Maghemite nanoparticles protectively coated with poly(ethylene imine) and poly(ethylene oxide)-block-poly(glutamic acid)

Superparamagnetic iron oxide particles (SPIO) of maghemite were prepared in aqueous solution and subsequently stabilized with polymers in two layer-by-layer deposition steps. The first layer around the maghemite core is formed by poly(ethylene imine) (PEI), and the second one is formed by poly(ethylene oxide)-block-poly(glutamic acid) (PEO-PGA). The hydrodynamic diameter of the particles increases stepwise from D(h) = 25 nm (parent) via 35 nm (PEI) to 46 nm (PEI plus PEO-PGA) due to stabilization. This is accompanied by a switching of their zeta-potentials from moderately positive (+28 mV) to highly positive (+50 mV) and finally slightly negative (-3 mV). By contrast, the polydispersity indexes of the particles remain constant (ca. 0.15). M?ssbauer spectroscopy revealed that the iron oxide, which forms the core of the particles, is only present as Fe(III) in the form of superparamagnetic maghemite nanocrystals. The magnetic domains and the maghemite crystallites were found to be identical with a size of 12.0 +/- 0.5 nm. The coated maghemite nanoparticles were tested to be stable in water and in physiological salt solution for longer than 6 months. In contrast to novel methods for magnetic nanoparticle production, where organic solvents are necessary, the procedure proposed here can dispense with organic solvents. Magnetic resonance imaging (MRI) experiments on living rats indicate that the nanoparticles are useful as an MRI contrast agent.     

Water-Soluble Magnetic Nanocomposites Based on Carboxymethyl Cellulose and Iron(III) Oxide

The one-step synthesis of water-soluble composites from maghemite (γ-Fe₂O₃) nanoparticles with a diameter of 12 ± 4 nm and a biocompatible polysaccharide, namely, sodium salt of carboxymethyl cellulose, is described. The role of the polymer matrix consists in stabilization of the resulting nanoparticles by the electrostatic interaction of polymer carboxyl groups with the surface atoms of iron in the (3+) oxidation state. The dissolution of the composites in water affords aggregatively stable dispersions responding to the external magnetic field. The content of the magnetic phase (iron oxide) in the formulation of the maghemite–carboxymethyl cellulose composite is defined by the ratio of components during the synthesis.     

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     

Maghemite (hematite) core (shell) nanorods via thermolysis of a molecular solid of Fe-complex

An Fe-metal complex with 2'-hydroxy chalcone (2'-HC) ligands [Fe(III) (2'-hydroxy chalcone)(3)] is synthesized by a chemical route and is subjected to different thermal treatments. Upon thermolysis in air at 450 °C for 3 h the complex yields maghemite (γ-Fe(2)O(3)) nanorods with a thin hematite (α-Fe(2)O(3)) shell. X-Ray diffraction (XRD), M?ssbauer spectroscopy, diffuse reflectance spectroscopy (UV-DRS), high resolution transmission electron microscopy (HR-TEM), field emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometry (VSM) are used to characterize the samples. The stability of the ligand and the Fe-complex is further examined by using thermogravimmetric/differential thermal analysis (TGA/DTA). We suggest a residual ligand controlled mechanism for the formation of an anisotropic nanostructure in a crumbling molecular solid undergoing ligand decomposition. Since the band gap of iron oxide is in the visible range, we explored the use of our core shell nano-rod sample for photocatalytic activity for H(2) generation by H(2)S splitting under solar light. We observed high photocatalytic activity for hydrogen generation (75 ml h(-1)).     

Hamaker constants of iron oxide nanoparticles

The Hamaker constants for iron oxide nanoparticles in various media have been calculated using Lifshitz theory. Expressions for the dielectric responses of three iron oxide phases (magnetite, maghemite, and hematite) were derived from recently published optical data. The nonretarded Hamaker constants for the iron oxide nanoparticles interacting across water, A(1w1) = 33 - 39 zJ, correlate relatively well with previous reports, whereas the calculated values in nonpolar solvents (hexane and toluene), A(131) = 9 - 29 zJ, are much lower than the previous estimates, particularly for magnetite. The magnitude of van der Waals interactions varies significantly between the studied phases (magnetite < maghemite < hematite), which highlights the importance of a thorough characterization of the particles. The contribution of magnetic dispersion interactions for particle sizes in the superparamagnetic regime was found to be negligible. Previous conjectures related to colloidal stability and self-assembly have been revisited on the basis of the new Lifshitz values of the Hamaker constants.     

Phase behavior of nanoparticles in a thermotropic liquid crystal

In this work, we describe the outstanding behavior of a nanocomposite system composed of the thermotropic liquid crystal 5CB doped with nanoparticles of the magnetic iron oxide maghemite (gamma-Fe(2)O(3)). We show that the I-N transition is associated with a reversible gathering of nanoparticles inside droplets of the ferronematic phase coexisting with a nonmagnetic nematic host phase.     

2‐Arylation/alkylation of benzothiazoles using superparamagneticgraphene oxide‐Fe3O4 hybrid material as a heterogeneous catalystwith diisopropyl azodicarboxylate (DIAD) as an oxidant

In this report, we introduced Graphene oxide‐iron oxide (GO‐Fe₃O₄) nanocomposites as a heterogeneous catalyst for arylation/alkylation of benzothiazoles with aldehydes and benzylic alcohols in the presence of diisopropyl azodicarboxylate (DIAD) as an oxidant which exclusively produced 2‐aryl (alkyl)‐1H–benzothizoles in moderate to excellent yields. The absence of precious metals and toxic solvent, easy product isolation, and recyclability of the GO‐Fe₃O₄ with no loss of activity are notable advantages of this method.     

Magnetic poly(2‐hydroxyethyl methacrylate‐co‐ethylene dimethacrylate) microspheres by dispersion polymerization

Crosslinked poly(2‐hydroxyethyl methacrylate)‐based magnetic microspheres were prepared in a simple one‐step procedure by dispersion polymerization in the presence of several kinds of iron oxides. Cellulose acetate butyrate and dibenzoyl peroxide were used as steric stabilizer and polymerization initiator, respectively, and ethylene dimethacrylate was a crosslinking agent. The resulting product was characterized in terms of particle size, particle size distribution, iron(III) content, and magnetic properties. In the presence of needle‐like maghemite in the polymerization mixture and under suitable conditions, magnetic microspheres with relatively narrow size distribution were formed. An increase in the particle size and, at the same time, a decrease in molecular weight of uncrosslinked polymers resulted, as the continuous phase became richer in 2‐methylpropan‐1‐ol. Coercive force of needle‐like maghemite‐containing particles was higher than that of cubic magnetite‐loaded microspheres. Coercive force increased with the decreasing iron content in the particles. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1161–1171, 2000     

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.     

Co(II), Fe(III) or VO(II) Schiff base metal complexes immobilized on graphene oxide for styrene epoxidation

Cobalt(II), iron(III) or oxovanadium(II) Schiff base metal complexes have been covalently grafted onto graphene oxide ( GO ) previously functionalized with 3‐aminopropyltriethoxysilane. Potential catalytic behaviors were tested in the epoxidation of styrene, using air as the oxidant. The catalysts were characterized using infrared (IR) and Raman spectroscopies, thermogravimetric analyses, inductively coupled plasma atomic emission spectrometry (ICP‐AES), X‐ray diffraction, nitrogen adsorption–desorption, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). IR spectroscopy, thermogravimetric analyses and ICP‐AES confirmed the successful incorporation of the metal Schiff base complexes onto GO . X‐ray diffraction, nitrogen adsorption–desorption, Raman spectroscopy, SEM and TEM showed the intact structure of the GO . Co-GO and Fe-GO showed high styrene conversion (90.8 versus 86.7%) and epoxide selectivity (63.7 versus 51.4%). Nevertheless, VO-GO showed poorer catalytic performance compared with Co-GO and Fe-GO . The recycling results of these heterogeneous catalysts showed good recoverability without significant loss of activity and selectivity within four successive runs. Copyright © 2015 John Wiley & Sons, Ltd.     

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.

A general nonaqueous route to binary metal oxide nanocrystals involving a C-C bond cleavage

A widely applicable solvothermal route to nanocrystalline iron, indium, gallium, and zinc oxide based on the reaction between the corresponding metal acetylacetonate as metal oxide precursor and benzylamine as solvent and reactant is presented. Detailed XRD, TEM, and Raman studies prove that, with the exception of the iron oxide system, where a mixture of the two phases magnetite and maghemite is formed, only phase pure materials are obtained, gamma-Ga(2)O(3), zincite ZnO, and cubic In(2)O(3). The particle sizes lie in the range of 15-20 nm for the iron, 10-15 nm for the indium, 2.5-3.5 nm for gallium, and around 20 nm for zinc oxide. GC-MS analysis of the final reaction solution after removal of the nanoparticles showed that the composition is rather complex consisting of more than eight different organic compounds. Based on the fact that N-isopropylidenebenzylamine, 4-benzylamino-3-penten-2-one, and N-benzylacetamide were the main species found, we propose a detailed formation mechanism encompassing solvolysis of the acetylacetonate ligand, involving C-C bond cleavage, as well as ketimine and aldol-like condensation steps.     

Determination of metallic iron, iron(II) oxide, and iron(III) oxide in a mixture

A procedure is described for the estimation of metallic iron, ferrous oxide, and ferric oxide when present together. The sample is treated with bromine dissolved in ethanol, and filtered. Iron in the filtrate is titrated iodometrically, and corresponds to the metallic iron present in the mixture. The oxide residue is dissolved in hydrochloric acid under a carbon dioxide atmosphere. The iron(II) formed, equivalent to FeO present, is titrated with a standard vanadate solution, and the total iron(III) (FeO + Fe₂O₃) in the titrated solution is then estimated iodometrically.     

Synthesis and characterization of graphene oxide/modified poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) nanocomposite

In this study, the graphene oxide/poly(N-isopropylacrylamide) nanocomposite modified with 2-mercaptoethanol (GO/MPNIPAM) was synthesized in three stages. N-Isopropylacrylamide polymerization was firstly performed in the presence of azobisisobutyronitrile as an initiator, which was discovered by Homer, and 2-mercaptoethanol as a modifier. Then, the graphene oxide/modified polymer nanocomposite was synthesized by the covalent interactions between carboxylic acids of the graphene oxide and hydroxyl groups of the modified polymer during the esterification reaction. The GO/MPNIPAM nanocomposite includes some percentage of the polymer that improves solubility and stability of the GO sheets in physiological applications; due to the interaction between the MPNIPAM and the modified GO polymer, a bridge-like connection is formed between the GO sheets and the process that leads to remove a large number of hydrophilic groups on the GO nanocomposite and therefore, the GO/MPNIPAM is well dissolved in organic solvents. This property is beneficial for anti-cancer drug delivery as well as π–π interactions between the nanocomposite and aromatic drugs. The nanocomposite is not a toxic material for human body at all and has high capacity for drug delivery. Structure and morphology of the nanocomposite were studied by FTIR, SEM, XRD, UV, TGA and Raman analysis. The analysis done by X-ray diffraction pattern confirmed the presence of graphene oxide in nanocomposites and improved crystalline polymer in nanocomposites.     

Adsorption of microcystin-Lr onto iron oxide nanoparticles

In this study, the adsorption of microcystin-LR onto iron oxide (maghemite) nanoparticles from water was examined. Factors influencing the sorption behavior included microcystin and maghemite concentration, pH, ionic strength, and the presence of natural organic matter. Adsorption of microcystin-LR was strongly affected by pH. The adsorption increased with decreasing pH, with a maximum adsorption around pH 3. Adsorption of microcystin-LR on maghemite was primarily attributed to electrostatic interactions, although hydrophobic interactions may also play a role. The extent of microcystin-LR adsorption onto maghemite increased with increasing ionic strength at pH 6.4, since salt ions screened the electrostatic repulsion between adsorbed microcystin molecules. Adsorption of microcystin-LR was not significantly affected by the presence of Suwannee River Fulvic acid (SRFA) below 2.5 mg/L. However, adsorption decreased at higher SRFA concentrations (2.5–25 mg/L) due to competitive adsorption between SRFA and microcystin-LR for limited sorption sites.     

Study of kinetic,thermodynamic, and isotherm of Sr adsorption from aqueous solutions on graphene oxide (GO) and (aminomethyl)phosphonic acid–graphene oxide (AMPA–GO)

Journal of Radioanalytical and Nuclear Chemistry - In this work, graphene oxide (GO) and (aminomethyl)phosphonic acid–Graphene oxide (AMPA–GO) adsorbents were prepared by the modified...     

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.     

Graphene oxide assisted facile hydrothermal synthesis of LiMn_(0.6)Fe_(0.4)PO_4 nanoparticles as cathode material for lithium ion battery

Assisted by graphene oxide(GO),nano-sized LiMn_(0.6)Fe_(0.4)PO_4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn_(0.6)Fe_(0.4)PO_4(S2)was about 80 nm in diameter.The discharge capacity of LiMn_(0.6)Fe_(0.4)PO_4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn_(0.6)Fe_(0.4)PO_4 and it in situ reduction of GO could improve the electrical conductivity of LiMn_(0.6)Fe_(0.4)PO_4 material.     

Zirconium (IV) porphyrin graphene oxide: a new and efficient catalyst for the synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones

A covalently cross‐linked graphene oxide (GO) as a catalyst was prepared by a cross‐linking process using the nucleophilic reaction of zirconium (IV)‐coordinated 5,10,15,20‐tetrakis (aminophenyl)porphyrin (ZrPPh) with carboxyl groups of the edges of GO (GO‐ZrPPh). The chemical structure of catalyst was characterized by different analyses such as FT‐IR, SEM, TEM, EDS, ICP, TGA and UV. All analyses confirm the occurrence of successfully covalent immobilization of ZrPPh on the GO. Also, TEM and SEM images show that ZrPPh has been immobilized in the both of the edges and the basal plane of GO. The activity of the catalyst was studied for the synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones via Biginelli reaction. The cross‐linked catalyst is able to catalyze the reaction in short reaction times and good to excellent yields.     

Infrared study of the thermal transformation of goethite to magnetite in alkali-iodide disks

Synthetic and natural goethites (0.5–1.5 mg) were heated up to 600°C in alkali-halide disks (400 mg). The thermal transformations occurring at different temperatures are found to depend on the preparation of the disks. For mixtures of alkali-halides and goethite not ground during the preparation of the disks, heating at >200°C resulted in protohematite, which persisted up to 600°C. However, disks which were subjected to repeated grinding—pressing cycles before thermal treatments gave rise to protohematite at >200°C, which on further heating at >300°C was transformed to a transitional iron oxide. In CsI disks, the transitional oxide derived from synthetic goethite can be further transformed to maghemite at 500°C; however, almost no maghemite could be obtained from natural goethite. At 600°C, both the transitional oxide and the maghemite resulting from the synthetic goethite in CsI disks were reduced to magnetite. On the other hand, in KI disks, transitional oxides obtained from both synthetic and natural goethites were reduced to magnetite upon re-pressing and gradual heating of the disks at 600°C. In KI disks, magnetite can be formed only if the reduction temperature is reached gradually, whereas in CsI disks magnetite is formed upon direct heating of the disks to 600°C. The iron oxides referred to above, including the transitional oxides resulting from thermal treatments, were studied by IR absorption spectroscopy.