Surface modification of iron oxide nanoparticles by a phosphate‐based macromonomer and further encapsulation into submicrometer polystyrene particles by miniemulsion polymerization

A new strategy relying on the use of a phosphate‐based macromonomer (PAM200) to modify the surface of iron oxide nanoparticles was developed for the synthesis of submicrometer polystyrene (PS) magnetic particles. First, iron oxide nanoparticles were synthesized using the coprecipitation of ferrous and ferric salts in alkaline medium. Besides the classical oleic acid (OA)/octane‐based ferrofluid, styrene‐based ferrofluids were elaborated with either OA or PAM200 as the stabilizer. In all cases, maghemite (γ‐Fe₂O₃) was clearly identified, with nanoparticles rather spherical in shape but exhibiting broad particle size distribution (PSD). Both OA and PAM200 led to stable maghemite‐based ferrofluids showing superparamagnetic properties. Further use of these ferrofluids in styrene miniemulsion polymerization resulted in inhomogeneous distribution of maghemite among and inside the polymer particles with OA‐based ferrofluids, whereas PAM200/styrene‐based ferrofluids led to magnetic particles with homogeneous distribution of maghemite inside PS particles. Broad PSD and small nonmagnetic particles were however observed. The true mechanisms operating in these systems are still to elucidate, but this study validates PAM200 as an efficient compatibilizing agent between hydrophilic maghemite and hydrophobic PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 327–340, 2008     

Mechanochemical synthesis of ferromagnetic semiconducting material from polymer and nanosized iron particles

Mechanochemical synthesis, magnetic and electrical properties of organic polymer-based semiconductors containing para- and ferromagnetic particles have been considered. Semiconductors have been obtained from polyaniline (emeraldine base), polystyrene, FeCl₃ · 6H₂O, and elemental sulfur. The presence of iron nanoparticles is confirmed by means of scanning electron microscopy. The conductivity of polymer composites containing iron particles turns out to be several orders of magnitude higher than that of the initial undoped polyaniline. The temperature dependence of conductivity of composites exhibits the semiconducting pattern.     

Nonhydrolytic sol–gel and gram-scale synthesis of surfactant-free maghemite nanoparticles with high surface area

An organic molecule was used as a surfactant for nanoparticle synthesis in liquid phase. However, residual molecules on the surface of the nanoparticles limit their catalytic applications, because the interaction of a reactant with the nanoparticle surface is interrupted. Therefore, it is favorable for catalytic applications that the organic molecule used in the synthesis of nanoparticles only induces a sol–gel reaction of the metal precursors and the formation of nanoparticles and hardly adheres to the resulting nanoparticles. Herein, we report surfactant-free and high-surface area maghemite nanostructures via nonhydrolytic sol–gel reaction. Using Fe(acetylacetonate)₃ as an iron precursor and hexylamine as a solvent and growth inhibitor, Fe₂O₃ nanoparticles were generated by nonhydrolysis of the iron complex and condensation at 140 °C under an air atmosphere. Characterization revealed monodisperse nanoparticles with an average size of 2.3 nm and a crystalline phase of maghemite. Residual hexylamine is hardly observed, and thus their specific surface area is 403.7 m²/g. An experimental comparison of the Fe₂O₃ synthesis with hexylamine and benzylamine indicates that the cone angle of an organic molecule is an important factor in the synthesis of nanoparticles with a small size and high surface area.     

Synthesis of silanized maghemite nanoparticles onto reduced graphene sheets composites

Novel γ-Fe₂O₃@APTES@rGO composites are successfully synthesized by using graphene oxide and silanized maghemite nanoparticles. Graphene oxide and maghemite were obtained by Hummers and Massart methods, respectively. The silanization process was done to functionalize maghemite surface with a controllable quantity of amino groups. Then, by adding aqueous graphene oxide suspension, the bonding between graphene oxide and silanized maghemite nanoparticles was done in refluxing conditions. Afterwards, chemical reduced graphene oxide reaction was realized by addition of hydrazine solution. The characterization of γ-Fe₂O₃@APTES@rGO composites was studied by X-ray Diffraction, Fourier Transformed Infrared Spectroscopy, thermogravimetric analysis and scanning electron microscopy.     

Biodegradable magnetic gel: synthesis and characterization

Biodegradable polymer-based magnetic gels have been synthesized using hydroxypropyl cellulose and maghemite. These magnetic gels have a network of nanoparticles of hydroxypropyl cellulose (30–100 nm) and a homogeneous distribution of nanosized maghemite (~7 nm). This has been observed in a STEM micrograph. The surface structure of the gels has been observed by atomic force microscopy, while transmission electron microscopy has shown the distribution of iron oxide in HPC gel nanoparticles. These gels have magneto-elastic properties. The magnetic susceptibility and magnetization of these gels are measured by a superconducting quantum interference device magnetometer.     

Microwave-assisted one-step hydrothermal synthesis of pure iron oxide nanoparticles: magnetite, maghemite and hematite

A simple, rapid, one-step synthesis way of pure iron oxide nanoparticles: magnetite (Fe₃O₄), maghemite (γ-Fe₂O₃) and hematite (α-Fe₂O₃) was investigated. Nanoparticles were prepared by microwave synthesis, from ethanol/water solutions of chloride salts of iron (FeCl₂ and FeCl₃) in the presence of sodium hydroxide NaOH. X-ray powder diffraction (XRD), Transmission Electron Microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize these nanoparticles.     

Grafting of poly(ε‐caprolactone) onto maghemite nanoparticles

We report the coating of maghemite (γ‐Fe₂O₃) nanoparticles with poly(ε‐caprolactone) (PCL) through a covalent grafting to technique. ω‐Hydroxy‐PCL was first synthesized by the ring‐opening polymerization of ε‐caprolactone with aluminum isopropoxide and benzyl alcohol as a catalytic system. The hydroxy end groups of PCL were then derivatized with 3‐isocyanatopropyltriethoxysilane in the presence of tetraoctyltin. The triethoxysilane‐functionalized PCL macromolecules were finally allowed to react on the surface of maghemite nanoparticles. The composite nanoparticles were characterized by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). Effects of the polymer molar mass and concentration on the amount of polymer grafted to the surface were investigated. Typical grafting densities up to 3 μmol of polymer chains per m² of maghemite surface were obtained with this grafting to technique. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6011–6020, 2004     

Fabrication and characterization of CMC‐based magnetic superabsorbent hydrogel nanocomposites for crystal violet removal

In this research work, novel magnetic superabsorbent hydrogel nanocomposites (MSHNs) based on carboxymethyl cellulose were prepared via a facile “one‐pot” two step approach. Magnetic iron oxide nanoparticles were in situ synthesized and incorporated into carboxymethyl cellulose/poly(acrylic acid) polymer hydrogel. The morphology and chemical composition of MSHNs as well as the presence of magnetic iron oxide nanoparticles were evaluated by using Fourier transform infrared, scanning electron microscopy, transmission electron microscopy, X‐Ray diffraction, ultraviolet–visible spectroscopy, thermogravimetric analysis, and vibrating sample magnetometer. The effect of different reaction parameters on the swelling capacity of MSHNs was investigated. Furthermore, batch adsorption experiments of crystal violet dye onto MSHNs were studied by varying solution pH, initial dye concentration, and temperature. Evaluation of thermodynamic parameters of crystal violet adsorption confirmed that the adsorption was spontaneous and endothermic process in nature. The equilibrium study revealed that the dye adsorption behavior of MHSNs followed the Redlich‐Peterson isotherm model. Finally, the dye adsorption experiment data was well fitted by the pseudo‐second‐order kinetic model with the regression coefficient (R²) of 0.9979. Our results suggest that the MHSNs with facile preparation method, high swelling capacity, and high dye adsorption capacity may be used as promising adsorbents for fast removal of various dyes from aqueous solutions. Copyright © 2016 John Wiley & Sons, Ltd.     

Infrared laser synthesis and properties of magnetic nano‐iron–polyoxocarbosilane composites

Nano‐magnetic, thermally stable iron‐based composites were obtained by a one‐step procedure consisting of continuous‐wave infrared laser‐induced and ethylene‐sensitized co‐pyrolysis of gaseous iron pentacarbonyl and hexamethyldisiloxane in argon. The simultaneously occurring formation of iron from iron pentacarbonyl and that of organosilicon polymer from hexamethyldisiloxane yield iron nanoparticles surrounded by an organosilicon polymer shell. The particles were characterized by spectral analyses, electron microscopy, thermal gravimetry and magnetic measurements. They become superficially oxidized in the atmosphere. Their composition, thermal behaviour and magnetic properties depend on the flow rates of the precursors and the total pressure of the procedure. Magnetization curves, exchange bias H_ex at T = 5 K and AC susceptibility were studied in the temperature range 5–400 K. The values of H_ex verified the observed degree of the particle surface oxidation. The system of the iron nanoparticles is in a ferromagnetic blocked state and the temperature dependence of the coercivity and susceptibility is in accord with the transmission electron microscopy data. Copyright © 2005 John Wiley & Sons, Ltd.     

Solid–liquid phase diagrams of binary mixtures

This study investigates the sorption of toluene and naphthalene by a sodium bentonite (BFN), an organoclay (WS35) and by their respective iron oxide hydrate composites Mag_BFN and Mag_S35. The organic matter content of WS35 and Mag_S35, determined by thermogravimetry, was used to obtain their organic matter sorption coefficients, which show that they are effective sorbents to remove organic contaminants from water, with a higher selectivity for naphthalene than for toluene sorption. The main iron oxide phase present in Mag_BFN and Mag_S35 is maghemite (γ-Fe₂O₃), which allows these sorbents to be separated from the effluent by a magnetic separation process after use.     

An investigation on polycaprolactone/chitosan/Fe3O4 nanofibrous composite used for hyperthermia

Hyperthermia is considered as an effective supplementary cancer treatment. However, the uneven temperature distribution is the major challenge in hyperthermia. Nanotechnology could solve this problem by applying magnetic nanoparticles directly or in nanofibers as implants. Low solubility, poor cancer targeting, and leakage are limitations of free magnetic nanoparticles. In this work, Fe₃O₄ nanoparticles were loaded into polycaprolactone/chitosan blended nanofibers in various contents. Magnetic, chemical, physical, and morphology of the derived nanofibrous composites were then studied. The results showed the magnetic properties of the nanocomposite had low coercivity, which was close to superparamagnetic particles. Chemical analysis showed that components had no interaction with each other. Nevertheless, Fe₃O₄ was slightly transformed to other iron oxides. However, the magnetic analysis showed this transformation had no significant effect on final magnetic content of the nanofibers. The results of X‐ray diffraction (XRD) (19.5 nm), transmittance electron microscopy (TEM) (21.6 nm), and vibration sample magnetometer (VSM) (17 nm) suggested that the magnetic nanoparticles were single domain. Thermal analysis results showed that 7% Fe₃O₄ nanofibers had more heat increase as oppose to other nanofibrous composites in the alternative magnetic field (AMF). Nonetheless, the heat performance of 3% Fe₃O₄ nanofibers was more than others according to its specific power absorption (SPA). Therefore, due to the importance of using nanoparticles in the least possible content, this method can be used as a postsurgical treatment by applying these nanofibrous composites as implants on the tumor site. Moreover, these nanofiber composites could carry anticancer drugs, which are applied as a multi‐mode treatment system.     

A molecularly imprinted polymer-coated nanocomposite of magnetic nanoparticles for estrone recognition

In this study, we synthesized Fe₃O₄ magnetic nanoparticles coated estrone-imprinted polymer with controlled size using a semi-covalent imprinting strategy. In this protocol, the estrone-silica monomer complex (EstSi) was synthesized by the reaction 3-(triethoxysilyl)propyl isocyanate with estrone, where the template was linked to the silica coating on the iron oxide core via a thermally reversible bond. The removal of the template by a simple thermal reaction produced specific estrone recognition sites on the surface of silica shell.The resulting estrone-imprinted polymer coating Fe₃O₄ magnetic hybrid nanoparticles exhibit a much higher specific recognition and saturation magnetization. The hybrid nanoparticles have been used for biochemical separation of estrone.     

Iron oxide film growth under ultrathin polysiloxane networks

This study focuses on the preparation and characterization of magnetic switchable thin iron oxide–polymer films. In a series of experiments, the formation and growth of iron oxide under ultrathin polysiloxane layers was controlled by changing the concentration of iron ions in the aqueous subphase or by varying the residence time of ammonia in the gas phase above the liquid sample. The growth of the combined film structures is studied in situ by interfacial rheology, optical microscopy, and x-ray scattering experiments and ex situ by scanning electron microscopy. Different stages of iron oxide aggregation, from a very thin layer of amorphous iron oxide with thickness of a few nanometers up to micrometer thick coatings of crystalline maghemite (γ-Fe₂O₃) were investigated. The specific interactions between the inorganic iron oxide and the polymer membranes cause the creation of new composite materials which are sensitive to magnetic forces.

Cellulose/silver nanoparticles composite microspheres: eco-friendly synthesis and catalytic application

Cellulose/silver nanoparticles (Ag NPs) composites were prepared and their catalytic performance was evaluated. Porous cellulose microspheres, fabricated from NaOH/thiourea aqueous solution by a sol–gel transition processing, were served as supports for Ag NPs synthesis by an eco-friendly hydrothermal method. The regenerated cellulose microspheres were designed as reducing reagent for hydrothermal reduction and also micro-reactors for controlling growth of Ag NPs. The structure and properties of obtained composite microspheres were characterized by Optical microscopy, UV–visible spectroscopy, WXRD, SEM, TEM and TG. The results indicated that Ag NPs were integrated successfully and dispersed uniformly in the cellulose matrix. Their size (8.3–18.6?nm), size distribution (3.4–7.7?nm), and content (1.1–4.9?wt%) were tunable by tailoring of the initial concentration of AgNO₃. Moreover, the shape, integrity and thermal stability were firmly preserved for the obtained composite microspheres. The catalytic performance of the as-prepared cellulose/Ag composite microspheres was examined through a model reaction of 4-nitrophenol reduction in the presence of NaBH₄. The composites microspheres exhibited good catalytic activity, which is much high than that of hydrogel/Ag NPs composites and comparable with polymer core–shell particles loading Ag NPs.     

Preparation and characterization of cellulose-ZnO nanocomposite based on ionic liquid ([C4mim]Cl)

Cellulose-ZnO composite was achieved by microwave assisted dissolution of cellulose in ionic liquid 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) followed by addition of premixed ground of Zn(CH₃COO)₂·2H₂O and NaOH. Surface characterization, optical property and thermal stability of nanocomposite were determined by X-ray diffraction, scanning electron microscopy (SEM), UV–Vis spectroscopy and thermo gravimetric analysis. XRD patterns showed the ZnO in polymer matrix has the wurtzite structure. Presence of zinc oxide nanoparticles and cellulose fibers in the composites were observed by SEM. Band-edge transition of zinc oxide in the nanocomposite occurs in lower wavelength than bulk zinc oxide. Thermal stability of nanocomposite was lower than regenerated cellulose due to catalyst behavior of zinc oxide nanoparticles in cellulose matrix.     

In situ synthesis of plate-like Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles in porous cellulose films with obvious magnetic anisotropy

Nanocomposite cellulose films with obvious magnetic anisotropy have been prepared by in situ synthesis of plate-like Fe₂O₃ nanoparticles in the cellulose matrix. The influence of the concentrations of FeCl₂ and FeCl₃ solutions on the morphology and particle size of the synthesized Fe₂O₃ nanoparticles as well as on the properties of the composite films has been investigated. The Fe₂O₃ nanoparticles synthesized in the cellulose matrix was γ-Fe₂O₃, and its morphology was plate-like with size about 48 nm and thickness about 9 nm, which was totally different from those reported works. The concentration of FeCl₂ and FeCl₃ solution has little influence on the particle size and morphology of the Fe₂O₃ nanoparticles, while the content of Fe₂O₃ nanoparticles increased with the increase of the concentration of the precursor solution, indicating that porous structured cellulose matrix could modulate the growth of inorganic nanoparticles. The unique morphology of the Fe₂O₃ nanoparticles endowed the composite films with obvious magnetic anisotropy, which would expand the applications of the cellulose based nanomaterials.     

Fabrication of mesoporous SiO2–C–Fe3O4/γ–Fe2O3 and SiO2–C–Fe magnetic composites

A synthetic method for the fabrication of silica-based mesoporous magnetic (Fe or iron oxide spinel) nanocomposites with enhanced adsorption and magnetic capabilities is presented. The successful in situ synthesis of magnetic nanoparticles is a consequence of the incorporation of a small amount of carbon into the pores of the silica, this step being essential for the generation of relatively large iron oxide magnetic nanocrystals (10 ± 3 nm) and for the formation of iron nanoparticles. These composites combine good magnetic properties (superparamagnetic behaviour in the case of SiO₂–C–Fe₃O₄/γ–Fe₂O₃ samples) with a large and accessible porosity made up of wide mesopores (>9 nm). In the present work, we have demonstrated the usefulness of this kind of composite for the adsorption of a globular protein (hemoglobin). The results obtained show that a significant amount of hemoglobin can be immobilized within the pores of these materials (up to 180 mg g⁻¹ for some of the samples). Moreover, we have proved that the composite loaded with hemoglobin can be easily manipulated by means of an external magnetic field.     

Soap-free synthesis of highly monodisperse magnetic polymer particles with amphoteric initiator

A method applying soap-free emulsion polymerization with an amphoteric initiator, 2,2′-azobis[N-(2-carboxyethyl)-2-2-methyl-propionamidine], is proposed for synthesis of highly monodisperse particles composed of magnetic nanoparticles (Fe₃O₄/γ–Fe₂O₃) and polystyrene. The magnetic nanoparticles were pretreated by surface modification for introducing double bonds onto the particles. In the polymerization, magnetic nanoparticles were continuously supplied to the system for a certain period after the initiation of polymerization at various pH. Dissociation degrees of ionizable groups in the initiator molecules were controlled through pH by changing NH₃ concentrations at a constant NH₄Cl concentration. Selection of suitable pH in the polymerization could produce polymer particles that perfectly incorporated the supplied magnetic nanoparticles. The magnetic polymer particles had a coefficient of variation of size distribution as low as 4.3% with an average diameter of 515 nm and a saturation magnetization of 7.3 emu/g-sample. Electrophoresis measurements indicated that the magnetic polymer particles had an isoelectric point of pH 4.1.     

Synthesis of polyhedral iron oxide nanocrystals bound by high-index facets

High surface energy of high-index facets endows nanocrystals with high activities and thus promotes potential applications such as highly efficient catalysts,special optical,electrical and magnetic devices.But the high surface energy of the high-index facets usually drives them to grow faster than the other facets and finally disappear during the crystal growth,which leads the synthesis of nanocrystals with high-indexed facets exposed to be a great challenge.Herein,we introduced two routes to control the synthesis of-Fe2O3polyhedrons with different sets of high-index facets,one using different metal ions(Ni2+,Cu2+or Zn2+)as structure-directing agents and the other applying polymer surfactant sodium carboxymethyl cellulose(CMC)as additive.The growth process of high-index-Fe2O3polyhedrons was also discussed and possible growth mechanism was proposed.     

Synthesis and characterization of micron‐sized monodisperse superparamagnetic polymer particles with amino groups

Micron‐sized monodisperse superparamagnetic polyglycidyl methacrylate (PGMA) particles with functional amino groups were prepared by a process involving: (1) preparation of parent monodisperse PGMA particles by the dispersion polymerization method, (2) chemical modification of the PGMA particles with ethylenediamine (EDA) to yield amino groups, and (3) impregnation of iron ions (Fe²⁺ and Fe³⁺) inside the particles and subsequently precipitating them with ammonium hydroxide to form magnetite (Fe₃O₄) nanoparticles within the polymer particles. The resultant magnetic PGMA particles with amino groups were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X‐ray diffractometry (XRD), and vibrating sample magnetometry (VSM). SEM showed that the magnetic particles had an average size of 2.6 μm and were highly monodisperse. TEM demonstrated that the magnetite nanoparticles distributed evenly within the polymer particles. The existence of amino groups in the magnetic polymer particles was confirmed by FTIR. XRD indicated that the magnetic nanoparticles within the polymer were pure Fe₃O₄ with a spinel structure. VSM results showed that the magnetic polymer particles were superparamagnetic, and saturation magnetization was found to be 16.3 emu/g. The Fe₃O₄ content of the magnetic particles was 24.3% based on total weight. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3433–3439, 2005