Synthesis and surface modification of hydrophobic magnetite to processible magnetite@silica-propylamine

Hydrophobic magnetite nanoparticles with a narrow size distribution were prepared by thermal decomposition of Fe(CO)₅ in octyl ether solution of oleic acid and by consecutive aeration. The nanoparticles were converted into magnetite core/silica shell (magnetite@silica) structured particles with hydrophilic and processible aminopropyl groups on their surfaces.     

Oleic acid coating on the monodisperse magnetite nanoparticles

Monodisperse magnetite nanoparticles provide a more factual model to study the interface interactions between the surfactants and magnetic nanoparticles. Monodisperse magnetite nanoparticles of 7 and 19 nm coated with oleic acid (OA) were prepared by the seed-mediated high temperature thermal decomposition of iron(III) acetylacetonate (Fe(acac)₃) precursor method. Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS) reveal that the OA molecules were adsorbed on the magnetic nanoparticles by chemisorption way. Analyses of transmission electron microscopy (TEM) shows the OA provided the particles with better isolation and dispersibility. Thermogravimetric analysis (TGA) measurement results suggest that there were two kinds of different binding energies between the OA molecules and the magnetic nanoparticles. The cover density of OA molecules on the particle surface was significantly various with the size of magnetite nanoparticles. Magnetic measurements of the magnetite nanoparticles show the surface coating reduced the interactions among the nanoparticles.     

Ion dependence of magnetic anisotropy in MFe2O4 (MFe,Co, Mn) nanoparticles synthesized by high-temperature reaction

The influence of different M²⁺ cations on the effective magnetic anisotropy of systems composed of MFe₂O₄ (M=Fe, Co and Mn) nanoparticles was investigated. Samples were prepared by the high-temperature (538 K) solution phase reaction of Fe (acac)₃, Co (acac)₂ and Mn (acac)₂ with 1,2 octanodiol in the presence of oleic acid and oleylamine. The final particles are coated by an organic layer of oleic acid that prevents agglomeration. Transmission electron microscopy (TEM) images show that particles present near spherical form and a narrow grain size distribution, with mean diameters in the range of 4.5–7.6 nm. Powder samples were analyzed by ac susceptibility and Mössbauer measurements, and K_eff for all samples was evaluated using both techniques, showing a strong dependence on the nature of the divalent cation.     

Ion dependence of magnetic anisotropy in MFe2O4 (MFe, Co, Mn) nanoparticles synthesized by high-temperature reaction

The influence of different M²⁺ cations on the effective magnetic anisotropy of systems composed of MFe₂O₄ (M=Fe, Co and Mn) nanoparticles was investigated. Samples were prepared by the high-temperature (538 K) solution phase reaction of Fe (acac)₃, Co (acac)₂ and Mn (acac)₂ with 1,2 octanodiol in the presence of oleic acid and oleylamine. The final particles are coated by an organic layer of oleic acid that prevents agglomeration. Transmission electron microscopy (TEM) images show that particles present near spherical form and a narrow grain size distribution, with mean diameters in the range of 4.5–7.6 nm. Powder samples were analyzed by ac susceptibility and Mössbauer measurements, and K_eff for all samples was evaluated using both techniques, showing a strong dependence on the nature of the divalent cation.     

Study of molecular surface coating on the stability of maghemite nanoparticles

In this study γ-Fe₂O₃ nanoparticle, surface-coated with increasing amount of oleic acid, have been prepared while the stability against particle degradation under laser excitation intensity was investigated. Maghemite nanoparticle was obtained via oxidation of magnetite nanoparticle, the latter synthesized by co-precipitation of Fe (II) and Fe (III) ions in alkaline medium. By varying the experimental conditions of surface-coating maghemite nanoparticles with oleic acid, samples with different grafting coefficient were obtained and investigated using X-ray diffraction and different spectroscopic techniques, namely Raman, Mössbauer, and infrared. The amount of oleic acid adsorbed on the maghemite surface was estimated via the carbon content obtained from elemental analysis.     

Transforming single domain magnetic CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles from hydrophobic to hydrophilic by novel mechanochemical ligand exchange

Single-phase uniform-sized (~9 nm) cobalt ferrite (CFO) nanoparticles have been synthesized by hydrothermal synthesis using oleic acid as a surfactant. The as-synthesized oleic acid-coated CFO (OA-CFO) nanoparticles were well dispersible in nonpolar solvents but not dispersible in water. The OA-CFO nanoparticles have been successfully transformed to highly water-dispersible citric acid-coated CFO (CA-CFO) nanoparticles using a novel single-step ligand exchange process by mechanochemical milling, in which small chain citric acid molecules replace the original large chain oleic acid molecules available on CFO nanoparticles. The OA-CFO nanoparticle’s hexane solution and CA-CFO nanoparticle’s water solution remain stable even after 6 months and show no agglomeration and their dispersion stability was confirmed by zeta-potential measurements. The contact angle measurement shows that OA-CFO nanoparticles are hydrophobic whereas CA-CFO nanoparticles are superhydrophilic in nature. The potentiality of as-synthesized OA-CFO and mechanochemically transformed CA-CFO nanoparticles for the demulsification of highly stabilized water-in-oil and oil-in-water emulsions has been demonstrated.     

The influence of thermal annealing on the structural and magnetic properties of gold nanoparticles

In the past few years ferromagnetic-like behavior has been reported in metal gold nanoparticles coated with diverse organic surfactants. In this work we report on the effect of thermal annealing on the ferromagnetic-like behavior of oleic acid and oleylamine coated gold nanoparticles of about 7 nm size. The magnetic moment of the “as prepared” sample is about 3×10⁻² emu/g and the coercive field is 200 Oe at 10 kOe and 5 K, after the annealing the behavior changes from ferromagnetic-like to paramagnetic and the magnetization at 10 kOe decreases at a factor of 10. These results are compared with those obtained for oleylamine coated gold nanoparticles, which are diamagnetic at room temperature.     

Preparation of poly(styrene-glucidylmethacrylate)/Fe3O4 composite microspheres with high magnetite contents

Magnetic polymer composite microspheres with high magnetite contents were prepared by dispersion polymerization of styrene (St) and glucidylmethacrylate (GMA), in which Fe₃O₄ nanoparticles were co-stabilized by oleic acid and silane surfactants. The microstructure of the composite microspheres was characterized by Fourier transform infrared (FTIR) spectrometry, X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results demonstrated the presence of a hybrid morphology with organic polymer-encapsulated inorganic particles. Subsequently, thermogravimetric analysis (TGA) and vibrating sample magnetometry (VSM) were used to evaluate the magnetite content of the microspheres. It was found that an accordant magnetite content of about 70 wt%, could be obtained for the magnetic polymer microspheres, a value significantly higher than those reported thus far. The possible mechanism for the formation of the microspheres was proposed.     

Magnetic and Mössbauer studies of fucan-coated magnetite nanoparticles for application on antitumoral activity

Fucan-coated magnetite (Fe₃O₄) nanoparticles were synthesized by the co-precipitation method and studied by Mössbauer spectroscopy and magnetic measurements. The sizes of the nanoparticles were 8–9 nm. Magnetization measurements and Mössbauer spectroscopy at 300 K revealed superparamagnetic behavior. The magnetic moment of the Fe₃O₄ is partly screened by the Fucan coating aggregation. When the magnetite nanoparticles are capped with oleic acid or fucan, reduced particle-particle interaction is observed by Mössbauer and TEM studies. The antitumoral activity of the fucan-coated nanoparticles were tested in Sarcoma 180, showing an effective reduction of the tumor size.     

A solid phospholipid-bile salts-mixed micelles based on the fast dissolving oral films to improve the oral bioavailability of poorly water-soluble drugs

Magnetic iron oxide nanoparticles surface covered with oleic acid layer followed by a second layer of hydrophobized oxidized dextran aldehyde were prepared and tested for physico-chemical properties and ligand- and cell-specific binding. It was demonstrated that oleic acid–iron oxide nanoparticles coated with an additional layer of hydrophobized oxidized dextran were dispersible in buffer solutions and possess surface aldehyde active groups available for further binding of ligands or markers via imine or amine bond formation. Hydrophobized dextrans were synthesized by periodate oxidation and conjugation of various alkanamines to oxidized dextran by imination. Physico-chemical properties, as separation using magnetic field, magnetite concentration, and particle diameter, of the prepared magnetic samples are reported. The biotin-binding protein, neutravidin, was coupled to the particle surface by a simple reductive amination procedure. The particles were used for specific cell separation with high specificity.     

Synthesis and characterization of superparamagnetic iron oxide nanoparticles for biomedical applications

Monodisperse iron oxide nanoparticles (NPs) of 4 nm were obtained through high-temperature solution phase reaction of iron (III) acetylacetonate with 1, 2-hexadecanediol in the presence of oleic acid and oleylamine. The as-synthesized iron oxide nanoparticles have been characterized by X-ray diffraction, transmission electron microscopy, Mössbauer spectroscopy and magnetic measurements. The species obtained were Fe₃O₄ and/or $\upgamma$ -Fe₂O₃. These NPs are superparamagnetic at room temperature and even though the reduced particle size they show a high saturation magnetization (MS ≈ 90 emu/g).     

Preparation of Fe3O4/polystyrene composite particles from monolayer oleic acid modified Fe3O4 nanoparticles via miniemulsion polymerization

Fe₃O₄/polystyrene composite particles were prepared from oleic acid (OA) modified Fe₃O₄ nanoparticles via miniemulsion polymerization. It was concluded that the surface properties of OA modified magnetite nanoparticles have a great effect on preparation of the composite particles. When Fe₃O₄ nanoparticles coated by multilayer of OA was employed, there were large amounts of free polystyrene particles in the product. Fe₃O₄/polystyrene composite particles with defined structure and different magnetite content can be readily prepared from monolayer OA modified Fe₃O₄ nanoparticles. It was concluded that surface of the monolayer OA modified Fe₃O₄ nanoparticles is more hydrophobic than that of the multilayer coated ones, thus improving the dispersibility of the Fe₃O₄ nanoparticles in styrene monomer and allowing preparation of the Fe₃O₄/polystyrene composite particles with defined structure and controllable magnetite content.     

One-pot synthesis of amphiphilic superparamagnetic FePt nanoparticles and magnetic resonance imaging in vitro

Monodispersed amphiphilic FePt nanoparticles with the diameter of about 4 nm were synthesized by high temperature pyrolysis of iron(III) acetylacetonate and platinum(II) acetylacetonate. Their amphiphilicity is contributed to the tetraethylene glycol (TEG) and oleic acid (OA) on the surface, which is confirmed by FTIR and XPS spectra. They provide a superparamagnetic property with the saturation magnetization (Ms) of about 25 emu/g and the transverse relaxivity (r₂) of about 122.6 mM⁻¹ s⁻¹ in aqueous solutions. Furthermore, FePt nanoparticles show low cytotoxicity in living cells. They can be uptaken by HeLa cells effectively and result in the obvious decrease of T₂ relaxation time after internalization.     

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.     

Electronic states of self stabilized L10 FePt alloy nanoparticles

The ligand capped bimetallic FePt alloys were prepared by using the chemical coreduction method in the presence of oleic acid and oleylamine. An X-ray photoelectron spectroscopy (XPS) study on the as prepared and annealed samples reveals the degradation of hydrocarbon capping with annealing temperature along with a phase transformation to a L1₀ phase. This degradation of organic capping results in formation of capping layer over FePt which has been observed using High Resolution Transmission electron microscopy (HRTEM). This capping layer over the FePt nanoparticles was further investigated with Raman studies confirming the presence of the graphitic carbon. The presence of the graphitic layer enhances the stability of FePt nanoparticles by protecting the surface against oxidation. This was confirmed by the magnetic measurements which show a high coercivity of 11.8 kOe, retained over a period of one year.     

Biomimetic nucleation and growth of hydrophobic vaterite nanoparticles with oleic acid in a methanol solution

Hydrophobic vaterite nanoparticles were prepared via crystallization of CaCO₃ with oleic acid in methanol by mimicking the process of biomineralization. The molar ratio of oleic acid to calcium ion was varied from 0.1 to 0.5. By changing the concentration of the oleic acid, CaCO₃ particles with different shapes and polymorphism were obtained. High concentration of the oleic acid gave stable vaterite crystals, the polymorph of which did not change when the composite was kept in water for more than one week. Fourier transform infrared spectroscopy (FT-IR) and TGA analysis of the obtained product indicated that the oleic acid was bound to the crystalline CaCO₃. The contact angle of the modified vaterite reached 122°. We have succeeded in crystallization of hydrophobic CaCO₃ nanoparticles in situ.     

Roles of oleic acid during micropore dispersing preparation of nano-calcium carbonate particles

In the present work, nano-calcium carbonate powder was prepared by micropore dispersion method with assistance of oleic acid as surfactant. CO₂ gas was dispersed into the Ca(OH)₂/H₂O slurry via a glass micropore-plate with the diameter of micropore about 20 μm. To investigate the effect of oleic acid on the size of CaCO₃ particles, different amount of oleic acid was added in Ca(OH)₂/H₂O slurry at 5 °C and 25 °C, respectively. XRD patterns show that cubic calcite is the only crystalline phase in all cases. ZPA data and TEM photo indicate that the average particle size synthesized at 5 °C without oleic acid is of about 40 nm, slightly smaller than that of prepared at 25 °C, and that the dispersity of sample prepared at 5 °C is better than that of 25 °C. When oleic acid is added in both temperatures, the average particle size decreases a little. FT-IR spectra demonstrate that oleic acid interacts with Ca²⁺ and carbon-carbon double bond existed on the surface of particle. Consequently, two opposite roles of oleic acid during the process of preparation of nano-CaCO₃ were proposed, namely preventing nanoparticles from growing during reaction and making nanoparticles reunite to a certain extent after reaction.     

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.     

Synthesis of aqueous ferrofluids of ZnxFe3−xO4 nanoparticles by citric acid assisted hydrothermal-reduction route for magnetic hyperthermia applications

Superparamagnetic and monodispersed aqueous ferrofluids of Zn substituted magnetite nanoparticles (Zn_xFe_3−xO₄, x=0, 0.25, 0.3, 0.37 and 0.4) were synthesized via hydrothermal-reduction route in the presence of citric acid, which is a facile, low energy and environmental friendly method. The synthesized nanoparticles were characterized by X ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and the dynamic light scattering (DLS) method. The results showed that a certain amount of citric acid was required to obtain single phase Zn substituted magnetite nanoparticles. Citric acid acted as a modulator and reducing agent in the formation of spinel structure and controlled nanoparticle size and crystallinity. Mean particle sizes of the prepared nanoparticles were around 10 nm. The results that are obtained from XRD, magnetic and power loss measurements showed that the crystallinity, saturation magnetization (M_S) and loss power of the synthesized ferrofluids were all influenced by the substitution of Zn in the structure of magnetite. The Zn substituted magnetite nanoparticles obtained by this route showed a good stability in aqueous medium (pH 7) and hydrodynamic sizes below 100 nm and polydispersity indexes below 0.2. The calculated intrinsic loss power (ILP) for the sample x=0.3 (e.g. 2.36 nH m²/kg) was comparable to ILP of commercial ferrofluids with similar hydrodynamic sizes.     

Cobalt nanoparticles synthesis from Co(CH3COO)2 by thermal decomposition

Nontoxic cobalt acetate tetrahydrate was used as a precursor to prepare cobalt nanoparticles of 8–200 nm in average diameter by thermal decomposition. The different combinations of trioctylphosphine, oleylamine and oleic acid were added as surfactants to control the particle size. These combinations resulted in the particles with saturation magnetization and coercive force ranging from 55.0 to 100.1 emu/g and from 0 to 459.3 Oe, respectively.