Facile Hydrogen‐Bond‐Assisted Polymerization and Immobilization Method to Synthesize Hierarchical Fe3O4@Poly(4‐vinylpyridine‐co‐divinylbenzene)@Au Nanostructures and Their Catalytic Applications

Hierarchical Fe₃O₄@poly(4‐vinylpyridine‐co‐divinylbenzene)@Au (Fe₃O₄@P(4‐VP–DVB)@Au) nanostructures were fabricated successfully by means of a facile two‐step synthesis process. In this study, well‐defined core–shell Fe₃O₄@P(4‐VP–DVB) microspheres were first prepared with a simple polymerization method, in which 4‐VP was easily polymerized on the surface of Fe₃O₄ nanoparticles by means of strong hydrogen‐bond interactions between ? COOH groups on poly(acrylic acid)‐modified Fe₃O₄ nanoparticles and a 4‐VP monomer. HAuCl₄ was adsorbed on the chains of a P(4‐VP) shell and then reduced to Au nanoparticles by NaBH₄, which were embedded into the P(4‐VP) shell of the composite microspheres to finally form the Fe₃O₄@P(4‐VP–DVB)@Au nanostructures. The obtained Fe₃O₄@P(4‐VP–DVB)@Au catalysts with different Au loadings were applied in the reduction of 4‐nitrophenol (4‐NP) and exhibited excellent catalytic activity (up to 3025 h^?1 of turnover frequency), facile magnetic separation (up to 31.9 emu g^?1 of specific saturation magnetization), and good durability (over 98 % of conversion of 4‐NP after ten runs of recyclable catalysis and almost negligible leaching of Au).     

General Preparation of Heme Protein Functional Fe3O4@Au‐Nps Magnetic Nanocomposite for Sensitive Detection of Hydrogen Peroxide

Stable magnetic nanocomposite of gold nanoparticles (Au‐NPs) decorating Fe₃O₄ core was successfully synthesized by the linker of Boc‐L‐cysteine. Transmission electron microscope (TEM), energy dispersive X‐ray spectroscopy (EDX) and cyclic voltammograms (CV) were performed to characterize the as‐prepared Fe₃O₄@Au‐Nps. The results indicated that Au‐Nps dispersed homogeneously around Fe₃O₄ with the ratio of Au to Fe₃O₄ nanoparticles as 5–10/1 and the apparent electrochemical area as 0.121 cm². After self‐assembly of hemoglobin (Hb) on Fe₃O₄@Au‐Nps by electrostatic interaction, a hydrogen peroxide biosensor was developed. The Fe₃O₄@Au‐Nps/Hb modified GCE exhibited fast direct electron transfer between heme center and electrode surface with the heterogeneous electron transfer rate constant (Ks ) of 3.35 s⁻¹. Importantly, it showed excellent electrocatalytic activity towards hydrogen peroxide reduction with low detection limit of 0.133 μM (S /D =3) and high sensitivity of 0.163 μA μM⁻¹, respectively. At the concentration evaluated, the interfering species of glucose, dopamine, uric acid and ascorbic acid did not affect the determination of hydrogen peroxide. These results demonstrated that the introduction of Au‐Nps on Fe₃O₄ not only stabilized the immobilized enzyme but also provided large surface area, fast electron transfer and excellent biocompatibility. This facile nanoassembly protocol can be extended to immobilize various enzymes, proteins and biomolecules to develop robust biosensors.     

Magnetically Encoded Luminescent Composite Nanoparticles through Layer‐by‐Layer Self‐Assembly

Sensitive and rapid detection of multiple analytes and the collection of components from complex samples are important in fields ranging from bioassays/chemical assays, clinical diagnosis, to environmental monitoring. A convenient strategy for creating magnetically encoded luminescent CdTe@SiO₂@n Fe₃O₄ composite nanoparticles, by using a layer‐by‐layer self‐assembly approach based on electrostatic interactions, is described. Silica‐coated CdTe quantum dots (CdTe@SiO₂) serve as core templates for the deposition of alternating layers of Fe₃O₄ magnetic nanoparticles and poly(dimethyldiallyl ammonium chloride), to construct CdTe@SiO₂@n Fe₃O₄ (n=1, 2, 3, …?) composite nanoparticles with a defined number (n) of Fe₃O₄ layers. Composite nanoparticles were characterized by zeta‐potential analysis, fluorescence spectroscopy, vibrating sample magnetometry, and transmission electron microscopy, which showed that the CdTe@SiO₂@n Fe₃O₄ composite nanoparticles exhibited excellent luminescence properties coupled with well‐defined magnetic responses. To demonstrate the utility of these magnetically encoded nanoparticles for near‐simultaneous detection and separation of multiple components from complex samples, three different fluorescently labeled IgG proteins, as model targets, were identified and collected from a mixture by using the CdTe@SiO₂@n Fe₃O₄ nanoparticles.     

Facile fabrication of magnetic MoO2–Salen‐modified graphene‐based catalyst for epoxidation of alkenes

A facile, green and efficient method for the immobilization of MoO₂–Salen onto graphene hybridized with glucose‐coated magnetic Fe₃O₄ nanoparticles is proposed to fabricate a magnetic organic–inorganic hybrid heterogeneous RGO/Fe₃O₄@C‐Salen‐MoO₂ catalyst for the epoxidation of cyclooctene and geraniol using tert ‐butyl hydroperoxide or H₂O₂ as oxidant. Carbon‐coated Fe₃O₄ can improve the stability and add functional ─OH groups on the surface of Fe₃O₄. The fabricated composite exhibited good performance due to good dispersion of MoO₂–Salen active sites. The catalyst can be easily separated from the reaction system using a permanent magnet and used three times without significantly losing its catalytic activity and selectivity.     

Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe3O4@polyaniline composites as a highly efficient,magnetically separable and atom‐economical catalyst for reduction of nitrobenzenes

The preparation of Ni@Pd core–shell nanoparticles immobilized on yolk–shell Fe₃O₄@polyaniline composites is reported. Fe₃O₄ nanoclusters were first synthesized through the solvothermal method and then the SiO₂ shell was coated on the Fe₃O₄ surface via a sol–gel process. To prepare Fe₃O₄@SiO₂@polyaniline composites, polyvinylpyrrolidone was first grafted on to the surface of Fe₃O₄@SiO₂ composites and subsequently polymerization of aniline was carried out via an ultrasound‐assisted in situ surface polymerization method. Selective etching of the middle SiO₂ layer was then accomplished to obtain the yolk–shell Fe₃O₄@polyaniline composites. The approach uses polyaniline (PANI) conductive polymer as a template for the synthesis of Ni@Pd core–shell nanoparticles. The catalytic activity of the synthesized yolk–shell Fe₃O₄@PANI/Ni@Pd composite was investigated in the reduction of o‐nitroaniline to benzenediamine by NaBH₄, which exhibited conversion of 99% in 3 min with a very low content of the catalyst. Transmission electron microscopy, X‐ray photoelectron spectroscopy, TGA, X‐ray diffraction, UV–visible, scanning electron microscopy, X‐ray energy dispersion spectroscopy and FT‐IR were employed to characterize the synthesized nanocatalyst. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis,characterization and catalytic performance of core‐shell structure magnetic Fe3O4/P(GMA‐EGDMA)‐NH2/HPG‐COOH‐Pd catalyst

A strategy has been developed for the synthesis, characterization and catalysis of magnetic Fe₃O₄/P(GMA‐EGDMA)‐NH₂/HPG‐COOH‐Pd core‐shell structure supported catalyst. The P(GMA‐EGDMA) polymer layer was coated on the surface of hollow magnetic Fe₃O₄ microspheres through the effect of KH570. The core‐shell magnetic Fe₃O₄/P(GMA‐EGDMA) modified by ‐NH₂ could be grafted with HPG. Then, the hyperbranched glycidyl (HPG) with terminal ‐OH were modified by ‐COOH and adsorbed Pd nanoparticles. The hyperbranched polymer layer not only protected the Fe₃O₄ magnetic core from acid–base substrate corrosion, but also provided a number of functional groups as binding sites for Pd nanoparticles. The prepared catalyst was characterized by UV–vis, TEM, SEM, FTIR, TGA, ICP‐OES, BET, XRD, DLS and VSM. The catalytic tests showed that the magnetic Fe₃O₄/P(GMA‐EGDMA)‐NH₂/HPG‐COOH‐Pd catalyst had excellent catalytic performance and retained 86% catalytic efficiency after 8 consecutive cycles.     

Novel synthesis of Fe2O3–Pt ellipsoids coated by double‐shelled La2O3 as a catalyst for the reduction of 4‐nitrophenol

A facile strategy is reported for the fabrication of Pt‐loaded core–shell nanocomposite ellipsoids (Fe₂O₃‐Pt@DSL) consisting of ellipsoidal Fe₂O₃ cores, double‐layered La₂O₃ shells and deposited Pt nanoparticles (NPs). The formation of the doubled‐shelled structure uses Fe₂O₃‐Pt@mSiO₂ as template sacrificial agent and it involves the re‐deposition of silica and self‐assembly of metal oxide units. The preparation methods of double‐shelled metal oxides avoid repeated coating and etching and could be utilized to fabricate other shaped double‐shelled composites. Characterization results indicated that the Fe₂O₃‐Pt@DSL nanocomposites possessed mesoporous structure and tunable shell thickness. Moreover, due to the formation of Fe₂O₃ and La₂O₃ composites, Pt NPs can also be stabilized via deposition on chemically active oxides with a synergistic effect. Therefore, as a catalyst for the reduction of 4‐nitrophenol, Fe₂O₃‐Pt@DSL showed superior catalytic activity and reusability due to structural superiority and enhanced composite synergy. Finally, well‐dispersed Pt NPs were encapsulated into the void between the shell layers to construct the Fe₂O₃‐Pt@DSL‐Pt catalyst.     

Carbon Electrodes Modified by Nanoscopic Iron(III) Oxides to Assemble Chemical Sensors for the Hydrogen Peroxide Amperometric Detection

In this study we show that nanoparticles of various ferric oxides (hematite, maghemite, amorphous Fe₂O₃, β‐Fe₂O₃ and ferrihydrite) incorporated into carbon paste exhibit electro‐catalytic properties towards hydrogen peroxide reduction. The modified paste electrode performances were evaluated and compared with those obtained with Prussian Blue‐modified carbon paste electrode, which represents an excellent chemical mediator towards the H₂O₂ redox reaction (as widely described in literature). The best catalytic activity was found for carbon paste modified by amorphous ferric oxide with 2–4 nm particle size, which was further tested for possible application as hydrogen peroxide sensor. At pH 7, the limit of detection was 2×10^?5 M H₂O₂ (S/N=3), the calibration curves were linear upto 8.5 mM H₂O₂ (R²=0.998), the measurement reproducibility (RSD=97%, n=4), the interelectrode reproducibility (RSD=16%, n_electrodes=5) and <3 s response time.     

Facile one‐step synthesis of electromagnetic functionalized polypyrrole/Fe3O4 nanotubes via a self‐assembly process

This article reports a simple self‐assembly process for facile one‐step synthesis of novel electromagnetic functionalized polypyrrole (PPy)/Fe₃O₄ composite nanotubes using p‐toluenesulfonic acid (p‐TSA) as the dopant and FeCl₃ as the oxidant. The key trick of the present method is to use FeCl₃ as the oxidant for both PPy and Fe₃O₄ in the same time to synthesize PPy/Fe₃O₄ composite nanotubes in one‐step. This facile one‐step method is much simpler than the conventional approach using the Fe₃O₄ nanoparticles as the additives. Compared to the similar composites synthesized using the conventional method, the as‐prepared PPy‐p‐TSA/Fe₃O₄ composite nanotubes using the facile one‐step self‐assembly process show much higher room‐temperature conductivity. Moreover, the composite nanotubes display interesting ferromagnetic behavior. The electrical properties of the PPy‐p‐TSA/Fe₃O₄ composite nanotubes are dominated by the amount of FeCl₃ while their magnetic properties are controlled by the amount of FeCl₂. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 320–326, 2010     

Amorphizing of Ag Nanoparticles under Bioinspired One‐step Assembly of Fe3O4‐Ag/rGO Hybrids via Self‐redox Process with Enhanced Activity

Efficient and reusable nanocatalysts fabricated via a facile assembly are highly desirable for the cost‐effective hydrogenation reduction. Inspired by a fishing process with a fishnet, multifunctional nanostructured catalysts are rationally designed to combine interesting features via the self‐redox assembly of Fe₃O₄‐Ag composites on reduced graphene oxide (rGO) (Fe₃O₄‐Ag/rGO). In detail, Fe₃O₄ nanoparticles (NPs) endow the ternary hybrids with superparamagnetism (21.42 emu g^?1), facilitating catalysts to be separated from the reaction system. rGO could provide electron transfer pathways, enhancing catalytic activity. More interestingly, GO and Ag⁺ could behave as oxidants to oxidize Fe²⁺ for the in situ assembly of Fe₃O₄‐Ag/rGO without any addition of reductant/oxidant or organic solvents, and AgNPs endow the ternary hybrids with excellent catalytic behaviour. Meaningfully, the bioinspired process enables the ternary hybrids to possess more abundant micro?/nanopores, larger surface area, and more amorphization. They exhibit exceptional catalytic performance, and could be recycled with excellent activity by means of convenient magnetic separation (at least 7 times). Moreover, the ternary hybrids could degrade methylene blue under UV light due to different valence states of Fe in Fe₃O₄. Therefore, the proposed bioinspired assembly and structure design for hierarchical catalysts would pave a promising way to assemble other catalysts.     

Fe3O4@L‐arginine magnetic nanoparticles: A novel and magnetically retrievable catalyst for the synthesis of 1′3‐diaryl‐2N‐azaphenalene

The catalytic activity of l ‐arginine‐coated nano‐Fe₃O₄ particles (Fe₃O₄@l ‐arginine) proves they are a novel magnetic catalyst without the use of heat and reflux for the synthesis of 1,3‐diaryl‐2‐N‐azaphenalene derivatives and n‐acyl‐1,3‐diaryl‐2‐N‐azaphenylene derivatives in a one‐pot pseudo‐five‐component condensation reaction of compounds of 2,7‐naphthalene diol, aldehydes, and ammonia derivatives (ammonium acetate or ammonium hydrogen phosphate) and solvent (water and alcohol) with high yield and short reaction times, economical, and simple workup. The structure and magnetic properties of the obtained nanoparticles were characterized via Fourier transform infrared spectroscopy (IR) and field emission scanning electron microscopy (FE‐SEM). The results demonstrated that the average size of the synthesized magnetite nanoparticles is about 21 nm. In addition, the heterogeneous catalyst can be easily recovered magnetically and can be reused for further runs without significant loss of its catalytic activity.     

Magnetic solid‐phase extraction based on a polydopamine‐coated Fe3O4 nanoparticles absorbent for the determination of bisphenol A,tetrabromobisphenol A, 2,4,6‐tribromophenol,and (S)‐1,1’‐bi‐2‐naphthol in environmental waters by HPLC

Polydopamine‐coated Fe₃O₄ magnetic nanoparticles synthesized through a facile solvothermal reaction and the self‐polymerization of dopamine have been employed as a magnetic solid‐phase extraction sorbent to enrich four phenolic compounds, bisphenol A, tetrabromobisphenol A, (S)‐1,1′‐bi‐2‐naphthol and 2,4,6‐tribromophenol, from environmental waters followed by high‐performance liquid chromatographic detection. Various parameters of the extraction were optimized, including the pH of the sample matrix, the amount of polydopamine‐coated Fe₃O₄ sorbent, the adsorption time, the enrichment factor of analytes, the elution solvent, and the reusability of the nanoparticles sorbent. The recoveries of these phenols in spiked water samples were 62.0–112.0% with relative standard deviations of 0.8–7.7%, indicating the good reliability of the magnetic solid‐phase extraction with high‐performance liquid chromatography method. In addition, the extraction characteristics of the magnetic polydopamine‐coated Fe₃O₄ nanoparticles were elucidated comprehensively. It is found that there are hydrophobic, π–π stacking and hydrogen bonding interactions between phenols and more dispersible polydopamine‐coated Fe₃O₄ in water, among which hydrophobic interaction dominates the magnetic solid‐phase extraction performance.     

An Amperometric Hydrogen Peroxide Biosensor Based on a Hemoglobin‐Immobilized Dopamine‐Oxidation Polymer/Prussian Blue/Au Electrode

A novel method to immobilize hemoglobin (Hb) in a polymer grown from dopamine (DA) oxidation was proposed. The growth of the polymeric films during DA oxidation at the Prussian blue (PB) modified Au electrode in weak alkaline phosphate buffer (pH 9.18) and the immobilization of Hb into the polymeric films during their growth were traced by the electrochemical quartz crystal impedance analysis (EQCIA) method. A hydrogen peroxide (H₂O₂) biosensor was thus constructed, and effects of experimental parameters on the sensor performance, including the applied potential, solution pH and electroactive interferents, were examined. At an optimal potential of ?0.25 V vs. SCE, the current response of the biosensor in the selected phosphate buffer (pH 5.29) was linear with the concentration of H₂O₂ from 0.01 to 4.5 mM, with a lower limit of detection of 0.5 μM (S/N=3), short response time (within 10 s) and good anti‐interferent ability. The Michaelis constant (K_m^app) was estimated to be 3.80 mM. Compared with the separate film of PB or Hb, the composite film of Hb and PB exhibited a higher catalytic activity toward the reduction of H₂O₂, as a result of the additive effect of the chemical and biological catalyses.     

Magnetite Nanorods Stabilized by Polyaniline/Reduced Graphene Oxide as a Sensing Platform for Selective and Sensitive Non‐enzymatic Hydrogen Peroxide Detection

In this study, magnetite nanorods stabilized on polyaniline/reduced graphene oxide (Fe₃O₄@PANI/rGO) was synthesized via a wet‐reflux strategy. The possible formation of Fe₃O₄@PANI/rGO was morphologically and structurally verified by field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Furthermore, the thermal stability of Fe₃O₄@PANI/rGO was measured by a thermogravimetric analyzer (TGA); the composite had good thermal stability owing to the ceramic nature of Fe₃O₄. The Fe₃O₄@PANI/rGO has been applied as a potential sensing platform for electrochemical detection of hydrogen peroxide (H₂O₂). By the combined efforts of extended active surface area, active carbon support, more catalytic active sites and high electrical conductivity, the Fe₃O₄@PANI/rGO exhibited an improved performance toward the non‐enzymatic detection of H₂O₂ in 0.5 M KOH with a fast response time (5 s), high sensitivity (223.7 μA mM^?1 cm^?2), low limit of detection (4.45 μM) and wide linear range (100 μM–1.5 mM). Furthermore, the fabricated sensor exhibited excellent recovery rates (94.2–104.0 %) during real sample analysis.     

Enhanced stability of a Prussian blue/sol-gel composite for electrochemical determination of hydrogen peroxide

We have prepared a sol–gel that incorporates Prussian Blue (PB) as a redox mediator. It is shown that the PB in the pores of the sol–gel retains its electrochemical activity and is protected from degradation at acidic and neutral pH values. TEM and EDX studies revealed the PB nanoparticles to possess a cubic crystal structure and to be well entrapped and uniformly dispersed in the pores of the matrix. The electrocatalytic activity of the materials toward hydrogen peroxide (H₂O₂) was studied by cyclic voltammetry and amperometry. The modified electrode displays good sensitivity for the electrocatalytic reduction of H₂O₂ both in acidic (pH 1.4) and neutral media. The sensor has a dynamic range from 3 to 210 μM of H₂O₂, and the detection limit is 0.6 μM (at an SNR of 3).

Green synthesis of Fe3O4@SiO2‐Ag magnetic nanocatalyst using safflower extract and its application as recoverable catalyst for reduction of dye pollutants in water

This paper reports the green and in situ preparation of Fe₃O₄@SiO₂‐Ag magnetic nanocatalyst synthesized using safflower (Carthamus tinctorius L.) flower extract without the addition of any stabilizers or surfactants. The catalytic performance of the resulting nanocatalyst was examined for the reduction of 4‐nitrophenol (4‐NP), methylene blue (MB) and methyl orange (MO) in an environment‐friendly medium at room temperature. The main factors such as pH, temperature and amount of catalyst influencing the nanocatalyst performance were studied. The apparent rate constants for 4‐NP, MO and MB reduction were calculated, being 0.756 min^?1, 0.064 s^?1 and 0.09 s^?1, respectively. The catalyst was recovered using an external magnet and reused several times with negligible loss of catalytic activity. The as‐synthesized nanoparticles were characterized using powder X‐ray diffraction, transmission electron microscopy, UV–visible, Fourier transform infrared and inductively coupled plasma atomic emission spectroscopies, dynamic light scattering and vibrating sample magnetometry.     

Synthesis and characteristics of poly(N‐isopropylacrylamide‐co‐methacrylic acid)/Fe3O4 thermosensitive magnetic composite hollow latex particles

In this study, the poly(NIPAAm–MAA)/Fe₃O₄ hollow latex particles were synthesized by three steps. The first step was to synthesize the poly(methyl methacrylate‐co‐methylacrylate acid) (poly(MMA‐MAA)) copolymer latex particles by the method of soapless emulsion polymerization. Following the first step, the second step was to polymerize N‐isopropylacrylamide (NIPAAm), MAA, and crosslinking agent (N,N'‐methylene‐bisacrylamide (MBA)) in the presence of poly(MMA‐MAA) latex particles to form the linear poly(MMA‐MAA)/crosslinking poly (NIPAAm‐MAA) core‐shell latex particles. After the previous processes, the core‐shell latex particles were heated in the presence of NH₄OH to dissolve the linear poly(MMA‐MAA) core in order to form the poly(NIPAAm‐MAA) hollow latex particles. In the third step, Fe²⁺ and Fe³⁺ ions were introduced to bond with the ? COOH groups of MAA segments in the poly(NIPAAm‐MAA) hollow polymer latex particles. Further by a reaction with NH₄OH and then Fe₃O₄ nanoparticles were generated in situ and the poly(NIPAAm‐MAA)/Fe₃O₄ magnetic composite hollow latex particles were formed. The concentrations of MAA, crosslinking agent (N,N'‐methylene bisacrylamide), and Fe₃O₄ nanoparticles were important factors to influence the morphology of hollow latex particles and lower critical solution temperature of poly(NIPAAm–MAA)/Fe₃O₄ magnetic composite hollow latex particles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characteristics of poly(N‐isopropylacrylamide‐co‐methacrylic acid)/Fe3O4/poly(N‐isopropylacrylamide‐co‐methacrylic acid) two‐shell thermosensitive magnetic composite hollow latex particles

In this study, the poly(N‐isopropylacrylamide‐methylacrylate acid)/Fe₃O₄/poly(N‐isopropylacrylamide‐methylacrylate acid) (poly(NIPAAm‐MAA)/Fe₃O₄/poly(NIPAAm‐MAA)) two‐shell magnetic composite hollow latex particles were synthesized by four steps. The poly(methyl methacrylate‐co‐methylacrylate acid) (poly(MMA‐MAA)) copolymer latex particles were synthesized first. Then, the second step was to polymerize NIPAAm, MAA, and crosslinking agent in the presence of poly(MMA‐MAA) latex particles to form the linear poly(MMA‐MAA)/crosslinking poly(NIPAAm‐MAA) core–shell latex particles. Then, the core–shell latex particles were heated in the presence of NH₄OH to dissolve the linear poly(MMA‐MAA) core to form the poly(NIPAAm‐MAA) hollow latex particles. In the third step, the Fe₃O₄ nanoparticles were generated in the presence of poly(NIPAAm‐MAA) hollow polymer latex particles and formed the poly(NIPAAm‐MAA)/Fe₃O₄ magnetic composite hollow latex particles. The fourth step was to synthesize poly(NIPAAm‐MAA) in the presence of poly(NIPAAm‐MAA)/Fe₃O₄ latex particles to form the poly(NIPAAm‐MAA)/Fe₃O₄/poly(NIPAAm‐MAA) two‐shell magnetic composite hollow latex particles. The effect of various variables such as reactant concentration, monomer ratio, and pH value on the morphology and volume‐phase transition temperature of two‐shell magnetic composite hollow latex particles was studied. Moreover, the latex particles were used as carriers to load with caffeine, and the caffeine‐loading characteristics and caffeine release rate of latex particles were also studied. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2880–2891     

Preparation of novel palladium nanoparticles supported on magnetic iron oxide and their catalytic application in the synthesis of 2‐imino‐3‐phenyl‐2,3‐dihydrobenzo[d]oxazol‐5‐ols

Novel Pd nanoparticles were prepared in five successive stages: 1) preparation of the Fe₃O₄ magnetic nanoparticles (Fe₃O₄ MNPs), 2) coating of Fe₃O₄ MNPs with SiO₂ (Fe₃O₄@SiO₂), 3) functionalization of Fe₃O₄@SiO₂ with 3‐chloropropyltrimethoxy‐ silane (CPTMS) ligand (Fe₃O₄@SiO₂@CPTMS), 4) further functionalization with 3,5‐diamino‐1,2,4‐triazole (DAT) ligand (Fe₃O₄@SiO₂@CPTMS @DAT), and 5) the complexation of Fe₃O₄@SiO₂@CPTMS@DAT with PdCl₂ (Fe₃O₄@SiO₂@CPTMS@ DAT@Pd). Then, the obtained Pd nano‐catalyst characterized by different methods such as the elemental analysis (CHN), FT‐IR, XRD, EDX, SEM, TEM, TG‐DTA and VSM. Finally, the Pd catalyst was applied for the synthesis of various 2‐imino‐3‐phenyl‐2,3‐dihydrobenzo[d]oxazol‐5‐ols.     

A new nano‐Fe3O4‐supported organocatalyst based on 3,4‐dihydroxypyridine: an efficient heterogeneous nanocatalyst for one‐pot synthesis of pyrazolo[3,4‐b]pyridines and pyrano[2,3‐d]pyrimidines

A simple and practical strategy for the synthesis of a novel nano‐Fe₃O₄‐supported organocatalyst system based on 3,4‐dihydroxypyridine (Fe₃O₄/Py) has been developed. The prepared catalyst was characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopies, X‐ray diffraction, vibrating sample magnetometry and energy‐dispersive X‐ray analysis. Accordingly, the Fe₃O₄/Py nanoparticles show a superparamagnetic property with a saturation magnetization of 61 emu g^?1, indicating potential application in magnetic separation technology. Our experimental results reveal that the pyridine‐functionalized Fe₃O₄ nanoparticles are an efficient base catalyst for the domino condensation of various aromatic aldehydes, Meldrum's acid and 5‐methylpyrazol‐3‐amine under very mild reaction condition and in the presence of ethanol solvent. Moreover, the synthesized catalyst was used for one‐pot, three‐component condensation of aromatic aldehydes with barbituric acid and malononitrile to produce 7‐amino‐2,4‐dioxo‐5‐phenyl‐2,3,4,5‐tetrahydro‐1H‐pyrano[2,3‐d]pyrimidine‐6‐carbonitriles. All reactions are completed in short times and all products are obtained in good to excellent yields. Also, notably, the catalyst was reused five times without significant degradation in catalytic activity and performance. Copyright © 2016 John Wiley & Sons, Ltd.