Preparation and mechanism of magnetic carbonaceous polysaccharide microspheres by low-temperature hydrothermal method

In this study, the preparation method for magnetic carbonaceous polysaccharide (Fe₃O₄@CP) microspheres was developed to increase the yield and encapsulation efficiency using a suitable quantity of NaOH as the catalysis. The optimum fabrication condition was identified through a series of experiment, under which the resulting Fe₃O₄@CP microspheres show good magnetic properties. The saturation magnetization was 60.629 emu/g and the magnetite content increased up to 81.7%. The shell of the microspheres was carbonaceous polysaccharide with rich hydroxyl and carbonyl groups located on the surface, and the mean size was less than 300 nm. The formation mechanism of Fe₃O₄@CP was also discussed in this paper.     

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.     

Novel magnetic Fe onion-like fullerene micrometer-sized particles of narrow size distribution

Magnetic polydivinylbenzene (PDVB)/magnetite micrometer-sized particles of narrow size distribution were prepared by entrapping Fe(CO)₅ within the pores of uniform porous PDVB particles, followed by the thermal decomposition of the encapsulated Fe(CO)₅ at 300 °C in a sealed cell under inert atmosphere. Magnetic Fe onion-like fullerene micrometer-sized particles of narrow size distribution have been prepared by the thermal decomposition of the PDVB/magnetite magnetic microspheres at 1100 °C under inert atmosphere. The graphitic coating protects the elemental iron particles from oxidation and thereby preserves their very high magnetic moment for at least a year. Characterization of these unique magnetic carbon graphitic particles was also performed.     

Core-shell structure and magnetic properties of magnetite magnetic fluids stabilized with dextran

The adsorption process of different dextran molecules onto the surface of in water dispersed magnetite nanoparticles has been investigated to optimize the preparation of magnetite magnetic fluids (MMFs). An average magnetite core size of 7.1 nm was found by X-ray diffraction and that of 8 nm was found by transmission electron microscopy for the samples prepared at 90 °C. An average hydrodynamic diameter of 25 nm was observed by scanning electron microscopy and that of 25-300 nm was obtained by photon correlation spectroscopy. The dextran was adsorbed by physical adsorption, a molecular weight of 20 kDa gave the best stability of these MMFs. The shell layer of the particles was weakly negatively charged in buffer solutions of pH values between 5.5 and 9.5. The particles seem to be mainly stabilized by sterical repulsion. The maximum available saturation magnetization of the MMFs was 3.5 kA/m.     

Preparation of biodegradable magnetic microspheres with poly(lactic acid)-coated magnetite

Poly(lactic acid) (PLA)-coated magnetic nanoparticles were made using uncapped PLA with free carboxylate groups. The physical properties of these particles were compared to those of oleate-coated or oleate/sulphonate bilayer (W40) coated magnetic particles. Magnetic microspheres (MMS) with the matrix material poly(lactide-co-glycolide) (PLGA) or PLA were then formed by the emulsion solvent extraction method with encapsulation efficiencies of 40%, 83% and 96% for oleate, PLA and oleate/sulfonate-coated magnetic particles, respectively. MMS made from PLA-coated magnetite were hemocompatible and produced no hemolysis, whereas the other MMS were hemolytic above 0.3 mg/mL of blood.     

Studies of magnetite nanoparticles synthesized by thermal decomposition of iron (III) acetylacetonate in tri(ethylene glycol)

In this paper, water-soluble magnetite nanoparticles have been directly synthesized by thermal decomposition of iron (III) acetylacetonate, Fe(acac)₃ in tri(ethyleneglycol). Size and morphology of the nanoparticles are determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements while the crystal structure is identified using X-ray diffraction (XRD). Surface charge and surface coating of the nanoparticles are recognized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectra (XPS) and zeta potential measurements. Magnetic properties are determined using vibrating sample magnetometer (VSM) and superconducting quantum interference device (SQUID) measurements. The results show that as-prepared magnetite nanoparticles are relatively monodisperse, single crystalline and superparamagnetic in nature with the blocking temperature at around 100 K. The magnetite nanoparticles are found to be highly soluble in water due to steric and electrostatic interactions between the particles arising by the surface adsorbed tri(ethyleneglycol) molecules and associated positive charges, respectively. Cytotoxicity studies on human cervical (SiHa), mouse melanoma (B16F10) and mouse primary fibroblast cells demonstrate that up to a dose of 80 μg/ml, the magnetic nanoparticles are nontoxic to the cells. Specific absorption rate (SAR) value has been calculated to be 885 and 539 W/gm for samples with the iron concentration of 1 and 0.5 mg/ml, respectively. The high SAR value upon exposure to 20 MHz radiofrequency signifies the applicability of as-prepared magnetite nanoparticles for a feasible magnetic hyperthermia treatment.     

Oxygen adsorption and oxidation reactions on Au(2 1 1) surfaces: Exposures using O2 at high pressures and ozone (O3) in UHV

Nanosized gold particles supported on reducible metal oxides have been reported to show high catalytic activity toward CO oxidation at low temperature. This has generated great scientific and technological interest, and there have been many proposals to explain this unusual activity. One intriguing explanation that can be tested is that of Nørskov and coworkers [Catal. Lett. 64 (2000) 101] who suggested that the “unusually large catalytic activity of highly-dispersed Au particles may in part be due to high step densities on the small particles and/or strain effects due to the mismatch at the Au-support interface”. In particular, their calculations indicated that the Au(2 1 1) stepped surface would be much more reactive towards O₂ dissociative adsorption and CO adsorption than the Au(1 1 1) surface. We have now studied the adsorption of O₂ and O₃ (ozone) on an Au(2 1 1) stepped surface. We find that molecular oxygen (O₂) was not activated to dissociate and produce oxygen adatoms on the stepped Au(2 1 1) surface even under high-pressure (700 Torr) conditions with the sample at 300-450 K. Step sites do bind oxygen adatoms more tightly than do terrace sites, and this was probed by using temperature programmed desorption (TPD) of O₂ following ozone (O₃) exposures to produce oxygen adatoms up to a saturation coverage of θ_O = 0.90 ML. In the low-coverage regime (θ_O ? 0.15 ML), the O₂ TPD peak at 540 K, which does not shift with coverage, is attributed to oxygen adatoms that are bound at the steps on the Au(2 1 1) surface. At higher coverages, an additional lower temperature desorption peak that shifts from 515 to 530 K at saturation coverage is attributed to oxygen adsorbed on the (1 1 1) terrace sites of the Au(2 1 1) surface. Although the desorption kinetics are likely to be quite complex, a simple Redhead analysis gives an estimate of the desorption activation energy, E_d, for the step-adsorbed oxygen of 34 kcal/mol and that for oxygen at the terraces near saturation coverage of 33 kcal/mol, values that are similar to others reported on Au surfaces. Low Energy Electron Diffraction (LEED) indicates an oxygen-induced step doubling on the Au(2 1 1) surface at low-coverages (θ_O = 0.08-0.17 ML) and extensive disruption of the 2D ordering at the surface for saturation coverages of oxygen (θ_O ? 0.9 ML). Overall, our results indicate that unstrained step sites on Au(2 1 1) surfaces of dispersed Au nanoparticles do not account for the novel reactivity of supported Au catalysts for CO oxidation.     

Preparation and characterization of biodegradable magnetic carriers by single emulsion-solvent evaporation

This paper describes a single emulsion-solvent evaporation protocol to prepare PEGylated biodegradable/biocompatible magnetic carriers by utilizing hydrophobic magnetite and a mixture of poly(D,L lactide-co-glycolide) (PLGA) and poly(lactic acid-block-polyethylene glycol) (PLA-PEG) (26:1 by mass) polymers. We characterized the magnetic microspheres in terms of morphology, composite microstructure, size and size distribution, and magnetic properties. Results show that the preparation produces magnetic microspheres with a good spherical morphology, small size (mean diameter of 1.2–1.5 μm) by means of large size distributions, and magnetizations up to 20–30 emu/g of microspheres.     

Separation of PCR-ready DNA from dairy products using magnetic hydrophilic microspheres and poly(ethylene glycol)-NaCl water solutions

Carboxyl group-containing magnetic nonporous poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) (P(HEMA-co-GMA)) and magnetic glass microspheres were used for the isolation of bacterial DNA. P(HEMA-co-GMA) microspheres were prepared by the dispersion polymerization in toluene/2-methylpropan-1-ol mixture in the presence of magnetite nanoparticles obtained by coprecipitation of Fe(II) and Fe(III) salts with ammonium hydroxide. Carboxyl groups were then introduced by oxidation of the microspheres with potassium permanganate. The most extensive DNA recovery was achieved at PEG 6000 concentrations of 12% or 16% and 2 M NaCl. The method proposed was used for bacterial DNA isolation from different dairy products containing Bifidobacterium and Lactobacillus cells. The presence of target DNA and the quality of isolated DNA were checked by polymerase chain reaction (PCR) amplification with specific primers.     

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.     

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.     

An experimental study of the dynamic properties of nanoparticle colloids with identical magnetization but different particle size

Measurements of the frequency dependent complex magnetic susceptibility, χ(ω)=χ′(ω)−iχ″(ω), have been used to determine the dynamic properties of three specially prepared 400 G (0.04 T) magnetic fluids. The samples, denoted by sample 1, sample 2 and sample 3, consisted of magnetite particles of mean diameter 6.4 nm, 7.5 nm and 9 nm respectively and were identical in terms of carrier liquid, surfactant and particle material.     

Size-controlled synthesis of superparamagnetic iron oxide nanoparticles and their surface coating by gold for biomedical applications

The size mono-dispersity, saturation magnetization, and surface chemistry of magnetic nanoparticles (NPs) are recognized as critical factors for efficient biomedical applications. Here, we performed modified water-in-oil inverse nano-emulsion procedure for preparation of stable colloidal superparamagnetic iron oxide NPs (SPIONs) with high saturation magnetization. To achieve mono-dispersed SPIONs, optimization process was probed on several important factors including molar ratio of iron salts [Fe³⁺ and Fe²⁺], the concentration of ammonium hydroxide as reducing agent, and molar ratio of water to surfactant. The biocompatibility of the obtained NPs, at various concentrations, was evaluated via MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay and the results showed that the NPs were non-toxic at concentrations <0.1 mg/mL. Surface functionalization was performed by conformal coating of the NPs with a thin shell of gold (∼4 nm) through chemical reduction of attached gold salts at the surface of the SPIONs. The Fe₃O₄ core/Au shell particles demonstrate strong plasmon resonance absorption and can be separated from solution using an external magnetic field. Experimental data from both physical and chemical determinations of the changes in particle size, surface plasmon resonance optical band, phase components, core–shell surface composition, and magnetic properties have confirmed the formation of the mono-dispersed core–shell nanostructure.     

Clustering of magnetic nanoparticles using a double hydrophilic block copolymer, poly(ethylene oxide)-b-poly(acrylic acid)

The use of a double hydrophilic block copolymer (DHBC), poly(ethylene oxide)-block-poly(acrylic acid) (PEO-b-PAA) to prepare magnetic nanoparticle (MNP) clusters was investigated. In this one-pot synthesis method, the DHBC controlled the particle growth and served as both stabilizer and clustering agent. Depending on the iron-to-polymer ratio, the synthesized particles can be in the form of colonies of small iron oxide particles or clusters of these particles with size larger than 100 nm. Compared to the previous reported result using random copolymers, the clusters prepared with DHBC were more compact and homogeneous. The yield of clusters increased when the amount of polymer added was limiting. Insufficient amounts of polymer resulted in the formation of bare patches on the magnetite surface, and the strong van der Waals attraction induced cluster formation.     

In vitro study of magnetic particle seeding for implant assisted-magnetic drug targeting

The concept of using magnetic particles (seeds) as the implant for implant assisted-magnetic drug targeting (IA-MDT) was analyzed in vitro. Since this MDT system is being explored for use in capillaries, a highly porous (ε∼70%), highly tortuous, cylindrical, polyethylene polymer was prepared to mimic capillary tissue, and the seeds (magnetite nanoparticles) were already fixed within. The well-dispersed seeds were used to enhance the capture of 0.87 μm diameter magnetic drug carrier particles (MDCPs) (polydivinylbenzene embedded with 24.8 wt% magnetite) under flow conditions typically found in capillary networks. The effects of the fluid velocity (0.015–0.15 cm/s), magnetic field strength (0.0–250 mT), porous polymer magnetite content (0–7 wt%) and MDCP concentration (C=5 and 50 mg/L) on the capture efficiency (CE) of the MDCPs were studied. In all cases, when the magnetic field was applied, compared to when it was not, large increases in CE resulted; the CE increased even further when the magnetite seeds were present. The CE increased with increases in the magnetic field strength, porous polymer magnetite content and MDCP concentration. It decreased only with increases in the fluid velocity. Large magnetic field strengths were not necessary to induce MDCP capture by the seeds. A few hundred mT was sufficient. Overall, this first in vitro study of the magnetic seeding concept for IA-MDT was very encouraging, because it proved that magnetic particle seeds could serve as an effective implant for MDT systems, especially under conditions found in capillaries.     

Production of magnetic microspheres by ultrasonic atomisation

Magnetic microspheres, with mean particle sizes from 23 to 32 μm were produced by the ultrasonic atomisation of a suspension of magnetite particles, of approximately 200 nm diameter, in a solution of poly–l–lactic acid (PLLA). The mean particle diameter and the width of the particle diameter distribution both increased with increasing magnetite concentration. The particles appear to be suitable for magnetic hyperthermic treatment of liver cancers, with the hysteresis loop areas increasing linearly with nominal magnetite concentration up to 30 wt% magnetite.     

The study on magnetite particles coated with bilayer surfactants

Magnetite particles were prepared by co-precipitation, then sodium oleic (SO) and sodium dodecyl benzene sulfonate (SDBS) were applied as inner and outer surfactants, respectively. IR and TG were used to study the surface adsorption of SO and SDBS on magnetite particles. The experimental results demonstrated that SO molecules were linked to the magnetite particles through chemical bond and SDBS coated on the surface of magnetite particles covered with SO by means of Van der Waals attraction. Furthermore, based on the adsorption isotherms of surfactants on the magnetite particles and the dependence of Zeta potential of particles on the surfactants concentrations, the adsorption mechanisms of these two surfactants on the magnetite particles were studied. The isotherm adsorption model for SO on magnetite particles showed excellent correlation to Langmuir type and the adsorption equation was (25 °C), while that for SDBS on magnetite particles coated with SO showed excellent consistence with Freundlich type and the adsorption equation was Γ = 0.32c^0.475 (25 °C). In addition, the results demonstrated that both SO and SDBS formed monolayer adsorption on the surface of magnetite particles.     

Synthesis of magnetic and lightweight hollow microspheres/polyaniline/Fe3O4 composite in one-step method

After hollow microspheres (HM) were surface modified, a layer of electromagnetic polyaniline/Fe₃O₄ composite (PAN/Fe₃O₄) was successfully grafted onto the surface of the self-assembled monolayer coated HM, resulting in HM/PAN/Fe₃O₄ composites. In this approach, γ-aminopropyltriethoxy silane was adopted to form a well-coating monolayer with amino groups for the graft polymerization of aniline, which played an important role in fabricating the core-shell structure. FeCl₃ was used as the oxidant not only for aniline to form PAN, but also for FeCl₂ to prepare the magnets. The structure, morphologies, and magnetic properties of the as-prepared samples were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and vibrating sample magnetometer. The results indicated that the HM/PAN/Fe₃O₄ composites possess low density (ρ < 1.0 g/cm³), controllable morphology, and good magnetic properties at room temperature (saturation magnetization Ms = 8.32 emu g⁻¹ and coercive force Hc ≈ 0).     

Ni–Zn–Sm nanopowder ferrites: Morphological aspects and magnetic properties

Ni–Zn ferrites have been widely used in components for high-frequency range applications due to their high electrical resistivity, mechanical strength and chemical stability. Ni–Zn ferrite nanopowders doped with samarium with a nominal composition of Ni_0.5Zn_0.5Fe_2−xSm_xO₄ (x=0.0, 0.05, and 0.1 mol) were obtained by combustion synthesis using nitrates and urea as fuel. The morphological aspects of Ni–Zn–Sm ferrite nanopowders were investigated by X-ray diffraction, nitrogen adsorption by BET, sedimentation, scanning electron microscopy and magnetic properties. The results indicated that the Ni–Zn–Sm ferrite nanopowders were composed of soft agglomerates of nanoparticles with a high surface area (55.8–64.8 m²/g), smaller particles (18–20 nm) and nanocrystallite size particles. The addition of samarium resulted in a reduction of all the magnetic parameters evaluated, namely saturation magnetization (24–40 emu/g), remanent magnetization (2.2–3.5 emu/g) and coercive force (99.3–83.3 Oe).     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.