Synthesis,characterization and application of sulfonic acid supported on ferrite–silica superparamagnetic nanoparticles

In this study, the synthesis of sulfonic acid supported on ferrite–silica superparamagnetic nanoparticles (Fe₃O₄@SiO₂@SO₃H) as a nanocatalyst with large density of acidic groups is suggested. This nanocatalyst was prepared in three steps: preparation of colloidal iron oxide magnetic nanoparticles (Fe₃O₄ MNPs), coating of silica on Fe₃O₄ MNPs (Fe₃O₄@SiO₂) and incorporation of sulfonic acid as a functional group on the surface of Fe₃O₄@SiO₂ nanoparticles (Fe₃O₄@SiO₂@SO₃H). The properties of the prepared magnetic nanoparticles were characterized using transmission electron microscopy, infrared spectroscopy, vibrating sample magnetometry, X‐ray diffraction and thermogravimetric analysis. Finally, the applicability of the synthesized magnetic nanoparticles was tested as a heterogeneous solid acid nanocatalyst for one‐pot synthesis of diindolyloxindole derivatives in aqueous medium. Oxindole derivatives were produced by the coupling of indole and isatin compounds with good to high yields (60–98%). Copyright © 2016 John Wiley & Sons, Ltd.     

Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe2O3@TiO2 (γ‐Fe2O3@TiO2‐EG‐Cu(II)): A highly efficient magnetically separable heterogeneous nanocatalyst for one‐pot synthesis of highly substituted imidazoles

A simple, efficient and eco‐friendly procedure has been developed using Cu(II) immobilized on guanidinated epibromohydrin‐functionalized γ‐Fe₂O₃@TiO₂ (γ‐Fe₂O₃@TiO₂‐EG‐Cu(II)) for the synthesis of 2,4,5‐trisubstituted and 1,2,4,5‐tetrasubstituted imidazoles, via the condensation reactions of various aldehydes with benzil and ammonium acetate or ammonium acetate and amines, under solvent‐free conditions. High‐resolution transmission electron microscopy analysis of this catalyst clearly affirmed the formation of a γ‐Fe₂O₃ core and a TiO₂ shell, with mean sizes of about 10–20 and 5–10 nm, respectively. These data were in very good agreement with X‐ray crystallographic measurements (13 and 7 nm). Moreover, magnetization measurements revealed that both γ‐Fe₂O₃@TiO₂ and γ‐Fe₂O₃@TiO₂‐EG‐Cu(II) had superparamagnetic behaviour with saturation magnetization of 23.79 and 22.12 emu g^?1, respectively. γ‐Fe₂O₃@TiO₂‐EG‐Cu(II) was found to be a green and highly efficient nanocatalyst, which could be easily handled, recovered and reused several times without significant loss of its activity. The scope of the presented methodology is quite broad; a variety of aldehydes as well as amines have been shown to be viable substrates. A mechanism for the cyclocondensation reaction has also been proposed.     

Equilibrium and kinetic study of novel methyltrimethoxysilane magnetic titanium dioxide nanocomposite for methylene blue adsorption from aqueous media

Novel magnetic titanium dioxide nanoparticles decorated with methyltrimethoxysilane (Fe₃O₄@TiO₂‐MTMOS) were successfully fabricated via a sol–gel method at room temperature. The synthesized material was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis and vibrating sample magnetometry. The removal efficiency of the adsorbent was evaluated through the adsorption of methylene blue (MB) dye from water samples. The adsorption isotherm and kinetics were evaluated using various models. The Langmuir model indicated a high adsorption capacity (11.5 mg g^?1) of Fe₃O₄@TiO₂‐MTMOS. The nanocomposite exhibited high removal efficiency (96%) and good regeneration (10 times) compared to Fe₃O₄ and Fe₃O₄@TiO₂ at pH = 9.0. Based on the adsorption mechanism, electrostatic interaction plays a main role in adsorption since MB dye is cationic in nature at pH = 9, whereas the adsorbent acquired an anionic nature. The newly synthesized Fe₃O₄@TiO₂‐MTMOS can be used as a promising material for efficient removal of MB dye from aqueous media.     

89Zr Labeled Fe3O4@TiO2 Nanoparticles: In Vitro Afffinities with Breast and Prostate Cancer Cells

In this study, Fe₃O₄@TiO₂ nanoparticles were synthesized as a new Positron Emission Tomography/Magnetic Resonance Imaging (PET/MRI) hybrid imaging agent and radiolabeled with ⁸⁹Zr. In addition, Fe₃O₄ nanoparticles were synthesized and radiolabeled with ⁸⁹Zr. Df-Bz-NCS was used as bifunctional ligand. The nanoconjugates were characterized with transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. Radiolabeling yields were 100%. Breast and prostate cancer cell affinities and cytotoxicity were determined using in vitro cell culture assays. The results demonstrated that Fe₃O₄@TiO₂ nanoparticles are promising for PET/MR imaging. Finally, unlike Fe₃O₄ nanoparticles, Fe₃O₄@TiO₂ nanoparticles showed a fluorescence spectrum at an excitation wavelength of 250 nm and an emission wavelength of 314 nm. Therefore, in addition to bearing the magnetic properties of Fe₃O₄ nanoparticles, Fe₃O₄@TiO₂ nanoparticles display fluorescence emission. This provides them with photodynamic therapy potential. Therefore multimodal treatment was performed with the combination of PDT and RT by using human prostate cancer cell line (PC3). The development of ⁸⁹Zr-Df-Bz-NCS-Fe₃O₄@TiO₂ nanoparticles as a new multifunctional PET/MRI agent with photodynamic therapy and hyperthermia therapeutic ability would be very useful.     

Removal of Chromium Ions by Fe3O4‐containing Polypyrrole Matrix and Environmental Applications

In this work, the PPy/Fe₃O₄@TiO₂ composite was synthesized and characterized by X‐ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and magnetic measurements (using a vibrating sample magnetometer). The adsorption performance of PPy/Fe₃O₄@TiO₂ composite for Cr(VI) ions was evaluated by UV irradiation. The effects of pH, adsorbent dose, contact time, and the initial concentration on the adsorption performance of Cr(VI) onto PPy/Fe₃O₄@TiO₂ were investigated. The maximum adsorption capacity of Cr(VI) upon doped PPy/Fe₃O₄@TiO₂ is 85.30 mg/g at room temperature. The total adsorption process likely follows the Langmuir model and pseudo‐second‐order kinetics. Our study suggests that the PPy/Fe₃O₄@TiO₂ composite can be efficiently used for the adsorption of Cr(VI) ions.     

Silver,iron, and nickel immobilized on hydroxyapatite‐core‐shell γ‐Fe2O3 MNPs catalyzed one‐pot five‐component reactions for the synthesis of tetrahydropyridines by tandem condensation of amines,aldehydes, and methyl acetoacetate

In this study, Ag, Ni²⁺, and Fe²⁺ immobilized on hydroxyapatite‐core‐shell γ‐Fe₂O₃ nanoparticles (γ‐Fe₂O₃@HAp‐Ag, γ‐Fe₂O₃@HAp‐Ni²⁺, and γ‐Fe₂O₃@HAp‐Fe²⁺) as a new and reusable Lewis acid magnetic nanocatalyst was successfully synthesized and reported for an atom economic, extremely facile, and environmentally benign procedure for the synthesis of highly functionalized tetrahydropyridines derivatives 4a‐t is described by one‐pot five‐component reaction of 2 equiv of aldehydes 1 , 2 equiv of amines 2 , and 1 equiv of methyl acetoacetate 3 in EtOH at room temperature in good to high yields and short reaction time. The presented methodology offers several advantages such as easy work‐up procedure, reusability of the magnetic nanocatalyst, operational simplicity, green synthesis avoiding toxic reagents and solvent, mild reaction conditions, and no tedious column chromatographic separation.     

Hierarchical Fe3O4@TiO2 Yolk–Shell Microspheres with Enhanced Microwave‐Absorption Properties

A facile and efficient strategy for the synthesis of hierarchical yolk–shell microspheres with magnetic Fe₃O₄ cores and dielectric TiO₂ shells has been developed. Various Fe₃O₄@TiO₂ yolk–shell microspheres with different core sizes, interstitial void volumes, and shell thicknesses have been successfully synthesized by controlling the synthetic parameters. Moreover, the microwave absorption properties of these yolk–shell microspheres, such as the complex permittivity and permeability, were investigated. The electromagnetic data demonstrate that the as‐synthesized Fe₃O₄@TiO₂ yolk–shell microspheres exhibit significantly enhanced microwave absorption properties compared with pure Fe₃O₄ and our previously reported Fe₃O₄@TiO₂ core–shell microspheres, which may result from the unique yolk–shell structure with a large surface area and high porosity, as well as synergistic effects between the functional Fe₃O₄ cores and TiO₂ shells.     

Synthesis and characterization of Fe3O4@SiO2–polymer-imid–Pd magnetic porous nanospheres and their application as a novel recyclable catalyst for Sonogashira–Hagihara coupling reactions

We demonstrate herein the modification of magnetic nanoparticles and their use as a magnetic nanocatalyst in direct coupling reactions of aryl halides with terminal alkynes. Magnetite particles were prepared by simple co-precipitation method in aqueous medium, and then Fe₃O₄@ SiO₂ nanosphere was synthesized by using nano-Fe₃O₄ as the core, TEOS as the silica source and PVA as the surfactant. Fe₃O₄@SiO₂ was coated with polymeric N-heterocyclic carbene/Pd. The samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, field emission scanning electron microscopy, dynamic light scattering, thermogravimetric analysis, vibration sample magnetometer and N₂ adsorption–desorption isotherm analysis. Poly (N-vinyl imidazole) functionalized Fe₃O₄@SiO₂ nanoparticle was found to be an efficient nanocatalyst in Sonogashira–Hagihara cross-coupling reactions. The nanocatalyst can be easily recovered by a magnetic field and reused for six runs without appreciable loss of its catalytic activity.     

Fabrication and characterization of Fe_3O_4@SiO_2@TiO_2@Ho nanostructures as a novel and highly efficient photocatalyst for degradation of organic pollution

In this work we synthesize a novel and highly efficient photocatalyst for degradation of methyl orange and rhodamine B. In addition, a new method for synthesis of Fe_3O_4@SiO_2@TiO_2@Ho magnetic core-shell nanoparticles with spherical morphology is proposed. The crystal structures, morphology and chemical properties of the as-synthesized nanoparticles were characterized using Fourier transform infrared spectroscopy(FT-IR), scanning electron microscopy(SEM), transmission electron microscopy(TEM), energy dispersive X-ray(EDS), X-ray diffraction(XRD), UV–vis diffuse reflectance spectroscopy(DRS) and vibrating sample magnetometer(VSM) techniques. The photocatalytic activity of Fe_3O_4@SiO_2@TiO_2@Ho was investigated by degradation of methyl orange(MO) as cationic dye and rhodamine B(Rh B) as anionic dye in aqueous solution under UV/vis irradiation. The results indicate that about 92.1% of Rh B and78.4% of MO were degraded after 120 and 150 min, respectively. These degradation results show that Fe_3O_4@SiO_2@TiO_2@Ho nanoparticles are better photocatalyst than Fe3O4@Si O2@TiO 2@Ho for degradation of MO and Rh B. As well as, the catalyst shows high recovery and stability even after several separation cycles.     

Enantioselective synthesis of 3‐amino‐1‐aryl‐1H‐benzo[f]chromene‐2‐carbonitrile derivatives by Fe3O4@PS‐arginine as an efficient chiral magnetic nanocatalyst

A novel chiral magnetic nanocatalyst was prepared by the surface modification of Fe₃O₄ magnetic nanoparticles (MNPs) with a chloropropylsilane and further by arginine to form Fe₃O₄@propylsilan‐arginine (Fe₃O₄@PS‐Arg). After the structural confirmation of Fe₃O₄@PS‐Arg synthesized MNPs by Fourier transform‐infrared, X‐ray diffraction, field emission‐scanning electron microscopy, transmission electron microscopy, vibrating‐sample magnetometry and thermogravimetric analyses, their catalytic activity was evaluated for one‐pot enantioselective synthesis of 3‐amino‐1‐aryl‐1H‐benzo[f]chromene‐2‐carbonitrile derivatives. The results showed that in the presence of 0.07 g Fe₃O₄@PS‐Arg nanocatalyst and ethanol as solvent, the best reaction yield (96%) was obtained in the least time (5 min). Easy operation, reusability and stability, short reaction time, high reaction yields and good enantioselectivity are the major advantages of the newly synthesized nanocatalyst. Also, this study provides a novel strategy for further research and investigation on the synthesis of new reusable enantioselective catalysts and chiral compounds.     

Magnetic titanium oxide nanoparticles for hemimicelle extraction and HPLC determination of organophosphorus pesticides in environmental water

We report on a method for the extraction of organophosphorus pesticides (OPPs) from water samples using mixed hemimicelles and magnetic titanium dioxide nanoparticles (Fe₃O₄@TiO₂) modified by cetyltrimethylammonium. Fe₃O₄@TiO₂ nanoparticles were synthesized by a hydrothermal process and then characterized by scanning electron microscopy and Fourier transform IR spectrometry. The effects of the quantity of surfactant, extraction time, desorption solvent, pH value, extraction volume and reuse of the sorbent were optimized with respect to the extraction of OPPs including chlorpyrifos, dimethoate, and trichlorfon. The extraction method was applied to analyze OPPs in environmental water using HPLC along with UV detection. The method has a wide linear range (100–15,000 ng L^?1), good linearity (r?>?0.999), and low detection limits (26–30 ng L^?1). The enrichment factor is ~1,000. The recoveries (at spiked levels of 100, 1,000 and 10,000 ng L^?1) are in the range of 88.5–96.7 %, and the relative standard deviations range from 2.4 % to 8.7 %.

Nano‐Fe3O4@TiO2/Cu2O Core‐shell Composite: A Convenient Magnetic Separable Catalyst for A3 and KA2 Coupling

An eco‐efficient one‐pot three component reaction between different aldehydes or ketones with alkynes and amines for the synthesis of propargylamines was performed using Fe₃O₄@TiO₂/Cu₂O as a nano‐magnetic composite under solvent free condition. The catalyst showed remarkable catalytic activity by decreasing the time of the reaction in comparison of other reported magnetic catalysts. In addition, the Fe₃O₄@TiO₂/Cu₂O can be easily recycled and reutilized for five times without apparent loss of catalytic activity.     

Uniformly dispersed copper nanoparticles onto the modified magnetically recoverable nanocatalyst for aqueous synthesis of primary amides

Magnetically recoverable and environmentally friendly Cu‐based heterogeneous catalyst has been synthesized for the one‐pot conversion of aldehydes to their corresponding primary amides. The Fe₃O₄@SiO₂ nanocomposites were prepared by synthesis of Fe₃O₄ magnetic nanoparticles (MNPs) which was then coated with a silica shell via Stöber method. Bi‐functional cysteine amino acid was covalently bonded onto the siliceous shell of nanocatalyst. The Cu^II ions were then loaded onto the modified surface of nanocatalyst. Finally, uniformly dispersed copper nanoparticles were achieved by reduction of Cu^II ions with NaBH₄. Amidation reaction of aryl halides with electron‐withdrawing or electron‐donating groups and hydroxylamine hydrochloride catalyzed with Fe₃O₄@SiO₂@Cysteine‐copper (FSC‐Cu) MNPs in aqueous condition gave an excellent yield of products. The FSC‐Cu MNPs could be easily isolated from the reaction mixture with an external magnet and reused at least 8 times without significant loss in activity.     

One‐pot multicomponent synthesis of novel 2‐(piperazin‐1‐yl) quinoxaline and benzimidazole derivatives,using a novel sulfamic acid functionalized Fe3O4 MNPs as highly effective nanocatalyst

The immobilization of sulfonic acid on the surface of Fe₃O₄ magnetic nanoparticles (MNPs) as a novel acid nanocatalyst has been successfully reported. The morphological features, thermal stability, magnetic properties, and other physicochemical properties of the prepared superparamagnetic core–shell (Fe₃O₄@PFBA–Metformin@SO₃H) were thoroughly characterized using Fourier transform infrared (FTIR), X‐ray diffraction (XRD), energy‐dispersive X‐ray spectroscopy (EDS), field‐emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), thermogravimetric analysis–differential thermal analysis (TGA‐DTA), atomic force microscopy (AFM), dynamic light scattering (DLS), Brunauer–Emmett–Teller (BET), and vibrating sample magnetometer (VSM) techniques. It was applied as an efficient and reusable catalyst for the synthesis of 2‐(piperazin‐1‐yl) quinoxaline and benzimidazole derivatives via a one‐pot multiple‐component cascade reaction under green conditions. The results displayed the excellent catalytic activity of Fe₃O₄@PFBA–metformin@SO₃H as an organic–inorganic hybrid nanocatalyst in condensation and multicomponent Mannich‐type reactions. The easy separation, simple workup, excellent stability, and reusability of the nanocatalyst and quantitative yields of products and short reaction time are some outstanding advantages of this protocol.     

Synthesis and catalytic evaluation of Fe3O4/MWCNTs nanozyme as recyclable peroxidase mimetics: Biochemical and physicochemical characterization

In this research, the nanocomposite of multiwalled carbon nanotubes and magnetic metal oxide nanoparticles (Fe₃O₄/MWCNTs), as enzyme mimetic, was synthesized using an in situ chemical reduction method. The structure, composition and morphology of the prepared Fe₃O₄/MWCNT nanocomposite materials were characterized using X‐ray diffraction, FT‐IR and scanning electron microscopy with energy dispersive X‐ray spectroscopy, respectively. The magnetic properties of the nanocomposite were investigated by the vibrating sample magnetometer. A colorimetric system involving nanozyme, phenol/4‐aminoantipyrine and H₂O₂ was utilized for the determination of peroxidase mimetic catalytic assay. The obtained results confirmed that the synthesis of Fe₃O₄/MWCNTs nanostructures was successful. It was found that Fe₃O₄/MWCNTs nanohybrid exhibited peroxidase‐like activity without any pH limitation. Colorimetric data demonstrated that the prepared nanocatalyst had higher catalytic activity toward H₂O₂ than MWCNTs. The kinetic parameters of the nanozyme, K_m and V_max, were estimated to be 8.3 mm and 1.4 mm min^?1, respectively. The Fe₃O₄/MWCNTs nanostructures were also successfully applied for glucose detection. In addition, peroxidase‐like activity of the nanozyme increased in the presence of butyl‐imidazolium bromide ionic liquid. These biomimetic catalysts have some advantages, such as simplicity, stability, reusability and cost effectiveness, which makes them great candidates to be used in various fields of biotechnology applications.     

Sulfonated magnetic nanocatalyst and application for synthesis of novel Spiro[acridine-9,5′-thiazole]-1,4′-dione derivatives

Sulfonated Sulfurol supported Fe₃O₄ (Fe₃O₄@SiO₂-Pr-Sulfurol-SO₃H) a new magnetic reusable nanocatalyst was prepared using chemical modification of magnetic nanoparticles (MNPs) surface with Sulfurol-SO₃H. The Sulfurol-SO₃H moieties on the surface of MNPs act as acidic catalytic sites for catalysis purposes. Fe₃O₄@SiO₂-Pr-Sulfurol-SO₃H was authenticated by usual analytical and spectroscopic techniques. The prepared Fe₃O₄@SiO₂-Pr-Sulfurol-SO₃H MNPs were applied to the preparation of novel Spiro[acridine-9,5′-thiazole]-1,4′-dione derivatives via the three-component condensation of isatins, dimedone and thioamides or thioureas.

     

Threonine stabilizer‐controlled well‐dispersed small palladium nanoparticles on modified magnetic nanocatalyst for Heck cross‐coupling process in water

We report the synthesis of magnetically separable Fe₃O₄@Silica‐Threonine‐Pd⁰ magnetic nanoparticles with a core–shell structure. After synthesis of Fe₃O₄@Silica, threonine as an efficient stabilizer/ligand was bonded to the surface of Fe₃O₄@Silica. Then, palladium nanoparticles were generated on the threonine‐modified catalyst. The threonine stabilizer helps to generate palladium nanoparticles of small size (less than 4 nm) with high dispersity and uniformity. Magnetically separable Fe₃O₄@Silica‐Threonine‐Pd⁰ nanocatalyst was fully characterized using various techniques. This nanocatalyst efficiently catalysed the Heck cross‐coupling reaction of a variety of substrates in water medium as a green, safe and inexpensive solvent at 80°C. The Fe₃O₄@Silica‐Threonine‐Pd⁰ catalyst was used for at least eight successful consecutive runs with palladium leaching of only 0.05%.     

S‐Benzylisothiourea complex of palladium on magnetic nanoparticles: A highly efficient and reusable nanocatalyst for synthesis of polyhydroquinolines and Suzuki reaction

S ‐Benzylisothiourea complex of palladium supported on modified Fe₃O₄ magnetic nanoparticles (Pd‐SBTU@Fe₃O₄) is reported for carbon–carbon coupling through the Suzuki coupling reaction. Also, the synthesis of polyhydroquinoline derivatives is reported in the presence of Pd‐SBTU@Fe₃O₄ as nanocatalyst. The prepared nanoparticles were characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, vibrating sample magnetometry and inductively coupled plasma atomic emission spectroscopy. The nanocatalyst was easily recovered using an external magnet and reused several times without significant loss of its catalytic efficiency. The heterogeneity of Pd‐SBTU@Fe₃O₄ was studied using hot filtration.     

Efficient and selective oxidation of alcohols in water employing palladium supported nanomagnetic Fe3O4@hyperbranched polyethylenimine (Fe3O4@HPEI.Pd) as a new organic–inorganic hybrid nanocatalyst

Palladium immobilized magnetic nanoFe₃O₄@hyperbranched polyethylenimine (Fe₃O₄@HPEI.Pd) was prepared according to a simple and cost effective pathway and it was employed as a new efficient and selective organic–inorganic hybrid nanocatalyst for the aqueous oxidation of primary and secondary alcohols to their corresponding products in good yields applying oxone (potassium hydrogen monopersulfate) and H₂O₂ as an oxidant at room temperature. Moreover, the catalytic system was reused at least 13 times without significant loss of activity. The complete characterization of this efficient nanocatalyst was investigated by FTIR, UV–Vis, TEM, SEM, XRD, TGA, VSM, ICP and EDX techniques.     

Surface Modification of a Magnetic SiO2 Support and Immobilization of a Nano-TiO2 Photocatalyst on It

This study presented an effective method to modify the surface chemical reactivity of a SiO₂/Fe₃O₄ support. The unmodified SiO₂/Fe₃O₄ support was prepared by the hydrolysis and condensation of tetraethoxysilane on the surface of hydrophilic Fe₃O₄ nanoparticles. These were then modified by a heat treatment in an ethanol/water solution under reflux. The resulting samples were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and transmission/scanning electron microscopy. The immobilization of a TiO₂ nanocatalyst on both unmodified and modified supports was performed to investigate the effects of the modification of the magnetic silica support on the loading of a TiO₂ nanocatalyst and the photocatalytic activity. The loading of TiO₂ and the photocatalytic activity were both improved.