Magnetic Nanoparticles: Synthesis, Anisotropy, and Applications.

Anisotropy is an important and widely present characteristic of materials that provides desired direction-dependent properties. In particular, the introduction of anisotropy into magnetic nanoparticles (MNPs) has become an effective method to obtain new characteristics and functions that are critical for many applications. In this review, we first discuss anisotropy-dependent ferromagnetic properties, ranging from intrinsic magnetocrystalline anisotropy to extrinsic shape and surface anisotropy, and their effects on the magnetic properties. We further summarize the syntheses of monodisperse MNPs with the desired control over the NP dimensions, shapes, compositions, and structures. These controlled syntheses of MNPs allow their magnetism to be finely tuned for many applications. We discuss the potential applications of these MNPs in biomedicine, magnetic recording, magnetotransport, permanent magnets, and catalysis.

Shape Anisotropy-Governed High-Performance Nanomagnetosol for In Vivo Magnetic Particle Imaging of Lungs.

Caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), coronavirus disease 2019 (COVID-19) has shown extensive lung manifestations in vulnerable individuals, putting lung imaging and monitoring at the forefront of early detection and treatment. Magnetic particle imaging (MPI) is an imaging modality, which can bring excellent contrast, sensitivity, and signal-to-noise ratios to lung imaging for the development of new theranostic approaches for respiratory diseases. Advances in MPI tracers would offer additional improvements and increase the potential for clinical translation of MPI. Here, a high-performance nanotracer based on shape anisotropy of magnetic nanoparticles is developed and its use in MPI imaging of the lung is demonstrated. Shape anisotropy proves to be a critical parameter for increasing signal intensity and resolution and exceeding those properties of conventional spherical nanoparticles. The 0D nanoparticles exhibit a 2-fold increase, while the 1D nanorods have a > 5-fold increase in signal intensity when compared to VivoTrax. Newly designed 1D nanorods displayed high signal intensities and excellent resolution in lung images. A spatiotemporal lung imaging study in mice revealed that this tracer offers new opportunities for monitoring disease and guiding intervention.

Metal-Organic Framework as a New Type of Magnetothermally-Triggered On-Demand Release Carrier.

The development of external stimuli-controlled payload systems has been sought after with increasing interest toward magnetothermally-triggered drug release (MTDR) carriers due to their non-invasive features. However, current MTDR carriers present several limitations, such as poor heating efficiency caused by the aggregation of iron oxide nanoparticles (IONPs) or the presence of antiferromagnetic phases which affect their efficiency. Herein, a novel MTDR carrier is developed using a controlled encapsulation method that fully fixes and confines IONPs of various sizes within the metal-organic frameworks (MOFs). This novel carrier preserves the MOF's morphology, porosity, and IONP segregation, while enhances heating efficiency through the oxidation of antiferromagnetic phases in IONPs during encapsulation. It also features a magnetothermally-responsive nanobrush that is stimulated by an alternating magnetic field to enable on-demand drug release. The novel carrier shows improved heating, which has potential applications as contrast agents and for combined chemo and magnetic hyperthermia therapy. It holds a great promise for magneto-thermally modulated drug dosing at tumor sites, making it an exciting avenue for cancer treatment.

Enhancing the magnetic and inductive heating properties of Fe3O4 nanoparticles via morphology control.

Fe3O4 nanoparticles (NPs) with different shapes have been prepared by a 'solventless' synthesis approach to probe shape anisotropy effects on the magnetic and inductive heating properties. Various shapes including spheres, octahedrons, cubes, rods, wires, and multipods are obtained through alterations in reaction conditions such as the ratio of precursor to surfactant content and heating rate. Magnetic and Mössbauer measurements reveal better stoichiometry in anisotropic-shaped Fe3O4 NPs than that in the spherical and multipod NPs. As a result, the magnetization value of the anisotropic-shaped NPs approaches the value for bulk material (∼86 emu g-1). More surprisingly, the Verwey transition, which is a characteristic phase transition of bulk magnetite structure, is observed near 120 K in the anisotropic-shaped NPs, which further corroborates the fact that these NPs possess better stoichiometry compared to the spherical and multipod-shaped NPs. Other than the improved magnetic properties, these anisotropic-shaped NPs are more effective for hyperthermia applications. For example, compared to the conventional spherical NPs, the nanowires show much higher SAR value up to 846 W g-1, making them a potential candidate for practical hyperthermia treatment. In particular, the octahedral NPs shows an SAR value higher than the same size spherical NPs, which demonstrates the importance of occurrence of the Verwey transition in Fe3O4 NPs for better stoichiometric and higher heating.

Self-Assembly of CoPt Magnetic Nanoparticle Arrays and its Underlying Forces.

Nanoparticles covered with surfactants are often used to study particle motion patterns and self-assembly processes in solutions. Surfactants have influence on the interparticle interactions and therefore on the particle motion tracks and final patterns. In this study, CoPt nanoparticles are synthesized in aqueous solution without any surfactant. In situ transmission electron microscopy observation is performed to monitor the self-assemble process. Two types of magnetic nanoparticle superlattice arrays are formed: hexagonal equal distance superlattice arrays when particle size is 3 nm, and tight unequal distance superlattice arrays when particle size is 4.5 nm. It is interesting to observe that two small arrays merge into a large one through rotational and translational movements. A Monte Carlo simulation is carried out which successfully restores the whole process. It is identified that the underlying forces are van der Waals and magnetic dipolar interactions. The latter is responsible for orientation of each particle during the whole process. This investigation leads to a better understanding of the formation mechanism of magnetic nanoparticle superlattice arrays.

Size-dependent magnetic and inductive heating properties of Fe3O4 nanoparticles: scaling laws across the superparamagnetic size.

An efficient heat activating mediator with an enhanced specific absorption rate (SAR) value is attained via control of the iron oxide (Fe3O4) nanoparticle size from 3 to 32 nm. Monodispersed Fe3O4 nanoparticles are synthesized via a seed-less thermolysis technique using oleylamine and oleic acid as the multifunctionalizing agents (surfactant, solvent and reducing agent). The inductive heating properties as a function of particle size reveal a strong increase in the SAR values with increasing particle size up to 28 nm. In particular, the SAR values of ferromagnetic nanoparticles (>16 nm) are strongly enhanced with the increase of ac magnetic field amplitude than that for the superparamagnetic (3-16 nm) nanoparticles. The enhanced SAR values in the ferromagnetic regime are attributed to the synergistic contribution from the hysteresis and susceptibility loss. Specifically, the 28 nm Fe3O4 nanoparticles exhibit an enhanced SAR value of 801 W g-1 which is nearly an order higher than that of the commercially available nanoparticles.

Synthesis and characterization of FeCo nanowires with high coercivity.

Ferromagnetic FeCo nanocrystals with high coercivity have been synthesized using a reductive decomposition method. The sizes and shapes of the nanocrystals were found to be dependent on reaction parameters such as the surfactant ratio, the precursor concentration and the heating rate. Synthesized nanocrystals have a body-centered cubic crystal structure for both particles and nanowires and the (110) crystalline direction is along the long axis of the nanowires. The coercivity and magnetization of the FeCo nanocrystals are found to be dependent on morphology. Nanowires of Fe60Co40 with saturation magnetization of 92 emu g(-1) and coercive force of 1.2 kOe have been obtained in this study.

Synthesis of monodisperse FeCo nanoparticles by reductive salt-matrix annealing.

We report here a novel synthetic method to prepare monodisperse air-stable FeCo nanoparticles with average sizes of 8, 12 and 20 nm. CoFe2O4 nanoparticles of different sizes were first synthesized by a chemical solution method. The as-synthesized CoFe2O4 nanoparticles were then mixed with ball-milled NaCl powders and heated to 400-500 ° C in forming gas (Ar 93%+H2 7%). The salt powder worked as a separating medium that prevents the CoFe2O4 nanoparticles from agglomerating during the heat treatment while the forming gas reduces the CoFe2O4 nanoparticles to FeCo nanoparticles. Monodisperse FeCo nanoparticles were recovered by dissolving the NaCl in water and subsequently washing with ethanol and acetone. Structural analyses confirmed that FeCo nanoparticles retained the same size as their oxide precursors. The size of the FeCo nanoparticles can be well tuned by controlling the size of the CoFe2O4 nanoparticles. The saturation magnetization of FeCo nanoparticles is size dependent and increases with size.

Magnetic-field-induced self-assembly of FeCo/CoFe2O4 core/shell nanoparticles with tunable collective magnetic properties.

Self-assembly of nanoparticles into ordered patterns is a novel approach to build up new consolidated materials with desired collective physical properties. Herein, nanoparticle assemblies of composition-modulated bimagnetic nanoparticles have been produced via slow evaporation of their colloidal suspension in the absence or presence of magnetic fields. The assemblies obtained in the presence of the magnetic fields exhibit oriented nanoparticle chains in face-centered cubic superlattice structures, compared with the hexagonal closed-packed superlattice obtained without the magnetic field. The oriented structure has an alignment of the easy magnetization axis along the chains. This alignment leads to enhanced intra-superlattice interactions. As a result, the field-induced assembly displays collective magnetic properties with significantly enhanced magnetic anisotropy, remanent magnetization and coercivity. It is also found that the bimagnetic FeCo/CoFe2O4 core/shell nanostructure enhances the intra-particle interaction and thus is beneficial for the growth of oriented assembly of nanoparticles. Furthermore, the collective magnetic behavior is evidenced by the observation of a superferromagnetic-like magnetization relaxation in the ac-susceptibility curves.

Magnetic properties of Fe(x)Pt(y)Au(100-x-y) nanoparticles.

Fe(x)Pt(y)Au(100-x-y) nanoparticles of size 3.5 nm were prepared by polyol reduction of platinum acetylacetonate and gold acetate and the thermal decomposition of iron pentacarbonyl. The as-synthesized nanoparticles with disordered fcc structure were then heat treated to transform to the L1(0) structure with high magnetocrystalline anisotropy. By tuning the stoichiometry of the Fe(x)Pt(y)Au(100-x-y) nanoparticles, the phase transition temperature was reduced by more than 200 degrees C. After the annealing 500 degrees C, for instance, the highest coercivity of 18 kOe was obtained from the Fe51Pt36Au13 nanoparticles which is substantially higher compared to 2 kOe for Fe51Pt49 nanoparticles annealed at the same temperature. In addition to the high coercivity, the saturation magnetization value obtained from Fe51Pt36Au13 nanoparticles was 47 emu/g which is similar to that for the Fe51Pt49 nanoparticles, indicating that there is no trade-off between the coercivity and the saturation magnetization upon Au doping.

Combination of Disulfiram and Copper-Cysteamine Nanoparticles for an Enhanced Antitumor Effect on Esophageal Cancer.

Esophageal cancer (EC) is the sixth leading cause of cancer deaths worldwide with a low 5-year survival rate. More effective chemotherapeutic drugs, either new or repurposing ones, are urgently needed. Disulfiram (DSF) is a safe and public domain drug for alcohol addiction treatment and later shown to have anti-cancer capability, especially when administrated together with copper. The present study is to test the hypothesis that a newly developed copper-cysteamine (Cu-Cy) nanoparticles (NPs) can enhance the anti-tumor effect of DSF on esophageal cancer with reduced risk of copper poisoning. Our results showed that Cu-Cy NPs could greatly facilitate DSF to inhibit cell proliferation in cultured human esophageal cancer cells. Interestingly, the combined inhibitory function could be further enhanced when DSF and Cu-Cy NPs were present at an optimal molar ratio of 1:4. The results of the change in physical color, UV-vis absorption and fluorescence spectra, X-ray diffraction patterns, and FTIR spectra from a mixture of DSF and Cu-Cy NPs suggest a possible reaction between DSF and Cu-Cy NPs and the formation of new materials. Furthermore, cellular mechanistic studies revealed that the combination of DSF and Cu-Cy NPs resulted in reactive oxygen species (ROS) accumulation, and blocked nuclear translocation of NF-ƙB (p65) in esophageal cancer cells. Moreover, in xenograft nude mice, combined administration of DSF and Cu-Cy NPs greatly inhibited tumor growth without noticeable histological toxicity, while any single agent at the same doses presented no inhibitory function. Together, this study demonstrates an effective anti-cancer function of combined treatment of DSF and Cu-Cy NPs in vitro and in vivo, which could be a promising new chemotherapy for esophageal cancer patients.

Copper-Cysteamine Nanoparticles as a Heterogeneous Fenton-Like Catalyst for Highly Selective Cancer Treatment.

Herein, for the first time, we report copper-cysteamine (Cu-Cy) nanoparticles having Cu1+ instead of Cu2+ as an efficient heterogeneous Fenton-like catalyst for highly selective cancer treatment. Initial measurements of Cu-Cy's hydroxyl radical generation ability show that it behaves as a Fenton-like reagent in the presence of H2O2 (100 µM) at pH 7.4, and that its Fenton-like activity is dramatically enhanced under acidic conditions (pH 6.5 and 5.5). Notably, Cu-Cy exhibits high stability and minimal copper release during the Fenton-like reaction, demonstrating its potency as a heterogeneous Fenton-like catalyst with a low cytotoxic effect. Through extensive in vitro studies, Cu-Cy NPs are found to generate a significantly higher level of ROS, thereby causing significantly more destruction to cancerous cells than to normal cells without the need for exogenous additives, such as H2O2. To the best of our knowledge, the average IC-50 value of Cu-Cy to cancer cells (11 µg/mL) is the lowest among reported heterogeneous Fenton-like nanocatalyst so far. Additionally, compared to cancer cells, Cu-Cy NPs display substantially higher IC-50 value toward normal cells (50 µg/mL), suggesting high selectivity. Overall, Cu-Cy NPs can participate in heterogeneous Fenton-like activity with elevated H2O2 under acidic conditions to produce significantly higher levels of hydroxyl radicals in cancer cells when compared to normal cells, resulting in selective cytotoxicity to cancer cells.

Inductive Thermal Effect of Ferrite Magnetic Nanoparticles.

Localized heat induction using magnetic nanoparticles under an alternating magnetic field is an emerging technology applied in areas including, cancer treatment, thermally activated drug release and remote activation of cell functions. To enhance the induction heating efficiency of magnetic nanoparticles, the intrinsic and extrinsic magnetic parameters influencing the heating efficiency of magnetic nanoparticles should be effectively engineered. This review covers the recent progress in the optimization of magnetic properties of spinel ferrite nanoparticles for efficient heat induction. The key materials factors for efficient magnetic heating including size, shape, composition, inter/intra particle interactions are systematically discussed, from the growth mechanism, process control to chemical and magnetic properties manipulation.

Strong texture in nanograin bulk Nd-Fe-B magnets via slow plastic deformation at low temperatures.

Nanograin magnets are potential candidates for ultrastrong magnets with high coercivity and high energy product. However, existing nanograin bulk magnets exhibit modest energy products because desired structures with nanoscale grain size and strong orientation (texture) are often difficult to obtain. This study describes a synchrony of the nanoscale grain size and strong texture in bulk Nd-Fe-B magnets by plastic deformation with slow strain rates at temperatures well below the melting point of the Nd-rich phase. High grain orientation (>90%) has been achieved for nanoscale grain sizes of 80-110 nm, giving the nanograin bulk magnets record high energy products (≥45 MGOe). Loosely-packed thick grain boundaries and creep-like stress-strain curves have been observed. Grain boundary mediated creep-like deformation is proposed as the mechanism for the high-degree nanoscale grain alignment under the deformation conditions without liquid phase. The effect of the strain rate on the texture and magnetic properties has been investigated systematically.

A facile method for the synthesis of copper-cysteamine nanoparticles and study of ROS production for cancer treatment.

Copper-cysteamine (Cu-Cy) is a novel sensitizer that can be excited by ultraviolet (UV) light, microwave (MW), ultrasound, and X-rays to generate highly toxic reactive oxygen species (ROS) for cancer cell destruction. The purpose of this study is to present a facile method for the synthesis of Cu-Cy nanoparticles. Interestingly, we were able to decrease both the stirring and heating time by about 24 and 6 times, respectively, thus making Cu-Cy nanoparticles more economical than what was reported before. 1,4-Diazabicylo[2.2.2]octane (DABCO), a well-known singlet oxygen quencher, showed that the majority of ROS produced by Cu-Cy nanoparticles upon UV and MW exposure were singlet oxygen. Moreover, ROS generated by Cu-Cy nanoparticles upon UV and MW exposure were confirmed by a known ROS tracking agent, dihydrorhodamine 123, further serving as an additional piece of evidence that Cu-Cy is a promising ROS generating agent to destroy cancer cells as well as bacteria or viruses by a radical therapeutic approach. Additionally, for the first time, the hydroxyl radical (˙OH) produced by Cu-Cy nanoparticles upon MW activation was proved by a photoluminescence (PL) technique using coumarin as a probe molecule. Remarkably, newly synthesized nanoparticles were found to be much more effective for producing ROS and killing cancer cells, suggesting that the new method may have increased the reactivity of the Cu-Cy nanoparticles due to an overall size reduction. Overall, the new method not only reduced the synthesis time but also enhanced the effectiveness of Cu-Cy nanoparticles for photodynamic therapy.

Zinc ferrite nanoparticles as MRI contrast agents.

Mixed spinel hydrophobic ZnxFe1-xO x Fe2O3 (up to x = 0.34) nanoparticles encapsulated in polymeric micelles exhibited increased T2 relaxivity and sensitivity of detection over clinically used Feridex.

Dependence of exchange coupling on interfacial conditions in SmCo5/Co system: a first-principles study.

We have performed first-principles calculations to study the interfacial exchange coupling in a SmCo5/Co multilayer model system. The hard phase hcp SmCo5 and the soft phase hcp Co (or Co(1-x)Fe(x)) stacking along (1010) direction are structurally well matched. The atomic structure, including the alignment and the separation between layers, were optimized first. Then the non-collinear magnetic structures were calculated to explore the exchange coupling dependence on the variation of the atomic composition across the interface. We found that the inter-phase exchange coupling strength is strongly dependent on the interface condition between the hard and soft phase by comparing the exchange coupling strengths in different interface conditions. The findings were further confirmed by the calculated site-to-site exchange parameters across the interface.

Author Correction: Large T1 contrast enhancement using superparamagnetic nanoparticles in ultra-low field MRI.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.

Magnetic hardening of Nd-Ce-Fe-B films with high Ce concentration.

Partial substitution of Ce in Nd-Fe-B magnets is a feasible way to cope with the crisis of Nd and Dy in Nd-Fe-B production and reduce the cost of Nd-Fe-B magnets. In the present paper, the Nd-Ce-Fe-B films with high performance have been successfully fabricated by using an ultra-high vacuum (UHV) magnetron sputtering system. High magnetic performance with a ceorcivity of 13.3 kOe, a remanence of 11.4 kGs and a maximum energy product of 29.4 GMOe is obtained with the Ce substitution for more than 50 wt.% Nd without Dy addition. The high coercivity and (BH)max achieved in this work are much larger than those of previously reported Nd-Ce-Fe-B magnets with the same Ce concentration. The phase structure, microstructure and coercivity mechanism are analyzed. The coercivity mechanism is determined to be mainly dominated by nucleation. Based on the microstructure observation and coercivity mechanism analysis, the fine and well separated grains, smooth grain surface, small and less inhomogeneities should be responsible for the high coercivity. Our results encourage the further improvement of magnetic properties in Ce magnets including the bulk material with high Ce concentration.

Large T1 contrast enhancement using superparamagnetic nanoparticles in ultra-low field MRI.

Superparamagnetic iron oxide nanoparticles (SPIONs) are widely investigated and utilized as magnetic resonance imaging (MRI) contrast and therapy agents due to their large magnetic moments. Local field inhomogeneities caused by these high magnetic moments are used to generate T2 contrast in clinical high-field MRI, resulting in signal loss (darker contrast). Here we present strong T1 contrast enhancement (brighter contrast) from SPIONs (diameters from 11 nm to 22 nm) as observed in the ultra-low field (ULF) MRI at 0.13 mT. We have achieved a high longitudinal relaxivity for 18 nm SPION solutions, r1 = 615 s-1 mM-1, which is two orders of magnitude larger than typical commercial Gd-based T1 contrast agents operating at high fields (1.5 T and 3 T). The significantly enhanced r1 value at ultra-low fields is attributed to the coupling of proton spins with SPION magnetic fluctuations (Brownian and Néel) associated with a low frequency peak in the imaginary part of AC susceptibility (χ"). SPION-based T1-weighted ULF MRI has the advantages of enhanced signal, shorter imaging times, and iron-oxide-based nontoxic biocompatible agents. This approach shows promise to become a functional imaging technique, similar to PET, where low spatial resolution is compensated for by important functional information.