Uniform Magnetic Nanoparticles Research Articles

Size dependence of the surface spin disorder and surface anisotropy constant in ferrite nanoparticles.

The magnetic properties of nanoscale magnets are greatly influenced by surface anisotropy. So far, its quantification is based on the examination of the blocking temperature shift within a series of nanoparticles of varying sizes. In this scenario, the surface anisotropy is assumed to be a particle size-independent quantity. However, there is no solid experimental proof to support this simplified picture. On the contrary, our work unravels the size-dependent magnetic morphology and surface anisotropy in highly uniform magnetic nanoparticles using small-angle polarized neutron scattering. We observed that the surface anisotropy constant does not depend on the nanoparticle's size in the range of 3-9 nm. Furthermore, our results demonstrate that the surface spins are less prone to polarization with increasing nanoparticle size. Our study thus proves the size dependence of the surface spin disorder and the surface anisotropy constant in fine nanomagnets. These findings open new routes in materials based on a controlled surface spin disorder, which is essential for future applications of nanomagnets in biomedicine and magnonics.

Self-Limitations of Heat Release in Coupled Core-Shell Spinel Ferrite Nanoparticles: Frequency, Time, and Temperature Dependencies.

We explored a series of highly uniform magnetic nanoparticles (MNPs) with a core-shell nanoarchitecture prepared by an efficient solvothermal approach. In our study, we focused on the water dispersion of MNPs based on two different CoFe2O4 core sizes and the chemical nature of the shell (MnFe2O4 and spinel iron oxide). We performed an uncommon systematic investigation of the time and temperature evolution of the adiabatic heat release at different frequencies of the alternating magnetic field (AMF). Our systematic study elucidates the nontrivial variations in the heating efficiency of core-shell MNPs concerning their structural, magnetic, and morphological properties. In addition, we identified anomalies in the temperature and frequency dependencies of the specific power absorption (SPA). We conclude that after the initial heating phase, the heat release is governed by the competition of the Brown and Néel mechanism. In addition, we demonstrated that a rational parameter sufficiently mirroring the heating ability is the mean magnetic moment per MNP. Our study, thus, paves the road to fine control of the AMF-induced heating by MNPs with fine-tuned structural, chemical, and magnetic parameters. Importantly, we claim that the nontrivial variations of the SPA with the temperature must be considered, e.g., in the emerging concept of MF-assisted catalysis, where the temperature profile influences the undergoing chemical reactions.

(Super)paramagnetic nanoparticles as platform materials for environmental applications: From synthesis to demonstration

Over the past few decades, engineered, (super)paramagnetic nanoparticles have drawn extensive research attention for a broad range of applications based on their tunable size and shape, surface chemistries, and magnetic properties. This review summaries our recent work on the synthesis, surface modification, and environmental application of (super)paramagnetic nanoparticles. By utilizing hightemperature thermo-decomposition methods, first, we have broadly demonstrated the synthesis of highly monodispersed, (super)paramagnetic nanoparticles, via the pyrolysis of metal carboxylate salts in an organic phase. Highly uniform magnetic nanoparticles with various size, composition, and shape can be precisely tuned by controlled reaction parameters, such as the initial precursors, heating rate, final reaction temperature, reaction time, and the additives. These materials can be further rendered water stable via functionalization with surface mono/bi-layer coating structure using a series of tunable ionic/non-ionic surfactants. Finally, we have demonstrated platform potential of these materials for heavy metal ions sensing, sorption, and separation from the aqueous phase.

Coexistence of Van Hove singularities and pseudomagnetic fields in modulated graphene bilayer

The stacking and bending of graphene are trivial but extremely powerful agents of control over graphene’s manifold physics. By changing the twist angle, one can drive the system over a plethora of exotic states via strong electron correlation, thanks to the moiré superlattice potentials, while the periodic or triaxial strains induce discretization of the band structure into Landau levels without the need for an external magnetic field. We fabricated a hybrid system comprising both the stacking and bending tuning knobs. We have grown the graphene monolayers by chemical vapor deposition, using 12C and 13C precursors, which enabled us to individually address the layers through Raman spectroscopy mapping. We achieved the long-range spatial modulation by sculpturing the top layer (13C) over uniform magnetic nanoparticles (NPs) deposited on the bottom layer (12C). An atomic force microscopy study revealed that the top layer tends to relax into pyramidal corrugations with C3 axial symmetry at the position of the NPs, which have been widely reported as a source of large pseudomagnetic fields (PMFs) in graphene monolayers. The modulated graphene bilayer (MGBL) also contains a few micrometer large domains, with the twist angle ∼10°, which were identified via extreme enhancement of the Raman intensity of the G-mode due to formation of van Hove singularities (VHSs). We thereby conclude that the twist-induced VHSs coexist with the PMFs generated in the strained pyramidal objects without mutual disturbance. The graphene bilayer modulated with magnetic NPs is a non-trivial hybrid system that accommodates features of twist-induced VHSs and PMFs in environs of giant classical spins.

Effect of the Surface Charge on the Adsorption Capacity of Chromium(VI) of Iron Oxide Magnetic Nanoparticles Prepared by Microwave-Assisted Synthesis

Solid phase extraction using magnetic nanoparticles has represented a leap forward in terms of the improvement of water quality, preventing the contamination of industrial effluents from discharge in a more efficient and affordable way. In the present work, superparamagnetic iron oxide nanoparticles (MNP) with different surface charges are tested as nanosorbents for the removal of chromium(VI) in aqueous solution. Uniform magnetic nanoparticles (~12 nm) were synthesized by a microwave polyol-mediated method, and tetraethyl orthosilicate (TEOS) and (3-aminopropyl) triethoxysilane (APTES) were grafted onto their surface, providing a variation in the surface charge. The adsorptive process of chromium was evaluated as a function of the pH, the initial concentration of chromium and contact time. Kinetic studies were best described by a pseudo-second order model in all cases. TEOS@MNP barely removed the chromium from the media, while non-grafted particles and APTES@TEOS@MNP followed the Langmuir model, with maximum adsorption capacities of 15 and 35 mgCr/g, respectively. The chromium adsorption capacities abruptly increased when the surface became positively charged as the species coexisting at the experimental pH are negatively charged. Furthermore, these particles have proven to be highly efficient in water remediation due their 100% reusability after more than six consecutive adsorption/desorption cycles.

Preparation and Characterisation of Highly Stable Iron Oxide Nanoparticles for Magnetic Resonance Imaging

Magnetic nanoparticles produced using aqueous coprecipitation usually exhibit wide particle size distribution. Synthesis of small and uniform magnetic nanoparticles has been the subject of extensive research over recent years. Sufficiently small superparamagnetic iron oxide nanoparticles easily permeate tissues and may enhance the contrast in magnetic resonance imaging. Furthermore, their unique small size also allows them to migrate into cells and other body compartments. To better control their synthesis, a chemical coprecipitation protocol was carefully optimised regarding the influence of the injection rate of base and incubation times. The citrate-stabilised particles were produced with a narrow average size range below 2 nm and excellent stability. The stability of nanoparticles was monitored by long-term measurement of zeta potentials and relaxivity. Biocompatibility was tested on the Caki-2 cells with good tolerance. The application of nanoparticles for magnetic resonance imaging (MRI) was then evaluated. The relaxivities (r1,r2) and r2/r1 ratio calculated from MR images of prepared phantoms indicate the nanoparticles as a promising T2-contrast probe.

Facile microwave synthesis of uniform magnetic nanoparticles with minimal sample processing

We present a simple and rapid method for the synthesis of small magnetic nanoparticles (diameters in the order of 5–20nm) and narrow size distributions (CV's of 20–40%). The magnetite nanoparticles were synthesized in green solvents within minutes and the saturation magnetization of the particles was tunable by changes in the reaction conditions. We show that this particle synthesis method requires minimal processing steps and we present the successful coating of the particles with reactive bisphosphonates after synthesis without washing or centrifugation. We found minimal batch-to-batch variability and show the scalability of the particle synthesis method. We present a full characterization of the particle properties and believe that this synthesis method holds great promise for facile and rapid generation of magnetic nanoparticles with defined surface coatings for magnetic targeting applications.

A novel design strategy for nanoparticles on nanopatterns: interferometric lithographic patterning of Mms6 biotemplated magnetic nanoparticles.

Nanotechnology demands the synthesis of highly precise, functional materials, tailored for specific applications. One such example is bit patterned media. These high-density magnetic data-storage materials require specific and uniform magnetic nanoparticles (MNPs) to be patterned over large areas (cm2 range) in exact nanoscale arrays. However, the realisation of such materials for nanotechnology applications depends upon reproducible fabrication methods that are both precise and environmentally-friendly, for cost-effective scale-up. A potentially ideal biological fabrication methodology is biomineralisation. This is the formation of inorganic minerals within organisms, and is known to be highly controlled down to the nanoscale whilst being carried out under ambient conditions. The magnetotactic bacterium Magnetospirillum magneticum AMB-1 uses a suite of dedicated biomineralisation proteins to control the formation of magnetite MNPs within their cell. One of these proteins, Mms6, has been shown to control formation of magnetite MNPs in vitro. We have previously used Mms6 on micro-contact printed (μCP) patterned self-assembled monolayer (SAM) surfaces to control the formation and location of MNPs in microscale arrays, offering a bioinspired and green-route to fabrication. However, μCP cannot produce patterns reliably with nanoscale dimensions, and most alternative nanofabrication techniques are slow and expensive. Interferometric lithography (IL) uses the interference of laser light to produce nanostructures over large areas via a simple process implemented under ambient conditions. Here we combine the bottom-up biomediated approach with a top down IL methodology to produce arrays of uniform magnetite MNPs (86 ± 21 nm) with a period of 357 nm. This shows a potentially revolutionary strategy for the production of magnetic arrays with nanoscale precision in a process with low environmental impact, which could be scaled readily to facilitate large-scale production of nanopatterned surface materials for technological applications.

Cytokine adsorption/release on uniform magnetic nanoparticles for localized drug delivery

Attachment of cytokines to magnetic nanoparticles has been developed as a system for controlled local drug release in cancer therapy. We studied the adsorption/release of murine interferon gamma (IFN-γ) on negatively charged magnetic nanoparticles prepared by three different methods, including coprecipitation, decomposition in organic media, and laser pyrolysis. To facilitate IFN-γ adsorption, magnetic nanoparticles were surface modified by distinct molecules to achieve high negative charge at pH 7, maintaining small aggregate size and stability in biological media. We analyzed carboxylate-based coatings and studied the colloidal properties of the resulting dispersions. Finally, we incubated the magnetic dispersions with IFN-γ and determined optimal conditions for protein adsorption onto the particles, as well as the release capacity at different pH and as a function of time. Particles prepared by decomposition in organic media and further modified with dimercaptosuccinic acid showed the most efficient adsorption/release capacity. IFN-γ adsorbed on these nanoparticles would allow concentration of this protein or other biomolecules at specific sites for treatment of cancer or other diseases.

Immunogenicity of bioactive magnetic nanoparticles: Natural and acquired antibodies

Uniform magnetic nanoparticles (MNP) were prepared by nucleation followed by controlled growth of maghemite thin films onto porcine gelatin nuclei. The formed gelatin containing MNP (Gel-MNP) were then coated with dextran (Gel-MNP-Dex) followed by human serum albumin (Gel-MNP-Dex-HSA). Since these MNP are designated for clinical applications, studies concerning the immunogenicity of their antigenic components (porcine gelatin, dextran, and HSA) have been performed in BALB-C mice. These studies demonstrated that plasma of nonimmunized mice already contains basal levels of natural antibodies against all of these antigenic components. This work also demonstrated that the conjugated gelatin is a weak immunogen: Intraperitoneal injection of the various MNP (Gel-MNP, Gel-MNP-Dex dispersed in PBS emulsified with Incomplete Freund's Adjuvant (IFA) mineral oil and Gel-MNP-Dex-HSA dispersed in PBS) did not increase significantly the acquired anti-gelatin antibody titers. Exceptional behavior was observed following immunization with Gel-MNP-Dex-HSA dispersed in PBS emulsified with IFA, which exhibited an adjuvant effect and turned gelatin into a stronger immunogen. In contrast to gelatin, the conjugated HSA and dextran were found to be strong immunogens. The possibility that the various MNP will not induce an autoimmune response as a result of their clinical use is discussed in the contest of the protective role of the natural antibodies.

Toxicity estimation of magnetic fluids in a biological test

Uniform magnetic nanoparticles were prepared by chemical coprecipitation. Decanoic acid was used as the first surfactant to minimize the magnetic dipole–dipole interaction, and starch, citric acid, decanoic acid, polyethylene glycol and alginic acid were selected as the second surfactants for hydrophilicity. The applied second surfactants strongly influenced the biological toxicity of the magnetic particles as well as the properties of magnetic fluids.