Synthesis and properties of magnetic fluid based on iron nanoparticles prepared by a vapor-phase condensation process

Magnetic fluid containing metallic iron nanoparticles was successfully fabricated in this work. The iron nanoparticles were synthesized by chemical vapor condensation process and then dispersed in water-base solution (pH 11) with oleic acid as surfactant. More than 80% of iron nanoparticles were fully dispersed in the fluid and remained stable without any further oxidation over 200 h. Both the iron nanoparticles and the subsequent magnetic fluid exhibited typical ferromagnetic behavior.     

The effect of surfactants on the magnetic and optical properties of Co-doped SnO2 nanoparticles

A series of Co-doped SnO₂ nanoparticles have been synthesized by the co-precipitation route. Different amounts of surfactant have been used in order to study the effect of surfactants (CTAB) on the magnetic and optical properties. Structural analyses reveal that Co dopants are substituted into rutile SnO₂ nanoparticles without forming any secondary phase. The increase of the surfactant promotes the adsorption of organic molecules on the surfaces of nanoparticles. Meanwhile, both the ferromagnetism and the orange emission drop progressively. The dependence of ferromagnetic properties on the surfactant concentration could be explained based on the bound magnetic polaron, where the carriers are provided by oxygen vacancies. XANES spectra reveal that the electrons transfer from Co 3d bands to the surfactant ions. Such electron-transfer process suppresses the formation of oxygen vacancies and leads to the decline of the ferromagnetism and optical emission.     

Magneto-optical study of the orientation confinement of particles in ferrolyotropic systems

Ferrosmectics and ferrohexagonals are magnetic liquid crystals which consist of a lamellar and a hexagonal phase in which magnetic nanoparticles are incorporated. The magnetic field variation and the relaxation of the linear optical birefringence of ferrosmectics and ferrohexagonals and its time relaxation are measured in different geometries and compared with that of a ferrofluid sample. We interpret our data by the existence of a mean orientation of the magnetic particles in the lyotropic structure, which appears to be non-random in zero field. We conclude that the magnetic moments of the particles are preferentially aligned in the plane of the ferrosmectic layers and along the axis of the ferrohexagonal cylinders, respectively. To account for this preferred alignment, we propose that some of the particles in the ferrosmectic are adsorbed on the surfactant layers with their moment aligned in the lamellar plane, while the orientation of the moments in the ferrohexagonal is restricted to a cone around the cylinder axis. Received 31 December 1998 and Received in final form 22 September 1999     

Effects of surfactants on properties of polymer-coated magnetic nanoparticles for drug delivery application

The objective of this research was to compare the effects of two different surfactants on the physicochemical properties of thermo-responsive poly(N-isopropylacrylamide-acrylamide-allylamine) (PNIPAAm-AAm-AH)-coated magnetic nanoparticles (MNPs). Sodium dodecyl sulfate (SDS) as a commonly used surfactant in nanoparticle formulation process and Pluronic F127 as an FDA approved material were used as surfactants to synthesize PNIPAAm-AAm-AH-coated MNPs (PMNPs). The properties of PMNPs synthesized using SDS (PMNPs-SDS) and PF127 (PMNPs-PF127) were compared in terms of size, polydispersity, surface charge, drug loading efficiency, drug release profile, biocompatibility, cellular uptake, and ligand conjugation efficiency. These nanoparticles had a stable core–shell structure with about a 100-nm diameter and were superparamagnetic in behavior with no difference in the magnetic properties in both types of nanoparticles. In vitro cell studies showed that PMNPs-PF127 were more cytocompatible and taken up more by prostate cancer cells than that of PMNPs-SDS. Cells internalized with these nanoparticles generated a dark negative contrast in agarose phantoms for magnetic resonance imaging. Furthermore, a higher doxorubicin release at 40 °C was observed from PMNPs-PF127, and the released drugs were pharmacologically active in killing cancer cells. Finally, surfactant type did not affect the conjugation efficiency to the nanoparticles when folic acid was used as a targeting ligand model. These results indicate that PF127 might be a better surfactant to form polymer-coated magnetic nanoparticles for targeted and controlled drug delivery.     

Ultrasonic investigation of magnetic nanoparticles suspension with PEG biocompatible coating

Water suspension of nanoparticles was studied by ultrasound spectroscopy. Nanoparticles have a core-shell structure with magnetic core Fe₃O₄ and surfactant shells. The surface of magnetic particles was coated with oleate sodium as the primary layer and polyethylene glycol as the secondary layer. The acoustic properties of suspensions, such as velocity and attenuation of ultrasonic waves, have been measured. From experimental data mechanical properties have been determined. Adiabatic compressibility of nanoparticles suspension decreased with increase of temperature. The changes of ultrasonic wave attenuation under the influence of the external magnetic field, show that magnetic liquids with high concentration of magnetic material (despite two surfactant shells) show tendency to aggregate.     

Surface modification of magnetic metal nanoparticles through irradiation graft polymerization

To tailor the interfacial interaction in magnetic metal nanoparticles filled polymer composites, the surfaces of iron, cobalt and nickel nanoparticles were grafted by irradiation polymerization. In the current report, effects of grafting conditions, including irradiation atmosphere, irradiation dose and monomer concentration, on the grafting reaction are presented. The interaction between the nanoparticles and the grafted polymer was studied by thermal analysis and X-ray photoelectron spectrometry. It was found that there is a strong interfacial interaction in the form of electrostatic bonding in the polymer-grafted nanoparticles. The dispersibility of the modified nanoparticles in chloroform was significantly improved due to the increased hydrophobicity.     

Study of polydiethylsiloxane-based ferrofluid with excellent frost resistance property

The polydiethylsiloxane-based ferrofluid was prepared by dispersing finely divided magnetic Fe₃O₄ particles which are modified with oleoyl sarcosine and lauroyl sarcosine. The optimized experiment parameters including molar ratio of surfactant to Fe₃O₄ (1:5), temperature (80 °C), stirring rate (300 RPM), the surfactant content of lauroyl sarcosine (0 to 33 mol%) and the modification time (25 min) were obtained by the orthogonal test. The magnetic liquid was characterized by a transmission electron microscope (TEM), infrared (IR) spectrometer, X-ray diffractometer (XRD), thermogravimetry (TG), vibrating sample magnetometer (VSM) and differential scanning calorimetry (DSC). It is indicated that the surfactant is mainly bonded to the surface of Fe₃O₄ nanoparticles through covalent bond between carboxylate (COO⁻) and Fe atom. The modified magnetic particles are equally dispersed into the carrier and remain stable below −12 °C over 4 months. The ferrofluids exhibit excellent frost resistance property and distinctly reduced temperature coefficient of viscosity compared with polydimethylsiloxane-based ferrofluids and hydrocarbon-based ferrofluids, respectively. The saturation magnetization could reach up to 27.7 emu/g.     

Formation of zinc sulfide nanoparticles in HMTA matrix

A hydrothermal method has been optimized for the synthesis of ZnS nanoparticles. The nanoparticles were stabilized using Hexamethylenetetramine (HMTA) as surfactant in aqueous solution. The self-assembling of the surfactant molecules in the water solution forms a unique architecture that can be adopted as the reaction template for the formation of nanomaterials. The average grain size of the nanoparticles calculated from the XRD pattern was of the order of 2 nm which exhibits cubic zinc-blende structure. TEM results showed that the synthesized nanoparticles were uniformly dispersed in the HMTA matrix without aggregation. The spectroscopic results revealed that the synthesized ZnS nanoparticles exhibits strong quantum confinement effect as the optical band gap energy increased significantly compared to the bulk ZnS material. Formation of HMTA capped ZnS nanoparticles were confirmed by FTIR studies. The PL spectra exhibit a strong green emission peak around 502 nm attributed to some self-activated defect centers related to Zn-vacancies.     

Self-assembled and fluorescence enhancement of semiconductor nanoparticles induced by surfactant adsorption

When semiconductor colloidal CdS nanoparticles and nonylphenol are mixed together in dimethyl sulfoxide at room temperature, a self-assembling process is induced. In the course, the size tunable properties of CdS nanoparticles are amplified. A blue shift in the emission spectrum and a strong photoluminescence enhancement are observed without significant change in the absorption features of the colloidal nanoparticles. These results are attributed to the adsorption of nonylphenol onto the nanoparticles surface and to the association process of the surfactant molecules. The surfactant adsorption process provides a nanoparticle surface passivation and induces an associative phase that enlarges the photoluminescence stability. This strategy opens the possibility to improve simultaneously physicochemical and photoluminescence properties of nanocrystals in solution as well as to control their deposition on two-dimensional surfaces.     

Desorption of surfactant and sintering of surface-modified PdxNi1 − x nanoparticles

A series of Pd_xNi_1 − x nanoparticles in a diameter of 6-7 nm were prepared by wet chemical reduction. They were then modified with two surfactants, stearic acid (SA) and polyethylene glycol (PEG). Desorption of the surfactant was studied using a temperature programmed desorption technique, and the sintering behavior of surface-modified Pd_xNi_1 − x nanoparticles was examined. Since surface energy of the nanoparticles depends on the alloy composition, it can be correlated with the desorption temperature of surfactant from the nanoparticle surface. Because Ni has a higher surface energy, the surfactant desorption temperature increases as the Ni content increases. With the same stoichiometry, the desorption temperature of SA is always higher than that of PEG. The SA-modified nanoparticles have higher thermal stability and are less sintered than PEG-modified nanoparticles. The sintering and growth behavior of the nanoparticles can be correlated with variation of surface energy due to different surface modification.     

Characterization of different magnetite–cobalt nanoparticles in hydrocarbon-based magnetic fluids by means of static and dynamic magnetization measurements

Magnetic nanoparticles with different compositions (Co_xFe_3−xO₄, 0?x?0.1) were synthesized from metal salts using a coprecipitation technique to produce magnetic fluids following a peptization technique. The liquid carrier was the hydrocarbon Isopar M and the surfactant was oleic acid. The colloidal-sized ferrimagnetic nanoparticles produced were found to be superparamagnetic. Measurements of the complex magnetic susceptibility were carried out to evaluate the resonant frequency f_res, the anisotropy constant K, and anisotropy field H_A. f_res was found to be a linear function of the cobalt content of the magnetic nanoparticles over the range of cobalt content studied.     

Influence of a surfactant on hyperfine magnetic interactions in goethite nanoparticles

Structural and magnetic characteristics of nanosized goethite (α-FeOOH) samples prepared by chemical precipitation of an iron (III) salt and alkali in aqueous solutions with different contents of a surfactant (ethyl alcohol) have been investigated. Changes in the morphology, structure, and sizes of antiferromagnetic nanoparticles, caused by the presence of the surfactant in the deposition solution, have been established by Mössbauer spectroscopy, magnetic measurements, X-ray diffraction, and electron microscopy. It is determined that an increase in the surfactant concentration leads to the bimodal size distribution of nanoparticles; in this case, the fraction of small (<10 nm) isolated particles in the sample increases and the degree of ordering of larger particles (50–100 nm) increases with a change in their shape from spherical to needle-like.     

Numerical micromagnetics of interacting superparamagnetic nanoparticles assembled in clusters with different dimensionalities

We analyze here the equilibrium magnetization state of densely packed interacting superparamagnetic nanoparticles assembled in clusters of various sizes and dimensionalities by comparison with the non-interacting case. We demonstrate that the average magnetization of individual particles is strongly increased in linear chains aligned parallel with the external magnetic field. Two-dimensional (2D) distributions of superparamagnetic nanoparticles present weaker increases of their average magnetization with respect to the non-interacting approximation whereas volume distributions (3D) are almost equivalent with the non-interacting case. A large number of nanoparticles densely packed in 2D superparamagnetic clusters present almost the same magnetic moment as infinite superparamagnetic chains. The effect of mutual interactions on the total magnetic moment of 3D surfaces (spheroids with various aspect ratios) uniformly covered with densely packed monolayers of superparamagnetic nanoparticles is also investigated.     

Thermal treatment effects in the self-assembly of FePt nanoparticle arrays

This work concentrates on the influence of synthetic mechanisms of FePt nanoparticles on their self-arrangement and some structural and magnetic properties as studied by means of different electron microscopy techniques and SQUID magnetometry. High-reflux points associated with long boiling durations seem adequate to increase the iron precursor's decomposition yield and facilitate the simultaneous cubic to tetragonal FePt transformation, in single-phase FePt nanoparticles. Nevertheless, such conditions also result in the loss of long-range arrangement and in the appearance of coalescence effects. A core–shell structure comprising of FePt and Fe₃O₄ is favored under mild thermal conditions during synthesis, which seems to confront the undesirable atomic diffusion. Additionally, particle isolation due to the surfactant coating leads in an hcp-symmetry self-assembly. Moreover, working at lower temperatures allows a homogeneous mixture between different phases producing binary composite arrays.     

Internal structure of magnetic endosomes

The internal structure of biological vesicles filled with magnetic nanoparticles is investigated using the following complementary analyses: electronic transmission microscopy, dynamic probing by magneto-optical birefringence and structural probing by Small Angle Neutron Scattering (SANS). These magnetic vesicles are magnetic endosomes obtained via a non-specific interaction between cells and anionic magnetic iron oxide nanoparticles. Thanks to a magnetic purification process, they are probed at two different stages of their formation within HeLa cells: (i) adsorption of nanoparticles onto the cellular membrane and (ii) their subsequent internalisation within endosomes. Differences in the microenvironment of the magnetic nanoparticles at those two different stages are highlighted here. The dynamics of magnetic nanoparticles adsorbed onto cellular membranes and confined within endosomes is respectively 3 and 5 orders of magnitude slower than for isolated magnetic nanoparticles in aqueous media. Interestingly, SANS experiments show that magnetic endosomes have an internal structure close to decorated vesicles, with magnetic nanoparticles locally decorating the endosome membrane, inside their inner-sphere. These results, important for future biomedical applications, suggest that multiple fusions of decorated vesicles are the biological processes underlying the endocytosis of that kind of nanometric materials.     

Stability and magnetorheological behaviour of magnetic fluids based on ionic liquids

This paper reports the preparation of magnetic fluids consisting of magnetite nanoparticles dispersed in an ionic liquid. Different additives were used in order to stabilize the fluids. Colloidal stability was checked by magnetic sedimentation, centrifugation and direct observation. The results of these tests showed that a true ferrofluid was only obtained when the nanoparticles were coated with a layer of surfactant compatible with the ionic liquid. These experiments also showed that stability could not be reached just by electrostatic repulsion. The conclusions of the stability tests were confirmed by calculations of the interparticle energies of interaction. The rheological behaviour of the magnetic fluids upon magnetic field application was also investigated. The experimental magnetoviscous response was fitted by a microstructural model. The model considered that the fluids consisted of two populations of particles, one with a magnetic core diameter of 9?nm, and another with a larger diameter. Upon field application chain-like structures are supposed to be induced. According to estimations particles of 9?nm are too small to aggregate upon field application. The results of the calculations showed that the intensity of the magnetoviscous response depends on the concentration and size of the large particles, and on the thickness of the surfactant layers.     

Magnetic nanoparticles: Internal probes and heaters within living cells

Tagging living cells with magnetic nanoparticles raised increasing interest in the fields of magnetic resonance imaging, magnetic hyperthermia, cell sorting or tissue engineering. Here, we demonstrate that the confinement of magnetic nanoparticles at the intracellular level, inside endosomes vesicles, allows developing original magnetic manipulations in response to different magnetic field solicitations. These manipulations are used to deform cellular internal membrane, to probe the cell architecture or to heat the cell from its inside.     

Synthesis, photoluminescence and bioconjugation of rare-earth (Eu) complexes-embedded silica nanoparticles

Eu(DBM)₃Phen-embedded silica nanoparticles were synthesized in water-in-oil (W/O) microemulsion containing aqueous phase of Eu(DBM)₃Phen, surfactant Triton X-100, cosurfactant octanol and oil-phase cyclohexane. The size and morphology of the nanoparticles were characterized by transmission electron microscopy (TEM). The low-temperature time-resolved emission spectra indicate that the Eu complex in the silica nanoparticles have longer lifetime than that of the pure complex. Under 355 nm continuous excitation, the nanoparticles show high resistance to photobleaching. The free amino groups were attached to silica surfaces by copolymerization of 3-aminopropyl(triethoxy)silane. Preliminary results demonstrated that the silica-coated Eu complex nanoparticles can be a probe in the detection of biomolecular interactions.     

Preparation of a biocompatible magnetic film from an aqueous ferrofluid

Very promising nanoparticles for biomedical applications or in medical drug targeting are superparamagnetic nanoparticles based on a core consisting of iron oxides (SPION) that can be targeted through external magnets. Polyvinyl alcohol (PVA) is a unique synthetic biocompatible polymer that can be chemically cross-linked to form a gel. Biotechnology applications of magnetic gels include biosensors, targeted drug delivery, artificial muscles and magnetic buckles. These gels are produced by incorporating magnetic materials in the polymer composites. In this paper we report the synthesis of an aqueous ferrofluid and the preparation of a biocompatible magnetic gel with polyvinyl alcohol and glutharaldehyde (GTA). HClO₄ was used to induce the peptization since this kind of ferrofluid does not have surfactant. The magnetic gel was dried to generate a biocompatible film.     

Low-temperature first-order reversal curves and interaction effects on assemblies of iron oxide nanoparticles

We present the synthesis and magnetic properties of high quality uncoated and gold-coated iron oxide magnetic nanoparticles. The structural properties of these nanoparticles are investigated by transmission electron microscopy, UV-visible spectroscopy and X-ray diffraction. Experimental results and theoretical simulations indicate that the synthesized nanoparticles present a very good monodispersity, and well defined size and shape. The coercive field of these particles is identified by low-temperature first-order reversal curves and the results used in order to fit zero-field-cooled magnetization processes with theoretical models. The identification of the parameters in this analysis suggests that the coating process hardly affects the morphology and the overall magnetic properties of the cores inside coated particles.