by the proposed method possess highly adjustable magnetic properties to satisfy the requirement of a wide range of possible applications. Further prepared nanoparticles were tested with bacterial culture to display the influence of chemical composition and magnetic structure on nanoparticles-bacterial cell interaction.

Multifunctional Fe3O4-Au Nanoparticles for the MRI Diagnosis and Potential Treatment of Liver Cancer.

Heterodimeric nanoparticles comprising materials with different functionalities are of great interest for fundamental research and biomedical/industrial applications. In this work, Fe3O4-Au nano-heterostructures were synthesized by a one-step thermal decomposition method. The hybrid nanoparticles comprise a highly crystalline 12 nm magnetite octahedron decorated with a single noble metal sphere of 6 nm diameter. Detailed analysis of the nanoparticles was performed by UV-visible spectroscopy, magnetometry, calorimetry and relaxometry studies. The cytotoxic effect of the nanoparticles in the human hepatic cell line Huh7 and PLC/PRF/5-Alexander was also assessed. These Fe3O4-Au bifunctional nanoparticles showed no significant cytotoxicity in these two cell lines. The nanoparticles showed a good theranostic potential for liver cancer treatment, since the r2 relaxivity (166.5 mM-1·s-1 and 99.5 mM-1·s-1 in water and HepG2 cells, respectively) is higher than the corresponding values for commercial T2 contrast agents and the Specific Absorption Rate (SAR) value obtained (227 W/gFe) is enough to make them suitable as heat mediators for Magnetic Fluid Hyperthermia. The gold counterpart can further allow the conjugation with different biomolecules and the optical sensing.

Magnetocrystalline and Surface Anisotropy in CoFe2O4 Nanoparticles.

The effect of the annealing temperature Tann on the magnetic properties of cobalt ferrite nanoparticles embedded in an amorphous silica matrix (CoFe2O4/SiO2), synthesized by a sol-gel auto-combustion method, was investigated by magnetization and AC susceptibility measurements. For samples with 15% w/w nanoparticle concentration, the particle size increases from ~2.5 to ~7 nm, increasing Tann from 700 to 900 °C. The effective magnetic anisotropy constant (Keff) increases with decreasing Tann, due to the increase in the surface contribution. For a 5% w/w sample annealed at 900 °C, Keff is much larger (1.7 × 106 J/m3) than that of the 15% w/w sample (7.5 ×105 J/m3) annealed at 700 °C and showing comparable particle size. This indicates that the effect of the annealing temperature on the anisotropy is not only the control of the particle size but also on the core structure (i.e., cation distribution between the two spinel sublattices and degree of spin canting), strongly affecting the magnetocrystalline anisotropy. The results provide evidence that the magnetic anisotropy comes from a complex balance between core and surface contributions that can be controlled by thermal treatments.

Progressive lysosomal membrane permeabilization induced by iron oxide nanoparticles drives hepatic cell autophagy and apoptosis.

Iron oxide nanoparticles (IONs) are frequently used in various biomedical applications, in particular as magnetic resonance imaging contrast agents in liver imaging. Indeed, number of IONs have been withdrawn due to their poor clinical performance. Yet comprehensive understanding of their interactions with hepatocytes remains relatively limited. Here we investigated how iron oxide nanocubes (IO-cubes) and clusters of nanocubes (IO-clusters) affect distinct human hepatic cell lines. The viability of HepG2, Huh7 and Alexander cells was concentration-dependently decreased after exposure to either IO-cubes or IO-clusters. We found similar cytotoxicity levels in three cell lines triggered by both nanoparticle formulations. Our data indicate that different expression levels of Bcl-2 predispose cell death signaling mediated by nanoparticles. Both nanoparticles induced rather apoptosis than autophagy in HepG2. Contrary, IO-cubes and IO-clusters trigger distinct cell death signaling events in Alexander and Huh7 cells. Our data clarifies the mechanism by which cubic nanoparticles induce autophagic flux and the mechanism of subsequent toxicity. These findings imply that the cytotoxicity of ION-based contrast agents should be carefully considered, particularly in patients with liver diseases.

Ultrasensitive Magnetic Field Sensors for Biomedical Applications.

The development of magnetic field sensors for biomedical applications primarily focuses on equivalent magnetic noise reduction or overall design improvement in order to make them smaller and cheaper while keeping the required values of a limit of detection. One of the cutting-edge topics today is the use of magnetic field sensors for applications such as magnetocardiography, magnetotomography, magnetomyography, magnetoneurography, or their application in point-of-care devices. This introductory review focuses on modern magnetic field sensors suitable for biomedicine applications from a physical point of view and provides an overview of recent studies in this field. Types of magnetic field sensors include direct current superconducting quantum interference devices, search coil, fluxgate, magnetoelectric, giant magneto-impedance, anisotropic/giant/tunneling magnetoresistance, optically pumped, cavity optomechanical, Hall effect, magnetoelastic, spin wave interferometry, and those based on the behavior of nitrogen-vacancy centers in the atomic lattice of diamond.

Magnetic-Assisted Treatment of Liver Fibrosis.

Chronic liver injury can be induced by viruses, toxins, cellular activation, and metabolic dysregulation and can lead to liver fibrosis. Hepatic fibrosis still remains a major burden on the global health systems. Nonalcoholic fatty liver disease (NAFLD) and nonalcoholic steatohepatitis (NASH) are considered the main cause of liver fibrosis. Hepatic stellate cells are key targets in antifibrotic treatment, but selective engagement of these cells is an unresolved issue. Current strategies for antifibrotic drugs, which are at the critical stage 3 clinical trials, target metabolic regulation, immune cell activation, and cell death. Here, we report on the critical factors for liver fibrosis, and on prospective novel drugs, which might soon enter the market. Apart from the current clinical trials, novel perspectives for anti-fibrotic treatment may arise from magnetic particles and controlled magnetic forces in various different fields. Magnetic-assisted techniques can, for instance, enable cell engineering and cell therapy to fight cancer, might enable to control the shape or orientation of single cells or tissues mechanically. Furthermore, magnetic forces may improve localized drug delivery mediated by magnetism-induced conformational changes, and they may also enhance non-invasive imaging applications.

Magnetic and Optical Properties of Gold-Coated Iron Oxide Nanoparticles.

In this work, magnetic and optical properties of magnetic nanoparticles were investigated, where the particles of iron oxide were prepared with a co-precipitation route and the component of gold was built up by reduction of AuCl4- on the surface of iron oxide to assemble nanocomposite structures in the form of an electrostatic stabilized suspension. The size of the particles obtained with TEM increased from of 8.9 ± 2.7 to 16 ± 6 nm after the procedure of hybridisation. In order to distinguish the impact of the gold on the optical properties, UV-Vis and Raman spectroscopy techniques were used. Magnetic properties were studied in the temperature range of 5-300 K and the superparamagnetic state of MNPs at room temperature was confirmed for both systems.