Magnetite nanoparticles embedded in biodegradable porous silicon

Magnetite nanoparticles, which are coated with oleic acid in a hexane solution and exhibit an average diameter of 7.7 nm, were embedded in a porous silicon (PS) matrix by immersion under defined parameters (e.g. concentration, temperature, time). The porous silicon matrix is prepared by anodization of a highly n-doped silicon wafer in an aqueous HF-solution. Magnetic characterization of the samples has been performed by SQUID-magnetometry. The superparamagnetic behaviour of the magnetite nanoparticles is represented by temperature-dependent magnetization measurements. Zero field (ZFC)/field cooled (FC) experiments indicate magnetic interactions between the particles. For the infiltration into the PS-templates different concentrations of the magnetite nanoparticles are used and magnetization measurements are performed in respect with magnetic interactions between the particles. The achieved porous silicon/magnetite specimens are not only interesting due to their transition between superparamagnetic and ferromagnetic behaviour, and thus for magnetic applications but also because of the non-toxicity of both materials giving the opportunity to employ the system in medical applications as drug delivery or in medical diagnostics.     

Biocompatible high-moment FeCo-Au magnetic nanoparticles for magnetic hyperthermia treatment optimization

A great deal of attention has been paid to the use of magnetite nanoparticles as heating elements in the research of magnetic fluid hyperthermia. However, these particles have a relatively low magnetization and as a result, have low heating efficiency as well as difficulties in detection applications. To maximize heating efficiency we propose and show the use of high-moment Fe(Co)-Au core-shell nanoparticles. Using a physical vapor nanoparticle-deposition technique the high-moment nanoparticles were synthesized. The water-soluble particles were placed in an AC magnetic field of variable magnetic field frequencies. The temperature rise was measured and compared to theory.     

Magnetite nanoparticles as-prepared and dispersed in Copaiba oil: study using magnetic measurements and Mössbauer spectroscopy

Study of magnetite nanoparticles, as-prepared and dispersed in Copaiba oil as magnetic fluid, by means of magnetic measurement and Mössbauer spectroscopy at various temperatures demonstrated differences in the saturation magnetization and Mössbauer hyperfine parameters which were related to the interactions of Copaiba oil polar molecules with iron cations on magnetite nanoparticle’s surface.     

Magnetic properties of single biogenic magnetite nanoparticles

Biogenic magnetite nanoparticles (MNP) extracted from the magnetotactic bacterium Magnetospirillum gryphiswaldense MSR-1 have been systematically studied by atomic force microscopy (AFM) and magnetic force microscopy (MFM). Isolated single MNP and chains of MNP were obtained from diluted MNP aqueous suspension dried on mica surfaces in a homogeneous in-plane magnetic field. The size of the MNP was determined by employing AFM tip deconvolution procedures. The obtained result has been confirmed by scanning electronic microscopy. Magnetic properties of isolated single MNP and chains of MNP in remanence and in the presence of external magnetic fields were investigated by MFM. In particular, the magnetization reversal of a two-particle chain has been revealed and the dipolar interaction between the MNP is estimated. The change in the magnetic contrast on application of an external magnetic field is consistent with the hysteresis curve obtained by cantilever magnetometry.     

Effective anisotropy field variation of magnetite nanoparticles with size reduction

Size effect on the internal magnetic structure has been investigated on weakly interacting magnetite (Fe₃O₄) nanoparticles by ferromagnetic resonance experiments at 9.5 GHz as a function of temperature (4–300 K). A set of three samples with mean particle size of 2.5 nm, 5.0 nm and 13.0 nm, respectively, were prepared by chemical route with narrow size distribution (σ < 0.27). To minimize the dipolar interaction, the particles were dispersed in a liquid and a solid polymer matrix at ∼0.6% in mass. By freezing the liquid suspension with an applied external field, a textured was obtained. Thus, both random and textured suspensions were studied and compared. The ferromagnetic resonance experiments in zero-field-cooled and field-cooled conditions were carried out to study the size effect on the effective anisotropy field. The dc magnetization measurements clearly show that the internal magnetic structure was strongly affected by the particle size.     

Simulating magnetic nanoparticle behavior in low-field MRI under transverse rotating fields and imposed fluid flow

In the presence of alternating-sinusoidal or rotating magnetic fields, magnetic nanoparticles will act to realign their magnetic moment with the applied magnetic field. The realignment is characterized by the nanoparticle's time constant, τ. As the magnetic field frequency is increased, the nanoparticle's magnetic moment lags the applied magnetic field at a constant angle for a given frequency, Ω, in rad s⁻¹. Associated with this misalignment is a power dissipation that increases the bulk magnetic fluid's temperature which has been utilized as a method of magnetic nanoparticle hyperthermia, particularly suited for cancer in low-perfusion tissue (e.g., breast) where temperature increases of between 4 and 7 °C above the ambient in vivo temperature cause tumor hyperthermia. This work examines the rise in the magnetic fluid's temperature in the MRI environment which is characterized by a large DC field, B₀. Theoretical analysis and simulation is used to predict the effect of both alternating-sinusoidal and rotating magnetic fields transverse to B₀. Results are presented for the expected temperature increase in small tumors ( radius) over an appropriate range of magnetic fluid concentrations (0.002-0.01 solid volume fraction) and nanoparticle radii (1-10 nm). The results indicate that significant heating can take place, even in low-field MRI systems where magnetic fluid saturation is not significant, with careful the goal of this work is to examine, by means of analysis and simulation, the concept of interactive fluid magnetization using the dynamic behavior of superparamagnetic iron oxide nanoparticle suspensions in the MRI environment. In addition to the usual magnetic fields associated with MRI, a rotating magnetic field is applied transverse to the main B₀ field of the MRI. Additional or modified magnetic fields have been previously proposed for hyperthermia and targeted drug delivery within MRI. Analytical predictions and numerical simulations of the transverse rotating magnetic field in the presence of B₀ are investigated to demonstrate the effect of Ω, the rotating field frequency, and the magnetic field amplitude on the fluid suspension magnetization. The transverse magnetization due to the rotating transverse field shows strong dependence on the characteristic time constant of the fluid suspension, τ. The analysis shows that as the rotating field frequency increases so that Ωτ approaches unity, the transverse fluid magnetization vector is significantly non-aligned with the applied rotating field and the magnetization's magnitude is a strong function of the field frequency. In this frequency range, the fluid's transverse magnetization is controlled by the applied field which is determined by the operator. The phenomenon, which is due to the physical rotation of the magnetic nanoparticles in the suspension, is demonstrated analytically when the nanoparticles are present in high concentrations (1-3% solid volume fractions) more typical of hyperthermia rather than in clinical imaging applications, and in low MRI field strengths (such as open MRI systems), where the magnetic nanoparticles are not magnetically saturated. The effect of imposed Poiseuille flow in a planar channel geometry and changing nanoparticle concentration is examined. The work represents the first known attempt to analyze the dynamic behavior of magnetic nanoparticles in the MRI environment including the effects of the magnetic nanoparticle spin-velocity. It is shown that the magnitude of the transverse magnetization is a strong function of the rotating transverse field frequency. Interactive fluid magnetization effects are predicted due to non-uniform fluid magnetization in planar Poiseuille flow with high nanoparticle concentrations.     

Energy contributions in magnetite nanoparticles: computation of magnetic phase diagram,theory, and simulation

In this study, we present a theoretical analysis of magnetization processes by considering energy contributions in magnetite fine particles. The focus is on the K _S-driven magnetic phase transition taking place between the low surface-anisotropy ferrimagnetic state and the hedgehog configuration obtained in the high surface-anisotropy limit. Analytical expressions of energy terms (exchange, magnetocrystalline anisotropy, surface-anisotropy) are presented and their magnitudes are computed for different particle sizes. Monte Carlo simulations were also carried out for comparison purposes. A core–shell model is implemented for simulating magnetite nanoparticles between 2 and 10 nm in diameter. Our simulation framework is based on a three-dimensional classical Heisenberg-like Hamiltonian with nearest magnetic neighbors interactions. It includes exchange coupling, cubic magnetocrystalline anisotropy for core ions, and single-ion site surface-anisotropy for those atoms belonging to the shell. The magnetic phase diagram and comparisons between analytical and numerical results are presented and discussed.     

Water-soluble magnetic nanoparticles with biologically active stabilizers

We present the results of the interaction of iron oxide nanoparticles with some biologically active surfactants, namely, oleic acid and cytotoxic alkanolamine derivatives. Physico-chemical properties, as magnetization, magnetite concentration and particle diameter, of the prepared magnetic samples were studied. The nanoparticle size of 11 nm for toluene magnetic fluid determined by TEM is in good agreement with the data obtained by the method of magnetogranulometry. In vitro cytotoxic effect of water-soluble nanoparticles with different iron oxide:oleic acid molar ratio were revealed against human fibrosarcoma and mouse hepatoma cells. In vivo results using a sarcoma mouse model showed observable antitumor action.     

Evidence for magnetic interactions among magnetite nanoparticles dispersed in photoreticulated PEGDA-600 matrix

Magnetite nanoparticles having mean diameter of about 8 nm have been prepared by a thermo-chemical route. Different amounts (5 and 10% wt) of a stable dispersion of magnetite nanoparticles in n-hexane were added to polyethylene glycol diacrylate (PEGDA-600) oligomer containing 2% wt of radicalic photoinitiator. The homogenized mixture was poured on a silica glass substrate and the resulting film was photoreticulated in N₂ atmosphere using a UV lamp. As a result, a polymer-based magnetic nanocomposite was obtained, where the magnetic nanoparticles are dispersed in the diamagnetic matrix, as checked by SEM. Morphology, composition, and size of as-prepared nanoparticles were checked by SEM and X-ray diffraction. The magnetic properties of magnetite nanoparticles prior to and after inclusion in the polymeric matrix have been studied by means of an alternating-gradient magnetometer (T interval: 10–300 K, H_MAX: 18 kOe). FC-ZFC curves were obtained in the same temperature interval. The results show that the nanocomposites cannot be simply described as containing superparamagnetic particles undergoing an anisotropy-driven blocking and that collective magnetic interactions play a non-negligible role. Low-temperature hysteretic properties indicate that the polymeric matrix affects the effective anisotropy of magnetite nanoparticles. Dispersion of magnetite NPs in PEGDA has non-trivial consequences on their magnetic properties.     

One-step hydrothermal synthesis of highly water-soluble secondary structural Fe3O4 nanoparticles

Magnetite nanoparticles (MNPs) were prepared using the ferric acetylacetonate as the sole iron source in a facile hydrothermal route, while poly(acrylic acid) (PAA) was chosen as the stabilizer via one-step functionalized MNPs for better hydrophilic properties. The orthogonal was used in the paper for the experimental parameters optimization, including the solvent, the reaction time, the amount of stabilizer and the presynthesis. The obtained highly water dispersible MNPs with uniform size from about 50 to about 100 nm was individually composed of many monodisperse magnetite crystallites approximately 6 nm in size. And the MNPs show high magnetic properties, whose magnetite content was up to 76.76% and the saturation magnetization was 39.0 emu/g. Later the formation mechanism of MNPs was also discussed. Thus the MNPs proved to be very promising for biomedical applications.     

Superparamagnetic silica nanoparticles with immobilized metal affinity ligands for protein adsorption

Superparamagnetic silica-coated magnetite (Fe₃O₄) nanoparticles with immobilized metal affinity ligands were prepared for protein adsorption. First, magnetite nanoparticles were synthesized by co-precipitating Fe²⁺ and Fe³⁺ in an ammonia solution. Then silica was coated on the Fe₃O₄ nanoparticles using a sol–gel method to obtain magnetic silica nanoparticles. The condensation product of 3-Glycidoxypropyltrimethoxysilane (GLYMO) and iminodiacetic acid (IDA) was immobilized on them and after charged with Cu²⁺, the magnetic silica nanoparticles with immobilized Cu²⁺ were applied for the adsorption of bovine serum albumin (BSA). Scanning electron micrograph showed that the magnetic silica nanoparticles with an average size of 190 nm were well dispersed without aggregation. X-ray diffraction showed the spinel structure for the magnetite particles coated with silica. Magnetic measurement revealed the magnetic silica nanoparticles were superparamagnetic and the saturation magnetization was about 15.0 emu/g. Protein adsorption results showed that the nanoparticles had high adsorption capacity for BSA (73 mg/g) and low nonspecific adsorption. The regeneration of these nanoparticles was also studied.     

A novel magnetic fluid based on starch-coated magnetite nanoparticles functionalized with homing peptide

Preparation and characterization in vitro and in vivo of a novel magnetic fluid based on starch-coated magnetite nanoparticles functionalized with homing peptide is reported in this paper. Precursory magnetic fluids stabilized with starch were prepared, in a polymeric starch matrix, by controlled chemical coprecipitation of magnetite phase from aqueous solutions. The average hydrodynamic diameter of starch-coated iron oxide nanoparticles (SIONs) was 46 nm. As a homing peptide, A54 is the most effective peptide specific to the human hepatocellular carcinoma cell line BEL-7402. Final magnetic fluids were obtained through chemical coupling of homing peptide labeled with 5-carboxyl-fluorescein (FAM-A54) and SIONs. Magnetic measurements showed the saturation magnetization value of SIONs amounted to 45 emu/g and the FAM-A54-coupled SIONs showed a good magnetic response in magnetic field. The results of experiments in vitro and in vivo showed that SIONs were endowed with specific affinity to corresponding tumor cells after coupling with FAM-A54 and the FAM-A54-coupled SIONs could be accumulated in the tumor tissue with more efficiency than individual magnetic targeting or biomolecular targeting. This novel magnetic fluid with dual function has great potential applications in diagnostics and therapeutics of human tumor such as drug targeting, magnetic hyperthermia, and magnetic resonance imaging.     

Effects of surfactant and polymerization method on the synthesis of magnetic colloidal polymeric nanoparticles

The addition of superparamagnetic iron nanoparticles into polystyrene matrix allows for the modification of the physical properties as well as the implementation of new features in the hybrid nanomaterials. These materials have excellent potential for biomedical and bioengineering applications. Nevertheless, it is necessary to achieve a good dispersion of magnetic nanoparticles for its successful incorporation into polymer particles. This can be obtained through the use of a stabilizer, which provides stability against aggregation. In this work, magnetic nanoparticles were dispersed using different stabilizers. Subsequently, ferrofluids stabilized using the mixture of ABEX/IGEPAL and acrylic acid (AA) were used to synthesize PS-Fe₃O₄ nanocomposites, through miniemulsion and emulsion polymerization conventional techniques. Semicontinuous and batch processes were compared, by varying surfactants and their concentrations. The PS-Fe₃O₄ nanoparticles were characterized by dynamic light scattering, scanning electron microscopy, Raman spectroscopy, and vibrating sample magnetometer. Magnetic nanoparticle dispersions show better results when the anionic and nonionic surfactants are used as a mixture rather than when used alone. Results of DLS showed that the semicontinuous process allowed obtaining monodisperse materials, whereas polidisperse systems are generated in batch process. Raman spectroscopy confirmed the presence of magnetite and polystyrene in the nanocomposites. PS-Fe₃O₄ nanoparticles showed superparamagnetic behavior with final magnetization of around 0.01 emu/g and low coercivity, properties that make them suitable for applications in wide fields of technology. Particle size (Dz), was lower than 300 nm in all cases. Moreover, the use of AA as stabilizer allows enhancing the PS-Fe₃O₄ composite properties. These findings showed that particle size, morphology, and agglomeration are directly influenced by the concentration and the type of surfactant employed.     

Synthesis of magnetite nanoparticles for AC magnetic heating

Magnetite particles with different average diameter (D_m) suitable for magnetic fluid hyperthermia (MFH) were synthesized by controlled coprecipitation technique. In this method, the reaction pH was stabilized using the pH buffer and the average particle diameter decreased with increasing reaction pH. The size-dependent magnetic behavior of the magnetite nanoparticles was studied and the optimum size range required for magnetic fluid hyperthermia (MFH) has been arrived at. Among the samples studied, the maximum specific absorption rate of 15.7 W/g was recorded for the magnetite sample with D_m of 13 nm, when exposed to an AC magnetic field strength of 3.2 kA/m and a frequency of 600 kHz. The AC magnetic properties suggested that the size distribution of the sample was bimodal with average particle size less than ∼13 nm.     

High-gradient magnetic separation of microparticles on membrane separation unit

A simple design of a magnetic separator based on a membrane made of a laser-perforated ferromagnetic foil has been proposed. The separator is primarily intended for analytical and research purposes. The developed magnetic separator of the proposed design has been tested in the separation of a composite aqueous suspension of magnetite nanoparticles adsorbed on hydroxyapatite microparticles. Separation efficiency has been determined via measuring the magnetic moment by the ferromagnetic resonance method; the suspension particle size has been found by dynamic light scattering before and after the separation process. It has been shown that all the particles with a diameter of more than 500 nm are retained during separation; the magnetization of the fraction decreases twofold after passing through the membrane.     

Space-selective modification of the magnetic properties of transparent Fe3+-doped glass by femtosecond-laser irradiation

We have demonstrated spatially selective modification of the magnetic properties of transparent iron-oxide-doped glass by femtosecond- (fs-) laser irradiation and subsequent annealing. A near-infrared fs-laser beam with a wavelength of 775 nm was focused 1 mm below the surfaces of glass samples. This produces absorption peaks due to the formation of hole-trap centers in the irradiated region. Transparency was recovered after annealing at 450°C. A ferrimagnetic component was observed in the M–H curve even at room temperature, whereas the diamagnetic component dominated in the M–H curve of the as-prepared glass sample. This indicates that fs-laser irradiation enhanced the magnetization in the irradiated area. The irradiated and annealed glass sample also exhibited superparamagnetic blocking in the temperature dependence of the magnetization with a blocking temperature higher than room temperature. This change in magnetism is presumably due to local crystallization of ferrimagnetic nanoparticles, such as magnetite, induced by fs-laser irradiation and annealing. The magnetic and optical properties of glass that had been annealed but not irradiated by a fs-laser beam remained unchanged.     

Dynamic effects of dipolar interactions on the magnetic behavior of magnetite nanoparticles

Isothermal magnetization and initial dc susceptibility of spheroidal, nearly monodisperse magnetite nanoparticles (typical diameter: 8 nm) prepared by a standard thermo-chemical route have been measured between 10 and 300 K. The samples contained magnetite nanoparticles in the form of either a dried powder (each nanoparticle being surrounded by a stable oleic acid shell as a result of the preparation procedure) or a solid dispersion in PEGDA-600 polymer; different nanoparticle (NP) concentrations in the polymer were studied. In all samples the NPs were not tightly agglomerated nor their ferromagnetic cores were directly touching. The high-temperature inverse magnetic susceptibility is always found to follow a linear law as a function of T, crossing the horizontal axis at negative temperatures ranging from 175 to about 1,000 K. The deviation from the standard superparamagnetic behavior is related to dipolar interaction among NPs; however, a careful analysis makes it hard to conclude that such a behavior originates from a dominant antiferromagnetic character of the interaction. The results are well explained considering that the studied samples are in the interacting superparamagnetic (ISP) regime. The ISP model is basically a mean field theory which allows one to straightforwardly account for the role of magnetic dipolar interaction in a NP system. The model predicts the existence of specific scaling laws for the reduced magnetization which have been confirmed in all studied samples. The interaction of each magnetic dipole moment with the local, random dipolar field produced by the other dipoles results in the presence of a large fluctuating energy term whose magnitude is comparable to the static barrier for magnetization reversal/rotation related to magnetic anisotropy. On the basis of the existing theories on thermal crossing of a barrier whose height randomly fluctuates in time it is predicted that the rate of barrier crossing is substantially driven by the rate of barrier fluctuations, which is fast (10⁸–10⁹ Hz) and almost independent of temperature. As a consequence, the standard picture of superparamagnetic NPs which undergo single-particle blocking by a static barrier below the blocking temperature should be substantially revised, at least in the present materials. The ISP model is perfectly matching with the view of activated magnetization rotation whose kinetics is significantly modified by barrier height fluctuations.     

Non-Langevin behaviour of the uncompensated magnetization in nanoparticles of artificial ferritin

The magnetic behaviour of nanoparticles of antiferromagnetic artificial ferritin has been investigated by ⁵⁷Fe M?ssbauer absorption spectroscopy and magnetization measurements, in the temperature range 2.5-250 K and with magnetic fields up to 7 T. Samples containing nanoparticles with an average number of ⁵⁷Fe atoms ranging from 400 to 2 500 were studied. By analysing the magnetic susceptibility and zero field M?ssbauer data, the anisotropy energy per unit volume is found, in agreement with some of the earlier studies, to have a value typical for ferric oxides, i.e. a few 10⁵ ergs/cm³. By comparing the results of the two experimental methods at higher fields, we show that, contrary to what is currently assumed, the uncompensated magnetization of the ferritin cores in the superparamagnetic regime does not follow a Langevin law. For magnetic fields below the spin-flop field, we propose an approximate law for the field and temperature variation of the uncompensated magnetization, which was early evoked by Néel but has so far never been applied to real antiferromagnetic systems. More generally, this approach should apply to randomly oriented antiferromagnetic nanoparticles systems with weak uncompensated moments. Received 20 January 2000     

Synthesis and characterization of uncoated and gold-coated magnetite nanoparticles

We report on the synthesis and characterization of uncoated and gold coated magnetite nanoparticles. Structural characterizations, carried out using X-ray diffraction, confirm the formation of magnetite phase with a mean size of ~7 and ~8 nm for the uncoated and gold covered magnetite nanoparticles, respectively. The value of the gold coated Fe₃O₄ nanoparticles is consistent with the mean physical size determined from transmission electron microscopy images. Mössbauer spectra at room temperature are consistent with the thermal relaxation of magnetic moments mediated by particle-particle interactions. The 77 K Mössbauer spectra are modeled with four sextets. Those sextets are assigned to the signal of iron ions occupying the tetrahedral and octahedral sites in the core and shell parts of the particle. The room-temperature saturation magnetization value determined for the uncoated Fe₃O₄ nanoparticles is roughly ~60 emu/g and suggests the occurrence of surface effects such as magnetic disorder or the partial surface oxidation. These surface effects are reduced in the gold-coated Fe₃O₄ nanoparticles. Zero-field–cooled and field-cooled curves of both samples show irreversibilities which are consistent with a superparamagnetic behavior of interacting nanoparticles.     

Influence of the inhomogeneity of local magnetic parameters on the curves of magnetization in an ensemble of Fe<Subscript>3</Subscript>C ferromagnetic nanoparticles encapsulated in carbon nanotubes

Methods have been proposed and tested for analyzing local magnetic parameters in a system of single-domain ferromagnetic nanoparticles using their magnetization curves. The magnetic inhomogeneity in ensembles of Fe₃C nanoparticles encapsulated in carbon nanotubes has been investigated. It has been established that the Fe₃C nanoparticles encapsulated in carbon nanotubes are characterized by two-modal distribution functions of the local magnetic anisotropy energy. The particle distribution over the blocking temperature is reconstructed from the experimental temperature dependence of the coercive force. The allowance made for the inhomogeneity of the local magnetic parameters of the Fe₃C nanoparticles, which were studied by the proposed methods, explains the discrepancy between the magnetic anisotropy energy determined by the method of the magnetization approaching saturation and the magnetic anisotropy energy estimated from the coercive force of single-domain nanoparticles.