Regioselective hydrothiolation of terminal acetylene catalyzed by magnetite (Fe3O4) nanoparticles

Herein, we report a new and solvent-free methodology for the preparation of vinyl thioethers from terminal alkynes and thiols, using magnetite (Fe₃O₄) nanoparticles as a recyclable catalyst. With this greener method, the desired vinyl thioethers were achieved in good yields and with good stereoselectivity. In addition, the catalyst was easily recovered using a simple external magnet and reused for further catalytic reactions without significant loss of activity up to the fifth cycle.     

Synthesis and Magnetic Properties of Pt3Co/Fe3O4 Nanocomposites

Bimagnetic Pt₃Co/Fe₃O₄ nanocomposite is synthesized in aqueous solution. The nanoparticles are characterized with TEM, FTIR, and magnetic measurements. The as‐synthesized nanocomposite exhibits ferromagnetic properties at room temperature due to the exchange coupling between Pt₃Co and Fe₃O₄. Magnetic properties of Pt₃Co/Fe₃O₄ nanoparticle can be tuned by varying of the molar ratio of iron to platinum. Pt₃Co/Fe₃O₄ nanoparticles exhibit higher saturation magnetization when the molar ratio of iron to platinum is 1.     

Adsorptive Removal of Cd,Cu, Ni and Mn from Environmental Samples Using Fe3O4-Zro2@APS Nanocomposite: Kinetic and Equilibrium Isotherm Studies

In this study, Fe₃O₄-ZrO₂ functionalized with 3-aminopropyltriethoxysilane (Fe₃O₄-ZrO₂@APS) nanocomposite was investigated as a nanoadsorbent for the removal of Cd(II), Cu(II), Mn (II) and Ni(II) ions from aqueous solution and real samples in batch mode systems. The prepared magnetic nanomaterials were characterized using X-ray powder diffraction (XRD), scanning electron microscopy/energy dispersion x-ray (SEM/EDX) Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Factors (such as adsorbent dose and sample pH) affecting the adsorption behavior of the removal process were studied using the response surface methodology. Under optimized condition, equilibrium data obtained were fitted into the Langmuir and Freundlich isotherms and the data fitted well with Langmuir isotherms. Langmuir adsorption capacities (mg/g) were found to be 113, 111, 128, and 123 mg/g for Cd, Cu, Ni and Mn, respectively. In addition, the adsorption kinetics was analyzed using five kinetic models, pseudo-first order, pseudo-second order, intraparticle diffusion and Boyd models. The adsorbent was successfully applied for removal of Cd(II), Cu(II), Mn (II) and Ni(II) ions in wastewater samples.     

Determination of Hydrogen Peroxide Using a Novel Sensor Based on Fe3O4 Magnetic Nanoparticles

Fe₃O₄ magnetic nanoparticles were synthesized by chemical co-precipitation with sodium citrate as a surfactant and were used with chitosan to construct a novel hydrogen peroxide sensor. The electrochemical behavior of hydrogen peroxide at the sensor was investigated by cyclic voltammetry. The composite film electrocatalyzed the reduction of hydrogen peroxide, and the peak current increased linearly with concentration from 1.00 × 10^?5 to 1.00 × 10^?3 mol · L^?1 (R = 0.9974) with a detection limit of 1.53 × 10^?6 mol · L^?1. This novel nonenzyme sensor provided good sensitivity, stability, and precision with potential applications.     

Preparation of a novel Fe3O4/graphene oxide hybrid for adsorptive removal of methylene blue from water

In this work, a novel Fe₃O₄/graphene oxide (GO) hybrid was prepared and its removal ability of cationic methylene blue dye from water was investigated. To improve the dispersability of Fe₃O₄/GO hybrid in water, GO was first modified by polyethylene glycol (PEG) via a click approach before deposition of Fe₃O₄ nanoparticles onto its surface. The successful modification of GO surface and the deposition of Fe₃O₄ nanoparticles were confirmed by transmission electron microscopy directly. The saturation magnetization of the resultant Fe₃O₄/GO hybrid is 7.8 eum/g. The adsorption capacities of Fe₃O₄/GO hybrid for methylene blue at 35 and 60°C were as high as 96.05 and 120.05 mg/g, respectively. Moreover, the Langmuir, Freundlich, and Temkin models are used to investigate the isothermal adsorption behavior of Fe₃O₄/GO hybrid.     

Adsorption of asphaltene from crude oil by applying polythiophene coating on Fe3O4 nanoparticles

The objective of the present study was to investigate the potential use of applying polythiophene coating on magnetic Fe₃O₄ nanoparticles for the enhancement of asphaltene adsorption. Two stages of experimental were conducted. In the first stage, the ability of coated nanoparticles for asphaltene adsorption in synthetic asphaltene-toluene solution was evaluated. The effects of parameters such as nanoparticles concentration, initial concentration of asphaltene, and temperature were studied. In the second stage, the performance of the coated nanoparticles for the adsorption of asphaltene from crude oil was investigated under atmospheric pressure and a pressure-volume-temperature (PVT) apparatus was utilized for simulated reservoir conditions. Fe₃O₄ and Fe₃O₄-PT MNPs were synthesized using an effective co-precipitation method. The results of the first-stage tests indicated that the maximum adsorption capacity values for Fe₃O₄ and Fe₃O₄-PT MNPs were 0.79 and 1.09?mg?m^?2, respectively. The optimum value of nanoparticles concentration was approximately determined as 10?g?L^?1. According to the adsorption isotherms and kinetics, the Langmuir and pseudo-second-order Lagergren models were consistent with the experimental data, respectively. The average adsorption efficiencies for Fe₃O₄-PT and Fe₃O₄ MNPs were 78.98 and 65.94%, respectively. The results of the performed experiments on crude oil showed that Fe₃O₄-PT MNPs could adsorb asphaltenes from crude oil in a similar trend as synthetic asphaltene-toluene solution.     

Hydrothermal Synthesis of Regular Octahedron Fe3O4 Microcrystals

Regular octahedron Fe₃O₄ microcrystals have been synthesized by a hydrothermal process on a large scale directly Fe substrates for the first time. X-ray diffraction (XRD) and scanning electron microscopy (SEM) have been used to investigate the novel fractal microcrystals. The results show that the regular octahedron Fe₃O₄ microcrystals can be obtained using this simple method. The size of microcrystals is evaluated to be from 2 to 20 μm. Moreover, one key fact has been found that the reaction temperature has a vital effect on the morphologies of the products.     

Thick Fe2O3, Fe3O4 films prepared by the chemical solution deposition method

Fe₂O₃, Fe₃O₄ films have been prepared from Fe(OCH₂CH(CH₃)₂)₃–(CH₃)₂CHCH₂OH–2.2′-diethanola- mine (DEA)–poly(vinylpyrrolidone) (PVP) solutions by the spin-(SC) and dip-coating (DC) technique on SiO₂ and Si substrates. The maximum film thickness achieved without crack formation has been increased by incorporation of PVP (relative molecular weights 40000 and 360000) into the precursor solution. The stability of the precursor solutions was remarkably increased by addition of DEA. Compact, dense, and crack-free Fe₂O₃ films with thicknesses 900 nm (DC), 450 nm (SC), have been obtained via single-step deposition cycle. Higher-molecular-weight PVP has been more effective in increasing the thickness. The minimum concentration of DEA, which results in pronounced increase of solutions stability, is about R _P (n(DEA)/n(Fe) = 0.1). The high content of carboneous residue in the pyrolysed Fe₂O₃ films promotes the formation of Fe₃O₄ films via reduction in a gas flow of H₂/N₂ gas mixture. Microstructure, surface morphology, and magnetic properties of the films have been also investigated using SEM, AFM, and SQUID, respectively.     

Fabrication of magnetite nanoparticles (Fe3O4-NPs) for catalytic pyrolysis of nutshells biomass

The fabrication of nanoparticles has been perused as a topic of critical importance in the present decades. Biosynthesis of nanoparticles employs plants extract instead of harmful chemicals. These plant extracts act as reducing and capping agents which is the most appropriate and eco-friendly method among all the preparative routs. In present study, the magnetite nanoparticles (Fe₃O₄-NPs) were fabricated using rapid, single step and benign biosynthetic rout by reduction of ferric nitrate nonahydrate solution with Ferocactus echidne aqueous extract containing ascorbic acid as a main reducing and capping agent. The structural and morphological properties of prepared iron oxide nanoparticles were investigated by Powder X-ray diffraction and scanning electron microscopy. The size of the synthesized nanoparticles was approximately 15 ± 2 nm as determined by Scherrer equation. The biosynthetically fabricated nanoparticles were employed as catalyst for pyrolysis of nutshells to produce biofuel. Catalytic pyrolysis of biomass yields biofuel as an alternative source of energy and chemical feed stock. Effect of temperature, heating rate, and amount of catalyst were investigated on conversion percentage and product yields. Aniline point, carbon residue, and cetane number of prepared bio-oil were also determined.     

Removal of Phenol Dyes Using a Photocatalytic Reactor with SnO2/Fe3O4 Nanoparticles

In this study, we present kinetics of phenol dyes removal by SnO₂/Fe₃O₄ nanoparticles in a photocatalytic reactor for optimization of this process. The effect of different concentrations of SnO₂ 5, 10, 15, 20% w/w on the photocatalytic reactor during removal of phenol red was investigated. The SnO₂/Fe₃O₄ nanoparticles were synthesized by core–shell method. The results of XRD and TEM showed the successful synthesis of these nanoparticles. Several other methods were applied to synthesis of these nanoparticles but none of them succeeded. This process composed of two-stage. The first stage was absorption by iron oxide nanoparticles and second stage was photocatalytic by tin oxide nanoparticles that followed pseudo-second-order kinetic and first-order kinetic, respectively. Optimization of this process was done corresponding to the parameters affecting the process with design expert software. In order to determine the optimal values of each of the parameters and the optimal conditions of the process, parameters were introduced to response surface methodology.     

Enhancing of asphaltene adsorption onto Fe3O4 nanoparticles coated with metal-organic framework Mil-101 (Cr) for the inhibition of asphaltene precipitation

In this study, the potential of MOF (Mil-101-Cr)-coated Fe₃O₄ magnetic nanoparticles (Fe₃O₄-MOF MNPs) for asphaltene adsorption was investigated for the first time and the results were compared with magnetic Fe₃O₄ nanoparticles (Fe₃O₄ MNPs). The coprecipitation method was used for the synthesis of both nanoparticles and were verified using x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and field emission scanning electron microscopy (FE-SEM). The initial asphaltene concentration, nanoparticles concentration, and temperature were the investigated parameters that influenced the adsorption capacity. Increasing the asphaltene concentration, decreasing the mass of nanoparticles, and reducing the temperature could enhance the maximum asphaltene adsorption capacities of 0.79 for Fe₃O₄ MNPs and 0.98?mg?m^?2 for Fe₃O₄-MOF MNPs. Adsorption isotherms tests showed that the Langmuir model was in agreement with the experimental data. In addition, the evaluation of adsorption kinetics demonstrated that the pseudo-second-order Lagergren model predicted the results more precisely. The amount of asphaltene adsorption for Fe₃O₄-MOF MNPs was higher than that for Fe₃O₄ MNPs. These results recommend the application of MOF as an appropriate and effective coating for enhancing asphaltene adsorption.     

Characterization of Fe3O4 Nanoparticles for Applications in Catalytic Activity in the Adsorption/Degradation of Methylene Blue and Esterification

The aim of this study is to evaluate the applicability of the catalytic activity (CA) of the Fe₃O₄ magnetic system in the adsorption/degradation of methylene blue and esterification. The thermal decomposition method allowed the preparation of Fe₃O₄ nanoparticles. The crystallites of the Fe₃O₄ structural phase present an acicular form confirmed by X-ray diffraction. Transmission electron microscopy results identified the acicular shape and agglomeration of the nanoparticles. Mössbauer spectroscopy showed that the spectrum is composed of five components at room temperature, a hyperfine magnetic field distribution (HMFD), two sextets, a doublet, and a singlet. The presence of the HMFD means that a particle size distribution is present. Fluorescence spectroscopy studied the CA of the nanoparticles with methylene blue and found adsorption/degradation properties of the dye. The catalytic activity of the nanoparticles was evaluated in the esterification reaction by comparing the results in the presence and absence of catalyst for the reaction with isobutanol and octanol, where it is observed that the selectivity for the products MIBP and MNOP is favored in the first three hours of reaction.     

Magnetic solid-phase extraction based on Fe3O4/graphene oxide nanoparticles for the determination of malachite green and crystal violet in environmental water samples by HPLC

This work describes a magnetic Fe₃O₄/graphene oxide (GO)-based solid-phase extraction (MSPE) technique for high performance liquid chromatography (HPLC) detection of malachite green (MG) and crystal violet (CV) in environmental water samples. Fe₃O₄/ GO magnetic nanoparticles were synthesised by a chemical co-precipitation method and characterised by scanning electron micrograph, transmission electron microscope, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and surface area analyser. The prepared Fe₃O₄/GO magnetic nanoparticles were used as the adsorbents of MSPE for MG and CV. By coupling with HPLC, a sensitive and cost-effective method for simultaneous determination of MG and CV was developed. The important parameters including the amount of Fe₃O₄/GO, pH of the sample solution, extraction time, salt effect, the type and volume of desorption solvent were investigated in detail. Under optimised conditions, the calibration curves were linear in the concentration range of 0.5–200 μg L^?1, and the limits of detection were 0.091 and 0.12 μg L^?1 for MG and CV, respectively. Finally, the established MSPE-HPLC method was successfully applied to determine MG and CV in environmental water samples with the recoveries ranging from 91.5% to116.7%.     

Investigation on The Thermal Properties of Fe2O(SO4)2. Part II

Fe₂O(SO₄)₂ is a secondary product of the decomposition of FeSO₄⋅H₂O. Part I of this study presents results on the synthesis of Fe₂O(SO₄)₂ in gaseous environment containing either low or high concentration of oxygen. In this paper the existence of differences between the structures of Fe₂O(SO₄)₂ and Fe₂(SO₄)₃ is proved on the basis of a detailed thermal study of Fe₂O(SO₄)₂ upon dynamic heating (differential thermal analysis) and upon isothermal heating (thermal-analytic balance) in various gaseous environments as well as by presenting kinetic data on the processes of decomposition of both compounds. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.     

Synthesis of orientedly bioconjugated core/shell Fe3O4@Au magnetic nanoparticles for cell separation

Orientedly bioconjugated core/shell Fe₃O₄@Au magnetic nanoparticles were synthesized for cell separation. The Fe₃O₄@Au magnetic nanoparticles were synthesized by reducing HAuCl₄ on the surfaces of Fe₃O₄ nanoparticles, which were further characterized in detail by TEM, XRD and UV-vis spectra. Anti-CD3 monoclonal antibody was orientedly bioconjugated to the surface of Fe₃O₄@Au nanoparticles through affinity binding between the Fc portion of the antibody and protein A that covalently immobilized on the nanoparticles. The oriented immobilization method was performed to compare its efficiency for cell separation with the non-oriented one, in which the antibody was directly immobilized onto the carboxylated nanoparticle surface. Results showed that the orientedly bioconjugated Fe₃O₄@Au MNPs successfully pulled down CD3⁺ T cells from the whole splenocytes with high efficiency of up to 98.4%, showing a more effective cell-capture nanostructure than that obtained by non-oriented strategy. This developed strategy for the synthesis and oriented bioconjugation of Fe₃O₄@Au MNPs provides an efficient tool for cell separation, and may be further applied to various fields of bioanalytical chemistry for diagnosis, affinity extraction and biosensor.     

Synthesis and application of polythiophene-coated Fe3O4 nanoparticles for preconcentration of ultra-trace levels of cadmium in different real samples followed by electrothermal atomic absorption spectrometry

In this research, magnetic Fe₃O₄ nanoparticles were synthesised by co-precipitation method and modified with polythiophene (PT) to produce Fe₃O₄-PT nanoparticles for preconcentration and determination of cadmium (??) ion followed by electrothermal atomic absorption spectrometry. The results of FT-IR spectroscopy, EDX analysis and SEM images show that Fe₃O₄-PT nanoparticles were synthesised successfully. Different parameters such as sample pH, amounts of adsorbent, sample volume, extraction time, type and concentration of eluent and desorption time were completely investigated and optimum conditions were selected.

Under the optimum conditions, the calibration curve was linear in the range of 0.01–0.25 µg L^?1 of cadmium (??). The relative standard deviation was 4.7% (n = 7, 0.10 µg L^?1 Cd²⁺) and limit of detection was 3.30 ng L^?1. The accuracy of the proposed method was verified by the analysis of a certified reference material and spike method. Finally, the proposed method was applied for the determination of ultra-trace levels of cadmium (??) in different water and food samples.     

Latent Fingerprints Enhancement Using a Functional Composite of Fe3O4@SiO2-Au

A functional composite of Fe₃O₄@SiO₂-Au was prepared and used for latent fingerprint detection. Material characterization results confirmed the successful fabrication of the Fe₃O₄@SiO₂-Au composite. In latent fingerprint detection, the Fe₃O₄@SiO₂-Au composite provides a better performance than commercial copper powder and also gold nanoparticles. More importantly, the Fe₃O₄@SiO₂-Au composite can be used in both powder and suspension forms, and also for common surfaces including glass, polyethylene bags, and paper. The favorable pH range (2.0–5.0) for the compositein finger marks detection is much wider than that of the traditional multi-metal deposition method (pH ranging from 2.0 to 3.0). The mechanism for the Fe₃O₄@SiO₂-Au composite in fingerprint detection was explored and discussed. This study provides a favorable choice for a one-step deposition method for latent fingerprint detection.     

Rapid magnetic solid phase extraction with in situ derivatization of methylmercury in seawater by Fe3O4/polyaniline nanoparticle

A new Fe(3)O(4)/polyaniline nanoparticle (PANI) material has been successfully developed as magnetic solid-phase extraction sorbent in dispersion mode for the determination of methylmercury (MeHg) in aqueous samples, via quantification by gas chromatography/mass spectrometry (GC-MS). The resultant core-shell magnetic solid-phase extraction nanoparticle (MSPE-NP) sorbent was characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS) and Fourier transform-infrared (FTIR) spectroscopy. Fe(3)O(4)/PANI composites showed fibrous structure with diameters between 50 and 100 nm for fibers. The MSPE-NP process involved the dispersion of the Fe(3)O(4)/PANI nanoparticles in water samples with sonication, followed by magnetic aided retrieval of the sorbent and then, solvent (hexane) desorption of extracted MeHg for GC-MS analysis. The extraction, derivatization and adsorption conditions were optimized by selecting the appropriate extraction parameters including the amount of sorbent, extraction time, derivatizing reagent volume and extraction solvent. The calibration graph was linear in the concentration range of 0.5-300 ng mL(-1) (R(2)>0.993) with detection limit of 0.1 ng mL(-1) (n=3), while the repeatability was 4.1% (n=5). Enrichment factor was obtained as 91. Seawater sample was analyzed as real sample and good recoveries (>98%) were obtained at different spiked values.     

Fabrication and Characterization of Nanocomposite Flexible Membranes of PVA and Fe3O4

Composite polymer membranes of poly(vinyl alcohol) (PVA) and iron oxide (Fe₃O₄) nanoparticles were produced in this work. X-ray diffraction measurements demonstrated the formation of Fe₃O₄ nanoparticles of cubic structures. The nanoparticles were synthesized by a coprecipitation technique and added to PVA solutions with different concentrations. The solutions were then used to generate flexible membranes by a solution casting method. The size and shape of the nanoparticles were investigated using scanning electron microscopy (SEM). The average size of the nanoparticles was 20±9 nm. Raman spectroscopy and Fourier-transform infrared spectroscopy (FTIR) were utilized to investigate the structure of the membranes, as well as their vibration modes. Thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) demonstrated the thermal stability of the membranes and the crystallinity degree. Electrical characteristics of the thin membranes were examined using impedance spectroscopy as a function of the nanoparticles’ concentrations and temperatures. The resistivity of the fabricated flexible membranes was possible to adjust by controlled doping with suitable concentrations of nanoparticles. The activation energy decreased with the nanoparticles’ concentrations due to the increase in charge carriers’ concentrations. Therefore, the fabricated membranes may be applied for practical applications that involve the recycling of nanoparticles for multiple application cycles.