Preparation and rheological studies of uncoated and PVA-coated magnetite nanofluid

Experimental studies of rheological behavior of uncoated magnetite nanoparticles (MNPs)U and polyvinyl alcohol (PVA) coated magnetite nanoparticles (MNPs)C were performed. A Co-precipitation technique under N₂ gas was used to prevent undesirable critical oxidation of Fe²⁺. The results showed that smaller particles can be synthesized in both cases by decreasing the NaOH concentration which in our case this corresponded to 35 nm and 7 nm using 0.9 M NaOH at 750 rpm for (MNPs)U and (MNPs)C. The stable magnetic fluid contained well-dispersed Fe₃O₄/PVA nanocomposites which indicated fast magnetic response. The rheological measurement of magnetic fluid indicated an apparent viscosity range (0.1–1.2) pa s at constant shear rate of 20 s⁻¹ with a minimum value in the case of (MNPs)U at 0 T and a maximum value for (MNPs)C at 0.5 T. Also, as the shear rate increased from 20 s⁻¹ to 150 s⁻¹ at constant magnetic field, the apparent viscosity also decreased correspondingly. The water-based ferrofluid exhibited the non-Newtonian behavior of shear thinning under magnetic field.     

Preparation and characterization of silica-coated Fe3O4 nanoparticles used as precursor of ferrofluids

Fe₃O₄ magnetic nanoparticles (MNPs) were synthesized by the co-precipitation of Fe³⁺ and Fe²⁺ with ammonium hydroxide. The sodium citrate-modified Fe₃O₄ MNPs were prepared under Ar protection and were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). To improve the oxidation resistance of Fe₃O₄ MNPs, a silica layer was coated onto the modified and unmodified MNPs by the hydrolysis of tetraethoxysilane (TEOS) at 50 °C and pH 9. Afterwards, the silica-coated Fe₃O₄ core/shell MNPs were modified by oleic acid (OA) and were tested by IR and VSM. IR results revealed that the OA was successfully grafted onto the silica shell. The Fe₃O₄/SiO₂ core/shell MNPs modified by OA were used to prepare water-based ferrofluids (FFs) using PEG as the second layer of surfactants. The properties of FFs were characterized using a UV-vis spectrophotometer, a Gouy magnetic balance, a laser particle size analyzer and a Brookfield LVDV-III+ rheometer.     

A novel approach to preparing magnetic protein microspheres with core-shell structure

Magnetic protein microspheres with core-shell structure were prepared through a novel approach based on the sonochemical method and the emulsion solvent evaporation method. The microspheres are composed of the oleic acid and undecylenic acid modified Fe₃O₄ cores and coated with globular bovine serum albumin (BSA). Under an optimized condition, up to 57.8 wt% of approximately 10 nm superparamagnetic Fe₃O₄ nanoparticles could be uniformly encapsulated into the BSA microspheres with the diameter of approximately 160 nm and the high saturation magnetization of 38.5 emu/g, besides of the abundant functional groups. The possible formation mechanism of magnetic microspheres was discussed in detail.     

Templated synthesis of monodisperse mesoporous maghemite/silica microspheres for magnetic separation of genomic DNA

A novel method is described for the preparation of superparamagnetic mesoporous maghemite (γ-Fe₂O₃)/silica (SiO₂) composite microspheres to allow rapid magnetic separation of DNA from biological samples. With magnetite (Fe₃O₄) and silica nanoparticles as starting materials, such microspheres were synthesized by the following two consecutive steps: (1) formation of monodispersed organic/inorganic hybrid microspheres through urea-formaldedyde (UF) polymerization and (2) removal of the organic template and phase transformation of Fe₃O₄ to γ-Fe₂O₃ by calcination at elevated temperatures. The as-synthesized particles obtained by heating at temperature 300 °C feature spherical shape and uniform particle size (d_particle=1.72 μm), high saturation magnetization (M_s=17.22 emu/g), superparamagnetism (M_r/M_s=0.023), high surface area (S_BET=240 m²/g), and mesoporosity (d_pore=6.62 nm). The composite microsphere consists of interlocked amorphous SiO₂ nanoparticles, in which cubic γ-Fe₂O₃ nanocrystals are homogeneously dispersed and thermally stable against γ- to α-phase transformation at temperatures up to 600 °C. With the exposed iron oxide nanoparticles coated with a thin layer of silica shell, the magnetic microspheres were used as a solid-phase adsorbent for rapid extraction of genomic DNA from plant samples. The results show that the DNA templates isolated from pea and green pepper displayed single bands with molecular weights greater than 8 kb and A₂₆₀/A₂₈₀ values of 1.60-1.72. The PCR amplification of a fragment encoding the endogenous chloroplast ndhB gene confirmed that the DNA templates obtained were inhibitor-free and amenable to sensitive amplification-based DNA technologies.     

The colloidal stability and core-shell structure of magnetite nanoparticles coated with alginate

The adsorption of alginate (Alg) onto the surface of in water dispersed Fe₃O₄ nanoparticles and zeta potential of alginate-coated Fe₃O₄ nanoparticles have been investigated to optimize the colloidal stability of Alg-coated Fe₃O₄ nanoparticles. The adsorption amount of Alg increased with the decrease of adsorption pH. The zeta potential of Fe₃O₄ nanoparticles shifted to a lower value after adsorption of Alg. The lower adsorption pH was the lower zeta potential of Fe₃O₄ nanoparticles became. The Alg-coated Fe₃O₄ nanoparticles were found to be stabilized by steric and electrostatic repulsions. Those prepared at pH 6 were not stable around pH 5, and those prepared at pH 4 became unstable at pH below 3.5. Alg of M_w 45 kDa was a little bit more adsorbed onto nanoparticles surface than that of M_w 24 kDa. An average Fe₃O₄ core size of 9.3 ± 1.7 nm was found by transmission electronic microscopy. An average hydrodynamic diameter of 30-150 nm was measured by photon correlation spectroscopy. However, an average core size of 10 nm and an average hydrodynamic diameter of 38 nm were estimated from the magnetization curve of the concentrated magnetic fluids (MFs). The maximum available saturation magnetization of MFs was about 3.5 kA/m.     

Synthesis of iron oxide nanoparticles under oxidizing environment and their stabilization in aqueous and non-aqueous media

Synthesis of magnetite (Fe₃O₄) nanoparticles under oxidizing environment by precipitation from aqueous media is not straightforward because Fe²⁺ gets oxidized to Fe³⁺ and thus the ratio of Fe³⁺:Fe²⁺=2:1 is not maintained during the precipitation. A molar ratio of Fe³⁺:Fe²⁺ smaller than 2:1 has been used by many to compensate for the oxidation of Fe²⁺ during the preparation. In this work, we have prepared iron oxide nanoparticles in air environment by the precipitation technique using initial molar ratios Fe³⁺:Fe²⁺?2:1. The phases of the resulting powders have been determined by several techniques. It is found that the particles consist mainly of maghemite with little or no magnetite phase. The particles have been suspended in non-aqueous and aqueous media by coating the particles with a single layer and a bilayer of oleic acid, respectively. The particle sizes, morphology and the magnetic properties of the particles and the ferrofulids prepared from these particles are reported. The average particle sizes obtained from the TEM micrographs are 14, 10 and 9 nm for the water, kerosene and dodecane-based ferrofluids, respectively, indicating a better dispersion in the non-aqueous media. The specific saturation magnetization (σ_s) value of the oleic-acid-coated particles (∼53 emu/g) is found to be lower than that for the uncoated particles (∼63 emu/g). Magnetization σ_s of the dodecane-based ferrofluid is found to be 10.1 emu/g for a volume fraction of particles ?=0.019. Zero coercivity and zero remanance on the magnetization curves indicate that the particles are superparamagnetic (SPM) in nature.     

Application of silica–magnetite nanocomposites to the isolation of ultrapure plasmid DNA from bacterial cells

The aim of this study was to develop a simple and rapid method for purification of ultrapure plasmid DNA with high yields from bacterial cultures. Nanosized superparamagnetic nanoparticles (Fe₃O₄) were prepared by chemical precipitation method using Fe²⁺, Fe³⁺ salt, and ammonium hydroxide under a nitrogen atmosphere. Silica–magnetite nanocomposites were prepared by the method of acid hydrolysis of tetraethoxysilane (TEOS) to coat the silica onto magnetite nanoparticles. DNA was adsorbed to the support under high salt conditions, and recovered directly in water for immediate downstream application, without the need for precipitation. We demonstrated that a useful plasmid, pRSETB-EGFP, encoding for the green fluorescent protein with T7 promoter, could be amplified in Escherichia coli of DE3 strain. Up to approximately 43 μg of high-purity (A₂₆₀/A₂₈₀ ratio=1.75) plasmid DNA was isolated from 3 ml of an overnight bacterial culture. The eluted plasmid DNA was used directly for restriction enzyme digestion, bacterial cell transformation and polymerase chain reaction (PCR) amplification with success. The protocol, starting from the preparation of bacterial lysate and ending with purified plasmid takes less than 8 min. The silica–magnetite nanocomposites deliver significant time-savings, overall higher yields, lower RNA contamination, and better PCR amplification compared to commercial available silica-based and other methods.     

Magnetic nanocomposite spinel and FeCo core-shell and mesoporous systems

The fabrication of condensed silica and mesoporous silica coated spinel CoFe₂O₄ and FeCo alloy magnetic nanocomposites are reported. The encapsulation of well-defined 5 nm thick uniform silica layer on CoFe₂O₄ magnetic nanoparticles was performed. The formation of mesopores in the shell was a consequence of removal of organic group of the precursor through annealing. The NiO nanoparticles were loaded into the mesoporous silica. The mesoporous silica shells leads to a larger coercivity than that of pure CoFe₂O₄ magnetic nanoparticles due to the decrease of interparticle interactions and magneto-elastic anisotropy. In addition, the FeCo nanoparticles were coated by condensed and mesoporous silica. The condensed silica can protect the reactive FeCo alloy from oxidation up to 300 °C. However, saturation magnetization of FeCo nanoparticles coated by silica after 400 °C annealing is dramatically decreased due to the oxidation of the FeCo core. The mesoporous silica coated magnetic nanostructure loaded with NiO as a final product could be used in the field of biomedical applications.     

Microwave synthesis of magnetic Fe3O4 nanoparticles used as a precursor of nanocomposites and ferrofluids

Methods to synthesize magnetic Fe₃O₄ nanoparticles and to modify the surface of particles are presented in the present investigation. Fe₃O₄ magnetic nanoparticles were prepared by the co-precipitation of Fe³⁺ and Fe²⁺, NH₃·H₂O was used as the precipitating agent to adjust the pH value, and the aging of Fe₃O₄ magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe₃O₄ magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe₃O₄ crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe₃O₄ magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe₃O₄ nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe₃O₄ nanoparticles. The dispersion of Fe₃O₄ in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe₃O₄/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe₃O₄ magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe₃O₄ nanoparticles. The Fe₃O₄ magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10⁻⁸ and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe₃O₄ nanoparticles in the fluid was 36.19 nm.     

Synthesis of magnetic hollow silica using polystyrene bead as a template

In this paper, we report a new route to synthesize novel magnetic hollow silica nanospheres (MHSNs) using polystyrene particles as sacrificial templates, and TEOS and Fe₃O₄ as precursors. TEM, EDS, XRD, and SQUID were applied to characterize MHSNs. TEM and EDS results show that the MHSNs consist of about 200 nm of hollow cores and ∼35 nm shells with ∼10 nm of Fe₃O₄ nanoparticles embedded. The polystyrene beads were successfully removed by immersing the as-prepared silica nanocomposite in a toluene solution. XRD results demonstrate that the Fe₃O₄ magnetic nanoparticles still keep spinel structure even heated at low temperature. The surface status of the polystyrene beads and Fe₃O₄ nanoparticles has an important effect on the formation of the MHSNs. The MHSNs present a superparamagnetism at room temperature by SQUID measurement. The MHSNs have potential applications in biosystem and nanomedicine.     

Magnetoresistance of magnetite thin films grown by pulsed laser deposition on GaAs(1 0 0) and Al2O3(0 0 0 1)

Magnetotransport properties of magnetite thin films deposited on gallium arsenide and sapphire substrates at growth temperatures between 473 and 673 K are presented. The films were grown by UV pulsed laser ablation in reactive atmospheres of O₂ and Ar, at working pressure of 8 × 10⁻² Pa. Film stoichiometry was determined in the range from Fe_2.95O₄ to Fe_2.97O₄. Randomly oriented polycrystalline thin films were grown on GaAs(1 0 0) while for the Al₂O₃(0 0 0 1) substrates the films developed a (1 1 1) preferred orientation. Interfacial Fe³⁺ diffusion was found for both substrates affecting the magnetic behaviour. The temperature dependence of the resistance and magnetoresistance of the films were measured for fields up to 6 T. Negative magnetoresistance values of ∼5% at room temperature and ∼10% at 90 K were obtained for the as-deposited magnetite films either on GaAs(1 0 0) or Al₂O₃(0 0 0 1).     

Preparation, characterization and MRI application of carboxymethyl dextran coated magnetic nanoparticles

Superparamagnetic nanoparticles functionalized with carboxymethyl dextran (CM-dextran) were synthesized by a two-step method. First, the magnetic nanoparticles (MNPs) coated with dextran (M_w ≈ 20000) were prepared by co-precipitation of Fe²⁺ and Fe³⁺ ions. Then, dextran on the surface of MNPs reacted with monochloroacetic acid (MCA) in alkaline condition. The influences of temperature and reactant concentration on the amount of -COOH on the surface of nanoparticles were systematically studied. The obtained MNPs coated with CM-dextran were stable over the entire range of pH and NaCl concentration. The MRI experiment indicated that the CM-dextran MNPs could potentially be used as MRI contrast agents for magnetic resonance molecular imaging.     

Synthesis and cation distribution of copper-substituted spinel-related lithium ferrite

Single-phased Cu²⁺-substituted spinel-related Li_0.5Fe_2.5O₄ was synthesized by sintering a mixture of Cu²⁺-substituted corundum-related α-Fe₂O₃ and Li₂CO₃ at 700 °C which is ∼325-400 °C lower than the temperature at which the material is prepared by the conventional ceramic methods. X-ray powder diffraction, X-ray photoelectron spectroscopy, Mössbauer spectroscopy and magnetic measurements were used to characterize the material. In contrast to high-temperature synthetic routes, the present one leads to a Cu⁺-and Fe²⁺-cation free material, thereby optimizing its technological value. Rietveld refinement of the XRD data favors a structural model in which Cu²⁺ substitutes for both Fe³⁺ and Li⁺ at the octahedral sites. Mössbauer and magnetic data are consistent with this model if spin thermal reversal and/or spin canting are taken into account for the later.     

Investigating the formation and magnetic properties of the Dy0.75Fe1.25O3 orthoferrite prepared by sol-gel method

In this paper, the Dy_0.75Fe_1.25O₃ orthoferrite nanoparticles were synthesized successfully by sol-gel method. Dy_0.75Fe_1.25O₃ orthoferrite nanoparticles are obtained by calcining the flakes at 600 and 700 °C. The magnetic properties of the different samples are investigated using Quantum Design MPMS SQUID magnetometer and MS-500 Mössbauer spectrometer. Magnetic phase γ-Fe₂O₃ coexists in the samples calcined at 600 °C and orthoferrite phase is completely recovered in the samples calcined at 700 °C. Although excessive Fe³⁺ ions were introduced, none of these iron spins couple magnetically with Dy³⁺ ions.     

Infrared and Raman spectroscopic studies on iron oxide magnetic nano-particles and their surface modifications

Iron oxide magnetic nano-particles (MNPs) have been prepared in aqueous solution by a modified co-precipitation method. Surface modifications have been carried out using tetraethoxysilane (TEOS), triethoxysilane (TES) and 3-aminopropyltrimethoxysilane (APTMS). The uncoated and coated particle products have been characterized with transmission electron microscope (TEM), energy dispersive X-ray (EDX) spectroscopy, infrared (IR) and Raman spectroscopy, and thermal gravimetric analysis (TGA). The particle sizes were determined from TEM images and found to have mean diameters of 13, 16 and 14 nm for Fe₃O₄, TES/Fe₃O₄ and APTMS/Fe₃O₄, respectively. IR and Raman spectroscopy has been applied to study the effect of thermal annealing on the uncoated and coated particles. The results have shown that magnetite nano-particles are converted to maghemite at 109 °C and then to hematite by 500 °C. In contrast, the study of the effect of thermal annealing of micro-crystalline magnetite by IR spectroscopy revealed that the conversion to hematite began by 300 °C and that no maghemite could be identified as an intermediate phase. IR spectra and TGA measurements revealed that the Si-H and 3-aminopropyl functional groups in TES and APTMS coated magnetite nano-particles decomposed below 500 °C while the silica layer around the iron oxide core remained unchanged. The molecular ratio of APTMS coating to iron oxide core was determined to be 1:7 from the TGA data. Raman scattering signals have indicated that MNPs could be converted to maghemite and then to hematite using increasing power of laser irradiation in a manner similar to that observed for thermal annealing.     

Application of citrate-stabilized gold-coated ferric oxide composite nanoparticles for biological separations

Gold-coated magnetic nanoparticles were synthesized with size ranging from 15 to 40 nm using sodium citrates as the reducing agent. Oxidized magnetites (Fe₃O₄) fabricated by co-precipitation of Fe²⁺ and Fe³⁺ in strong alkaline solution were used as magnetic cores. The structures of gold (Au) shell and magnetic core (Au–Fe) were studied by transmission electron microscopy (TEM) image and energy dispersive spectroscopy (EDS) spectrum. Results from high-resolution X-ray diffraction (HR XRD) show that the Au–Fe oxide nanoparticles have a face-centered cubic shape with the crystalline faces of {1 1 1}. The Au-coated magnetic nanoparticles exhibited a surface plasmon resonance peak at 528 nm. The nanoparticles are well dispersed in distilled water. A 3000 G permanent magnet was successfully used for the separation of the functionalized nanoparticles. Magnetic properties of the nanoparticles were determined by magnetic force microscope (MFM) in nanometric resolution and vibrating sample magnetometer (VSM). Magnetic separation of biological molecules using Au-coated magnetic oxide composite nanoparticles was examined after attachment of protein immunoglobulin G (IgG) through electrostatic interactions. Using this method, separation was achieved with a maximum yield of 35% at an IgG concentration of 400 ng/ml.     

One-step synthesis of Fe3O4@C/reduced-graphite oxide nanocomposites for high-performance lithium ion batteries

In this paper, we propose a facile one-step strategy to prepare Fe₃O₄@amorphous carbon/reduced graphite oxide nanocomposites (FCRGs) under hydrothermal conditions. A transmission electron microscopy image has shown that the as-formed Fe₃O₄ nanoparticles coated with a layer of amorphous carbon are wrapped by reduced graphite oxide (r-GO) sheets. The diameter of Fe₃O₄ nanoparticles is less than 50 nm. N₂ adsorption/desorption isotherms indicate that the specific surface area of FCRG is 31.6 m²/g with porous structure. FCRG exhibits improved cycling stability and rate performances as a potential anode material for high-performance lithium ion batteries.     

Thermal and magnetic behavior of Angustifolia Kunth bamboo fibers covered with Fe3O4 particles

Several Angustifolia Kunth bamboo fibers, which have been previously treated with an alkaline solution, were coated with magnetite particles. The coating of the fibers was achieved by an in-situ co-precipitation method with Fe²⁺ and Fe³⁺in NaOH or NH₄OH. The fibers were evaluated by chemical analysis using atomic absorption (A.A.) technique, structural characterization by X-ray diffraction (XRD), thermal stability with thermo-gravimetric analysis (TGA) in nitrogen at temperature range between 23 °C and 800 °C and magnetic behavior using vibrating sample magnetometry (VSM) applying a magnetic field between −27 KOe and 27 KOe at room temperature. We found that the thermal stability and magnetization depend of the synthesis method used to cover the Angustifolia Kunth bamboo fibers. In addition, an improved magnetic response was observed when NaOH solution is used to generate the magnetite coating on the fiber surface.     

Preparation and characterizations of SiO2-coated nanoparticles of Mn0.4Zn0.6Fe2O4

Core/shell nanoparticles consisting of a magnetic core of zinc-substituted manganese ferrite (Mn_0.4Zn_0.6Fe₂O₄) and a shell of silica (SiO₂) are prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) as a precursor material for silica and salts of iron, manganese and zinc as the precursor of the ferrite. Three weight percentages of the shell materials of SiO₂ are used to prepare the coated nanoparticles. The X-ray diffractograms (XRD) of the coated and uncoated magnetic nanoparticles confirmed that the magnetic nanoparticles are in their mixed spinel phase in an amorphous matrix of silica. Particles sizes of the samples annealed at different temperatures are estimated from the width of the (3 1 1) line of the XRD pattern using the Debye-Sherrer equation. The information regarding the crystallographic structure together with the particles sizes extracted from the high-resolution transmission electron microscopy (HRTEM) of a few selected samples are in agreement with those obtained from the XRD. HRTEM observations revealed that particles are coated with silica. The calculated thickness is in agreement with that obtained from the HRTEM pictures. Hysteresis loops observed in the temperature range 300 down to 5 K and Mössbauer spectra at room temperature indicate superparamagnetic relaxation of the nanoparticles.     

Surface functionalization of chitosan-coated magnetic nanoparticles for covalent immobilization of yeast alcohol dehydrogenase from Saccharomyces cerevisiae

A novel and efficient immobilization of yeast alcohol dehydrogenase (YADH, EC1.1.1.1) from Saccharomyces cerevisiae has been developed by using the surface functionalization of chitosan-coated magnetic nanoparticles (Fe₃O₄/KCTS) as support. The magnetic Fe₃O₄/KCTS nanoparticles were prepared by binding chitosan alpha-ketoglutaric acid (KCTS) onto the surface of magnetic Fe₃O₄ nanoparticles. Later, covalent immobilization of YADH was attempted onto the Fe₃O₄/KCTS nanoparticles. The effect of various preparation conditions on the immobilized YADH process such as immobilization time, enzyme concentration and pH was investigated. The influence of pH and temperature on the activity of the free and immobilized YADH using phenylglyoxylic acid as substrate has also been studied. The optimum reaction temperature and pH value for the enzymatic conversion catalyzed by the immobilized YADH were 30 °C and 7.4, respectively. Compared to the free enzyme, the immobilized YADH retained 65% of its original activity and exhibited significant thermal stability and good durability.