Fe3O4/MIL‐101(Fe) nanocomposite as an efficient and recyclable catalyst for Strecker reaction

A highly porous metal‐organic framework, MIL‐101(Fe), was prepared by a solvothermal method in the presence of amino‐modified Fe₃O₄@SiO₂ nanoparticles, in order to achieve Fe₃O₄/MIL‐101(Fe) nanocomposite, which was characterized by XRD, FT‐IR, SEM, TEM, BET, and VSM. This hybrid magnetic nanocomposite was employed as heterogeneous catalyst for α‐amino nitriles synthesis through three‐component condensation reaction of aldehydes (ketones), amines, and trimethylsilyl cyanide in EtOH, at room temperature. The recoverability and reusability was admitted for the heterogeneous magnetic catalyst; no significant reduction of catalytic activity was observed even after five consecutive reaction cycles.     

Preparation of a graphene-based magnetic nanocomposite for the extraction of carbamate pesticides from environmental water samples

A graphene-based magnetic nanocomposite was synthesized and used for the first time as an effective adsorbent for the preconcentration of the five carbamate pesticides (metolcarb, carbofuran, pirimicarb, isoprocarb and diethofencarb) in environmental water samples prior to high performance liquid chromatography-diode array detection. The properties of the magnetic nanocomposite were characterized by scanning electron microscopy and X-ray diffraction. This novel graphene-based magnetic nanocomposite showed great adsorptive ability towards the analytes. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid some of the time-consuming experimental procedures related to the traditional solid phase extraction. Various experimental parameters that could affect the extraction efficiencies have been investigated. Under the optimum conditions, the enrichment factors of the method for the analytes were in the range from 474 to 868. A linear response was achieved in the concentration range of 0.1-50 ng mL(-1). The limits of detection of the method at a signal to noise ratio of 3 for the pesticides were 0.02-0.04 ng mL(-1). Compared with the dispersive liquid-liquid microextraction and the ultrasound-assisted surfactant-enhanced emulsification microextraction, much higher enrichment factors and sensitivities were achieved with the developed method. The method has been successfully applied for the determination of the carbamate pesticides in environmental water samples.     

Design and characterization of Fe3O4/GO/Au-Ag nanocomposite as an efficient catalyst for the green synthesis of spirooxindole-dihydropyridines

A novel magnetic nanocomposite of Au-Ag nanoparticles anchored on Fe₃O₄/graphene oxide spheres (Fe₃O₄/GO/Au-Ag) was successfully fabricated by the layer-by-layer assembly technique. The prepared Fe₃O₄/GO/Au-Ag was fully characterized by Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) analysis, thermogravimetric analysis (TGA), field-emission scanning electron microscopy (FE-SEM), energy-dispersive x-ray spectroscopy (EDS), transmission electron microscopy (TEM), and Raman spectroscopy. This nanocomposite showed unique catalytic performance for the synthesis of Spiro[indoline-3,5′-pyrido[2,3-d:6,5-d’]dipyrimidine]-pentaone derivatives by the three-component condensation reaction of isatins, barbituric acids and 6-amino uracil at room temperature and in aqueous media. The significant advantages of this protocol include highly stable, easily separable and reusable catalyst, simple operation, environmental friendliness and excellent yields.     

Core‐shell structured magnetic mesoporous carbon nanospheres derived from metal‐polyphenol coordination polymer‐coated Fe3O4 and its application in the enrichment of phthalates from water samples

In this work, core‐shell structured magnetic mesoporous carbon nanospheres were fabricated from the carbonization of metal‐polyphenol coordination polymer‐coated Fe₃O₄ nanoparticles. The preparation method is simple, fast, versatile, and easy to scale up. Magnetic mesoporous carbon nanospheres exhibit a high specific surface area, high superparamagnetism, and high adsorption efficiencies for phthalates. Four phthalates were extracted from aqueous solutions by using magnetic mesoporous carbon nanospheres via magnetic solid phase extraction. Subsequent analysis was performed by using high‐performance liquid chromatography with ultraviolet detection. The analytical method has good linearity in the concentration range of 1–200 ng/mL for diethyl phthalate, diisobutyl phthalate, and dicyclohexyl phthalate, and 3–200 ng/mL for dipropyl phthalate. The limits of detection were in the range of 0.10–0.62 ng/mL. Compared with previous methods, this method has a lower detection limit, wider linearity range, and faster adsorption and desorption rates. The results indicate that magnetic mesoporous carbon nanospheres are suitable for the enrichment of hydrophobic substances from aqueous solutions.     

Determination of sulfadimethoxine in milk with aptamer‐functionalized Fe3O4/graphene oxide as magnetic solid‐phase extraction adsorbent prior to HPLC

An aptamer (Apt) functionalized magnetic material was prepared by covalently link Apt to Fe₃O₄/graphene oxide (Fe₃O₄/GO) composite by 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide hydrochloride and N‐hydroxysuccinimide, and then characterized by FTIR spectroscopy, X‐ray diffraction, and vibration sample magnetometry. The obtained composite of Fe₃O₄/GO/Apt was employed as magnetic solid‐phase extraction adsorbent for the selective preconcentration of sulfadimethoxine prior to analysis by high‐performance liquid chromatography. Under the optimal conditions (sample pH of 4.0, sorbent dosage of 20 mg, extraction time of 3 h, and methanol‐5% acetic acid solution as eluent), a good linear relationship was obtained between the peak area and concentration of sulfadimethoxine in the range of 5.0 to 1500.0 µg/L with correlation coefficient of 0.9997. The limit of detection (S/N = 3) was 3.3 µg/L. The developed method was successfully applied to the analysis of sulfadimethoxine in milk with recoveries in the range of 75.9‐92.3% and relative standard deviations less than 8.1%. The adsorption mechanism of Fe₃O₄/GO/Apt toward sulfadimethoxine was studied through the adsorption kinetics and adsorption isotherms, and the results show that the adsorption process fits well with the pseudo‐second‐order kinetic model and the adsorbate on Fe₃O₄/GO/Apt is multilayer and heterogeneous.     

Facile synthesis of PEG‐coated magnetite (Fe3O4) and embedment of gold nanoparticle as a nontoxic antimicrobial agent

In the present study, we carried out a chemical synthesis and characterization of Fe₃O₄@PEG‐Au as a core/shell nanocomposite in an aqueous solution by the chemical co‐precipitation of Fe³⁺ and Fe²⁺ ions and encapsulated it by polyethylene glycol (PEG) in order to enhance hydrophilicity and biocompatibility of gold ions and immobilize them in the presence of NaBH₄ as a reducing agent. The nanostructures were characterized with FT‐IR, FESEM, EDS, WDX, VSM, ICP‐MS, and TEM. The antimicrobial activities of the nanostructures were tested against pathogenic microorganisms, including Staphylococcus aureus , Escherichia coli , and Candida albicans by broth microdilution method according to the methods of the Clinical Laboratory Standard Institute (CLSI). The toxicity of the nanostructures was tested against animal cell line based on MTT assay. The synthesized core/shell nanostructures had a good activity against the representative microorganisms of public health concern and revealed an insignificant toxicity against animal cell line.     

The use of silica‐coated magnetic graphene microspheres as the adsorbent for the extraction of pyrethroid pesticides from orange and lettuce samples followed by GC–MS analysis

Graphene‐grafted ferroferric oxide microspheres were used as the adsorbent to extract some pyrethroid pesticides (bifenthrin, λ‐cyhalothrin, cyfluthrin, cypermethrin, fenvalerate, and deltamethrin) from orange and lettuce samples prior to their determination by GC–MS. The main variables that could affect the extraction, including the amount of the adsorbent, pH of the sample solution, extraction time, concentration of salt, and desorption conditions, were investigated and optimized. Under the optimized conditions, a linear response was obtained in the concentration range of 0.3–100.0 ng/g for the analytes with the coefficients of determination ranging from 0.9877 to 0.9925. The LODs for the pyrethroids ranged from 0.01 to 0.02 ng/g. The method provided a good repeatability with RSDs < 10.6%. The recoveries for the six pyrethroid pesticides were in the range from 90.0 to 103.7%. The method was applied to the determination of the pesticides in orange and lettuce samples with a satisfactory result.     

Preparation and characterization of polyvinyl alcohol‐grafted Fe3O4 magnetic nanoparticles through glutaraldehyde

Magnetic nanoparticles (MNPs) are of great interest owing to their numerous existing and potential biomedical applications. To further explore the potential of MNPs in biomedical and other fields, we have designed and synthesized polyvinyl alcohol (PVA) polymer grafted Fe₃O₄ MNPs through glutaraldehyde (GLA) link. The success of this process has been ascertained using Fourier transform infrared (FT‐IR) analysis, thermogravimetric analysis (TGA), X‐ray diffraction (XRD) analysis and scanning electron microscopy (SEM) analysis. The FT‐IR analysis of resultant MNPs show infrared peak characteristics of PVA. TGA analysis clearly shows two major stages of thermal degradation, one corresponding to organic phase of PVA and GLA and another corresponding to Fe₃O₄ nanoparticles. XRD results and SEM images further support the FT‐IR and TGA results and confirm the presence of PVA layer surrounding Fe₃O₄ MNP surface. Under SEM examination, the magnetic cores exhibit somewhat irregular shapes varying from spherical, to oval to cubic. Copyright © 2012 John Wiley & Sons, Ltd.     

The use of graphene-based magnetic nanoparticles as adsorbent for the extraction of triazole fungicides from environmental water

A graphene-based magnetic nanocomposite (graphene-ferriferrous oxide; G-Fe(3) O(4) ) was synthesized and used as an effective adsorbent for the preconcentration of some triazole fungicides (myclobutanil, tebuconazole, and hexaconazole) in environmental water samples prior to high-performance liquid chromatography-ultraviolet detection. The method, which takes the advantages of both nanoparticle adsorption and magnetic phase separation from the sample solution, could avoid the time-consuming experimental procedures commonly involved in the traditional solid phase extraction such as centrifugation and filtrations. Various experimental parameters affecting the extraction efficiencies such as the amount of the magnetic nanocomposite, extraction time, the pH values of the sample solution, salt concentration, and desorption conditions were investigated. Under the optimum conditions, the enrichment factors of the method for the three analytes were 5824, 3600, and 4761, respectively. A good linearity was observed in the range of 0.1-50 ng/mL for tebuconazole and 0.05-50 ng/mL for myclobutanil and hexaconazole, respectively, with the correlation coefficients ranging from 0.9992 to 0.9996. The limits of detection (S/N = 3) of the method were between 0.005 and 0.01 ng/mL. The results indicated that as a magnetic solid-phase extraction adsorbent, the graphene-ferriferrous oxide (G-Fe(3) O(4) ) has a great potential for the preconcentration of some compounds from liquid samples.     

Facile Preparation of a Stable Fe3O4@LDH@NiB Magnetic Core‐Shell Nanocomposite for Hydrogenation

A novel NiB deposited layered double hydroxide (LDH ) coated ferroferric oxide (Fe₃O₄ @LDH @NiB ) magnetic core‐shell nanocomposite was successfully fabricated by the combination of coprecipitation and impregnation‐reduction. During the Fe₃O₄ @LDH preparation, a facile template‐free approach was employed to introduce the LDH shell, which was more efficient than the conventional method for the preparation of mesoporous materials that always needs to introduce and remove templates. The resulted Fe₃O₄ @LDH has a relatively high surface area and abundant surface hydroxyl group, which can adsorb metal ions, making it favorable to disperse and stabilize the active Ni species, as demonstraed by TEM , XPS , FT‐IR and BET characterizations. Therefore, it exhibited good activity in the selective hydrogenation of cinnamic acid to hydrocinnamic acid with the conversion and selectivity both approaching to 100%. Notably, the obtained Fe₃O₄ @LDH @NiB can be easily separated by an external magnetic field and recycled eleven times without appreciable loss of its initial catalytic activity.     

Design and Preparation of Graphene/Fe2O3 Nanocomposite as Negative Material for Supercapacitor

The development of high specific capacitance electrode materials with high efficiency, scalability and economic feasibility is significant for the application of supercapacitors, however, the synthesis of electrode material still faces huge challenges. Herein, graphene(G)/Fe₂O₃ nanocomposite was prepared via a simple hydrothermal method connected with subsequent thermal reduction process. Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) results showed rod-like Fe₂O₃ nanoparticles were prepared and well-dispersed on graphene layers, providing a rich active site and effectively buffering the aggregation of Fe₂O₃ nanoparticles in the process of electrochemical reaction. The specific capacitance of the obtained G/Fe₂O₃ nanocomposite as negative electrode for supercapacitor was 378.7 F/g at the current density of 1.5 A/g, and the specific capacitance retention was 88.76% after 3000 cycles. Furthermore, the asymmetric supercapacitor(ASC) was fabricated with G/Fe₂O₃ nanocomposite as negative electrode, graphene as positive electrode, which achieved a high energy density of 64.09 W∙h/kg at a power density of 800.01 W/kg, maintained 30.07 W∙h/kg at a power density of 8004.89 W/kg, and retained its initial capacitance by 78.04% after 3000 cycles. The excellent result offered a promising way for the G/Fe₂O₃ nanocomposite to be applied in high energy density storage systems.     

A Novel Biomimetic Hydrogen Peroxide Biosensor Based on Pt Flowers‐decorated Fe3O4/Graphene Nanocomposite

A sensitive and selective amperometric H₂O₂ biosensor was obtained by utilizing the electrodeposition of Pt flowers on iron oxide‐reduced graphene oxide (Fe₃O₄/rGO) nanocomposite modified glassy carbon electrode (GCE). The morphology of Fe₃O₄/rGO and Pt/Fe₃O₄/rGO was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), respectively. The step‐wise modification and the electrochemical characteristics of the resulting biosensor were characterized by cyclic voltammetry (CV) and chronoamperometry methods. Thanks to the fast electron transfer at the Pt/Fe₃O₄/rGO electrode interface, the developed biosensor exhibits a fast and linear amperometric response upon H₂O₂. The linear range of Pt/Fe₃O₄/rGO is 0.1∼2.4 mM (R²=0.998), with a sensitivity of 6.875 μA/mM and a detection limit of 1.58 μM (S/N=3). In addition, the prepared biosensor also provides good anti‐interferent ability and long‐term stability due to the favorable biocompatibility of the electrode interface. The proposed sensor will become a reliable and effective tool for monitoring and sensing the H₂O₂ in complicate environment.     

Bio‐based hyperbranched polyurethane/Fe3O4 nanocomposites as shape memory materials

The bio‐based shape memory polymers have generated immense interest as advanced smart materials. Mesua ferrea L. seed oil‐based hyperbranched polyurethane (HBPU)/Fe₃O₄ nanocomposites were prepared by the in‐situ polymerization technique. The transmission electron microscopy confirmed the homogeneous distribution of the Fe₃O₄ nanoparticles in polymer matrix, whereas Fourier transform infrared spectroscopic study revealed the presence of strong interfacial interactions between them. The incorporation of Fe₃O₄ (0 to 10 wt%) into the HBPU resulted in an increase in tensile strength (5.5–15 MPa) and scratch resistance (3–6 kg). The thermo‐gravimetric analysis indicated the improvement of thermal stability (240–270°C) of the nanocomposites. The nanocomposites exhibited full shape fixity, as well as almost full shape recovery under the microwave stimulus. The shape recovery speed increased with the increase of Fe₃O₄ nanoparticles content in the nanocomposites. Thus, the studied nanocomposites might be used as advanced shape memory materials in different potential fields. Copyright © 2013 John Wiley & Sons, Ltd.     

Design and Application of a Non‐enzymatic Sensor Based on Metal‐organic Frameworks for the Simultaneous Determination of Carbofuran and Carbaryl in Fruits and Vegetables

A novel, stable and sensitive non‐enzymatic sensor was developed with metal‐organic frameworks (MOFs) that have attracted great attention in electrochemical sensors applications in recent years. The pore structures of MIL (Fe)‐101 and MIL (Fe)‐53 are the families of MOFs that were constructed via a simple solvothermal procedure. The 35MIL‐101(Fe)‐reduced graphene oxide nanocomposite has been used for modification of glassy carbon electrode for the determination of carbofuran (CBF) and carbaryl (CBR). The porosity of the composites increased the voltammetric responses significantly for CBF and CBR in a mixed solution that makes the simultaneous determination of both carbamate pesticides possible. Characterization of MIL (Fe)‐101 and MIL (Fe)‐53 were performed with FT‐IR, XRD, BET and SEM. Finally, the introduced sensor under the optimal conditions showed low detection limits of 1.2 and 0.5 nM within the linear ranges of 5.0–200.0 nM and 1.0–300.0 nM for CBF and CBR, respectively. The non‐enzymatic sensor was successfully used to monitoring of carbamates residue in vegetable and fruit samples.     

Extraction of organophosphorus pesticides by carbon‐coated Fe3O4 nanoparticles through response surface experimental design

In this paper, carbon‐coated Fe₃O₄ nanoparticles were successfully synthesized and used as a magnetic solid‐phase extraction absorbent for the preconcentration and extraction of organophosphorus pesticides in environmental water samples. The carbon‐coated Fe₃O₄ nanoparticles were characterized by transmission electron microscopy, X‐ray powder diffraction, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. The determination of organophosphorus pesticides in water samples with carbon‐coated Fe₃O₄ nanoparticles was investigated by high‐performance liquid chromatography with a diode array detector. Furthermore, the response surface model based on the central composite design was applied to quantitatively investigate the effect of some important variables influencing the extraction efficiency, such as pH, treatment time, amount of nanoparticle sorbents, and amount of salt and to find the optimized conditions providing the highest extraction efficiency. Under optimized conditions, the calibration curve was linear in the range of 0.5–15.0 ng/mL with a regression coefficient of 0.9948, 0.9958, and 0.9931 for fenitrothion, diazinon, and ethion, respectively. The obtained results showed that this analytical method would be useful for the analysis of fenitrothion, diazinon, and ethion in tap water with high precision and accuracy.     

Inclusion of sulfamethoxazole in a novel CuFe2O4 nanoparticles/mesoporous silica‐based nanocomposite: Release kinetics and antibacterial activity

In this work, we aimed to improve the antibacterial activity of sulfamethoxazole (SMX) via its inclusion in a newly synthesized nanocomposite composed of CuFe₂O₄ nanoparticles and poly(vinyl alcohol)/silica‐based mesoporous materials. Characterization of this formulation using different techniques confirmed the correct synthesis and showed that this mesoporous nanocomposite had an amorphous structure with relatively high surface area of 1,620.7 m² g^?1 and mean pore diameter of 1.6576 nm. Zeta potential of the formulation was obtained to be zero which led to its higher bioavailability in comparison to pure SMX with negative zeta potential. Antibacterial property of the prepared formulation against Staphylococcus aureus and Escherichia coli was evaluated. Minimum inhibitory concentration of the SMX‐loaded mesoporous nanocomposite was considerably lower than those of pure SMX, indicating the efficient function of the mesoporous material as a delivery system. Kinetics of SMX release was also studied using zero‐order, first‐order, Higuchi, and Korsmeyer–Peppas kinetics models. According to the obtained results, the release kinetics was found to obey zero‐order model. So the possibility of sustained release of SMX from the synthesized carrier may be suggested.     

Silica‐coated nano‐Fe3O4‐supported iminopyridine palladium complex as an active,phosphine‐free and magnetically separable catalyst for Heck reactions

A novel magnetic nanoparticle‐supported iminopyridine palladium complex was successfully prepared by attaching palladium acetate to iminopyridine ligand‐functionalized silica‐coated nano‐Fe₃O₄. The as‐prepared catalyst was well characterized and was evaluated in Heck reactions in terms of activity and recyclability. It was found to be highly efficient for the reactions of various aryl iodides and aryl bromides having electron‐withdrawing groups with olefins under phosphine‐free and inert atmosphere‐free conditions. Moreover, the catalyst could be conveniently recovered using an external magnet, and the recyclability was influenced by the base in the Heck reaction. The catalyst could be reused at least six times with no significant loss in activity when triethylamine acted as the base.     

Palladium supported on diaminoglyoxime‐functionalized Fe3O4 nanoparticles as a magnetically separable nanocatalyst in Heck coupling reaction

A hybrid material of palladium supported on diaminoglyoxime‐functionalized Fe₃O₄ was used as an effective and recyclable catalyst in Mizoroki–Heck coupling reactions. The catalyst was very effective for the Mizoroki–Heck reaction of aryl halides with styrene and conversion was in most cases excellent. The yields of the products were in the range 75–98%. The catalyst showed good stability and could be recovered and reused for six reaction cycles without significant leaching and loss its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and characterization of palladium immobilized on silica‐coated Fe3O4 and its catalytic performance for Suzuki reaction under microwave irradiation

Supported palladium catalyst (Pd/Fe₃O₄@SiO₂) was easily prepared by supporting PdCl₂ on silica‐coated magnetic nanoparticles Fe₃O₄ in ethylene glycol. The as‐prepared sample was characterized by infrared spectroscopy (IR), X‐ray diffraction (XRD) and X‐ray photoelectron spectrometer (XPS). The formation of active specie Pd(0) was confirmed by XRD and XPS, and the Pd loading for the fresh and recovered catalyst was determined by atomic absorption spectroscopy (AAS). Pd/Fe₃O₄@SiO₂ was employed for the synthesis of biphenyl derivatives via Suzuki reaction. In terms of the yield of biphenyl, the supported catalyst displayed nearly equal catalytic performance to that of homologous PdCl₂ under microwave irradiation for 30 min but higher than that obtained by traditional heating method for 12 h. The catalytic performance of Pd/Fe₃O₄@SiO₂ for Suzuki reactions involving various aryl halides and arylboronic acids were also examined. Impressive yield of biphenyl at 68.2% was obtained even in the presence of unreactive aryl chlorides. Pd/Fe₃O₄@SiO₂ was recovered by a permanent magnet and directly reused in the next run, and no obvious deactivation was observed for up to 6 times. Copyright © 2016 John Wiley & Sons, Ltd.     

Graphene oxide as a micro‐solid‐phase extraction sorbent for the enrichment of parabens from water and vinegar samples

A simple hydrophilic polyamide organic membrane protected micro‐solid‐phase extraction method with graphene oxide as the sorbent was developed for the enrichment of some parabens from water and vinegar samples prior to gas chromatography with mass spectrometry detection. The main experimental parameters affecting the extraction efficiencies, such as the type and amount of the sorbent, extraction time, stirring rate, salt addition, sample solution pH and desorption conditions, were investigated. Under the optimized experimental conditions, the method showed a good linearity in the range of 0.1–100.0 ng/mL for water samples and 0.5–100.0 ng/mL for vinegar samples, with the correlation coefficients varying from 0.9978 to 0.9997. The limits of detection (S/N = 3) of the method were in the range of 0.005–0.010 ng/mL for water samples and 0.01–0.05 ng/mL for vinegar samples, respectively. The recoveries of the method for the analytes at spiking levels of 5.0 and 70.0 ng/mL were between 84.6 and 106.4% with the relative standard deviations varying from 4.2 to 9.5%. The results indicated that the developed method could be a practical approach for the determination of paraben residues in water and vinegar samples.