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1.
A reversible addition‐fragmentation chain transfer (RAFT) agent was directly anchored onto Fe3O4 nanoparticles in a simple procedure using a ligand exchange reaction of S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate with oleic acid initially present on the surface of pristine Fe3O4 nanoparticles. The RAFT agent‐functionalized Fe3O4 nanoparticles were then used for the surface‐initiated RAFT copolymerization of N‐isopropylacrylamide and acrolein to fabricate structurally well‐defined hybrid nanoparticles with reactive and thermoresponsive poly(N‐isopropylacrylamide‐co‐acrolein) shell and magnetic Fe3O4 core. Evidence of a well‐controlled surface‐initiated RAFT copolymerization was gained from a linear increase of number‐average molecular weight with overall monomer conversions and relatively narrow molecular weight distributions of the copolymers grown from the nanoparticles. The resulting novel magnetic, reactive, and thermoresponsive core‐shell nanoparticles exhibited temperature‐trigged magnetic separation behavior and high ability to immobilize model protein BSA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 542–550, 2010  相似文献   

2.
A facile and effective approach to preparation of dual‐responsive magnetic core/shell composite microspheres is reported. The magnetite(Fe3O4)/poly(methacrylic acid) (PMAA) composite microspheres were synthesized through encapsulating γ‐methacryloxypropyltrimethoxysilane (MPS)‐modified magnetite colloid nanocrystal clusters (MCNCs) with crosslinked PMAA shell. First, the 200‐nm‐sized MCNCs were fabricated through solvothermal reaction, and then the MCNCs were modified with MPS to form active vinyl groups on the surface of MCNCs, and finally, a pH‐responsive shell of PMAA was coated onto the surface of MCNCs by distillation‐precipitation polymerization. The transmission electron microscopy (TEM) and vibrating sample magnetometer characterization showed that the obtained composite microspheres had well‐defined core/shell structure and high saturation magnetization value (35 emu/g). The experimental results indicated that the thickness and degree of crosslinking of PMAA shell could be well‐controlled. The pH‐induced change in size exhibited by the core/shell microspheres reflected the PMAA shell contained large amount of carboxyl groups. The carboxyl groups and high saturation magnetization make these microspheres have a great potential in biomolecule separation and drug carriers. Moreover, we also demonstrated that other magnetic polymeric microspheres, such as Fe3O4/PAA, Fe3O4/PAM, and Fe3O4/PNIPAM, could be synthesized by this approach. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
Magnetic poly(methyl methacrylate) (PMMA)/poly(methyl methacrylate‐co‐methacrylic acid) [P(MMA–MAA)] composite polymer latices were synthesized by two‐stage soapless emulsion polymerization in the presence of magnetite (Fe3O4) ferrofluids. Different types and concentrations of fatty acids were reacted with the Fe3O4 particles, which were prepared by the coprecipitation of Fe(II) and Fe(III) salts to obtain stable Fe3O4 ferrofluids. The Fe3O4/polymer particles were monodisperse, and the composite polymer particle size was approximately 100 nm. The morphology of the magnetic composite polymer latex particles was a core–shell structure. The core was PMMA encapsulating Fe3O4 particles, and the shell was the P(MMA–MAA) copolymer. The carboxylic acid functional groups (COOH) of methacrylic acid (MAA) were mostly distributed on the surface of the composite polymer latex particles. Antibodies (anti‐human immunoglobulin G) were then chemically bound with COOH groups onto the surface of the magnetic core–shell composite latices through the medium of carbodiimide to form the antibody‐coated magnetic latices (magnetic immunolatices). The MAA shell composition of the composite latex could be adjusted to control the number of COOH groups and thus the number of antibody molecules on the magnetic composite latex particles. With a magnetic sorting device, the magnetic immunolatices derived from the magnetic PMMA/P(MMA–MAA) core–shell composite polymer latex performed well in cell‐separation experiments based on the antigen–antibody reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1342–1356, 2005  相似文献   

6.
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  相似文献   

7.
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.  相似文献   

8.
A new method is applied to prepare stable aqueous dispersion of magnetic iron oxide nanoparticles (MNPs) by biocompatible maleate polymers. Fe3O4 magnetic core–shell nanoparticles are obtained via forming an inclusion complex between carboxylic acid groups of maleated biocompatible polymers shell and Fe3O4 MNPs core surface. Maleate polymers are synthesized via esterification of poly(ethylene glycol), poly(vinyl alcohol) and starch with maleic anhydride (MA). The Fe3O4 magnetic core–shell nanoparticles are characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy and vibrating sample magnetometer. The obtained magnetic core–shell nanoparticles exhibit superparamagnetic property and reveal long‐term aqueous stability. This work represents a valid methodology to produce highly stable aqueous dispersion of Fe3O4 MNPs ferrofluids which can be expected to have great potential as contrast agent for magnetic resonance imaging. Furthermore, the shell composition of biocompatible maleate polymers with double bond of MA as crosslinker agent allows the polymerization with other monomers to design preferred drug delivery systems. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

9.
Iron oxide@Poly(Glycidylmethacrylate‐methyl methacrylate‐divinyl benzene) magnetic composite core shell microspheres Fe3O4@P(GMA‐MMA‐DVB) with epoxy group on the surface was designed and synthesized by solvothermal process followed by distillation polymerization. The surface epoxy group was modified with amino group of ethylene diamine (EDA) to prepare Fe3O4@P(GMA‐MMA‐DVB)/NH2 microspheres, and then effects of modification on the structure, interfacial behavior and hence demulsification of the amino modified epoxy coating were examined. The prepared magnetic microspheres were characterized using a laser particle size analyzer, transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometry, and thermogravimetric analysis. Fourier transform infrared spectrometer analysis indicates the presence of epoxy group, amino group and Fe3O4 in the final Fe3O4@P(GMA‐MMA‐DVB) and Fe3O4@P(GMA‐MMA‐DVB)/NH2 magnetic core shell microspheres. Our experimental results show that Fe3O4@P(GMA‐MMA‐DVB)/NH2 magnetic core shell microspheres exhibit good interfacial and demulsification properties and able to remove emulsified water from stable emulsion. The resulting microspheres showed excellent magnetic properties and further these can be recycled and reused by magnetic separation.  相似文献   

10.
Au nanoparticles (Au NPs) play a vital role in heterogeneous catalytic reactions. However, pristine Au NPs usually suffer from poor selectivity and difficult recyclability. In this work, Fe3O4‐Au@CeO2 hybrid nanofibers were prepared via a simple one‐pot redox reaction between HAuCl4 and Ce (NO3)3 in the presence of Fe3O4 nanofibers. CeO2 shell was uniformly coated on the surface of Fe3O4 nanofibers to form a unique core‐shell structure, while Au NPs were encapsulated inside the CeO2 shell. The as‐prepared Fe3O4‐Au@CeO2 hybrid nanofibers have been proved to be positively surface charged due to the formation of CeO2 shell, enabling them to be good candidates for predominant selective catalytic activity towards the degradation of negatively charged organic dyes. In addition, the Fe3O4‐Au@CeO2 hybrid nanofibers showed magnetic properties, offering them excellent recyclable usability. This work presents a facile and effective solution to prepare magnetic noble metal/metal oxide hybrid nanomaterials with unique chemical structure and surface characteristic for promising applications in heterogeneous catalysis.  相似文献   

11.
The simple preparation of catalysts with superior catalytic activity and good reusability is highly desirable. Herein, we report a novel strategy to construct reduced graphene oxide (rGO)/Pd–Fe3O4@polypyrrole (PPy) catalysts with Pd and Fe3O4 nanoparticles anchored on a rGO nanosheet surface and wrapped in a PPy shell. The synthesis and assembly of both the Pd and Fe3O4 nanoparticles, the preparation of the PPy layer, and the reduction of graphene oxide nanosheets were finished in one step. In the system, the PPy layer not only prevented aggregation of Pd and Fe3O4 nanoparticles, but also generated a synergistic effect with precursor Pd2+ ions, which led to a high dispersity of as‐prepared Pd nanoparticles. Although the procedure was simplified to one step, the catalytic activity and reusability were not sacrificed. In the reduction of 4‐nitrophenol, their catalytic performance was better than that in recent reports. Moreover, the catalysts showed good reusability owing to their magnetic properties.  相似文献   

12.
Iron oxide (Fe3O4) magnetic nanoparticles as movable cores were used to synthesize yolk–shell nanoparticles with pH‐responsive shell composed of ethylene glycol dimethacrylate (EGDMA)‐crosslinked poly(acrylic acid) (PAA) via two different routes. In the first more common route, Fe3O4 nanoparticles were coated with silica layer via the Stöber process to yield Fe3O4@SiO2 core–shell nanoparticles, subsequently used as seeds in the distillation precipitation copolymerization of AA and EGDMA to yield Fe3O4@SiO2@P(AA‐EGDMA). The silica layer was selectively removed through alkali etching to yield Fe3O4@air@P(AA‐EGDMA). In the second route, Fe3O4 nanoparticles without any stabilization were used as seeds in the distillation precipitation copolymerization of AA and EGDMA to yield Fe3O4@P(AA‐EGDMA) core–shell nanoparticles. The nanoparticles were subsequently dispersed in acidic medium of pH = 2. Yolk–shell Fe3O4@air@P(AA‐EGDMA) nanoparticles were formed through deswelling of crosslinked PAA because of protonation of carboxyl groups at low pH values. Various techniques were utilized to investigate the characteristics of the synthesized core–shell nanoparticles. Formation of yolk–shell nanostructure was observed for both synthesis routes, namely etching of silica layer and deswelling approaches, from vibrating sample magnetometry and transmission electron microscopy results. Both types of nanoparticles showed pH‐responsive behaviour, i.e. decrease in absorption with increase in pH, as examined using UV–visible spectroscopy.  相似文献   

13.
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).  相似文献   

14.
DABCO (1,4‐diazabicyclo[2.2.2]octane)‐modified magnetite with silica‐MCM‐41 shell (Fe3O4@silica‐MCM‐41@DABCO) as an effective, magnetic and novel heterogeneous reusable nanocatalyst was synthesized and analysed using various techniques. Evaluation of the catalytic activity of this nanocatalyst was performed in the clean synthesis of substituted 2‐aminodihydropyrano[3,2‐b]pyran‐3‐cyano in high yields via in situ reaction of azido kojic acid, malononitrile and various aldehydes.  相似文献   

15.
A novel super acidic magnetic nanoparticle as catalyst was successfully synthesized. The preparation of this dendrimer sulfonic acid functionalized γ‐Fe2O3 magnetic core‐shell silica nanoparticles as a new recoverable and heterogeneous nanocatalyst was described. The new catalyst was characterized using various techniques such as scanning electron microscopy (SEM), energy dispersive spectrum (EDS), and thermo gravimetric synthesis (TGA). Moreover, we have examined the catalytic activity of the catalyst for one‐pot, efficient and facile synthesis of 2‐hydroxy‐1,4‐naphthoquinone derivatives via a three‐component condensation reaction of 2‐hydroxynaphthalene‐1,4‐dione, aromatic aldehydes and aniline derivatives. High yields of products, short reaction times, waste‐free, mild, ambient and solvent‐free reaction conditions are advantages of this protocol. Also, the catalyst can be easily recovered by an external magnetic and reused several times without significant loss of its catalytic activity.  相似文献   

16.
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 CuII ions were then loaded onto the modified surface of nanocatalyst. Finally, uniformly dispersed copper nanoparticles were achieved by reduction of CuII 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.  相似文献   

17.
This study describes the preparation of a nanocomposites fabricated from monodispersed 4‐nm iron oxide (Fe3O4) coated on the surface of carboxylic acid containing multi‐walled carbon nanotube (c‐MWCNT) and polypyrrole (PPy) by in situ chemical oxidative polymerization. High‐resolution transmission electron microscopy images and X‐ray diffraction (XRD) data indicate that the resulting Fe3O4 nanoparticles synthesized using the thermal decomposition are close to spherical dots with a particle size about 4 ± 0.2 nm. The resulting nanoparticles were further mixed with c‐MWCNT in an aqueous solution containing with anionic surfactant sodium bis(2‐ethylhexyl) sulfosuccinate to form one‐dimensional Fe3O4 coated c‐MWCNT template for further preparation of nanocomposite. Structural and morphological analysis using field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, and XRD showed that the fabricated Fe3O4 coated c‐MWCNT/PPy nanocomposites are one‐dimensional core (Fe3O4 coated c‐MWCNT)‐shell (PPy) structures. The conductivities of these Fe3O4 coated c‐MWCNT/PPy nanocomposites are about four times higher than those of pure PPy matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 727–733, 2008  相似文献   

18.
To address the obstacles facing the use of palladium‐based homogeneous and heterogeneous catalysts in C─C cross‐coupling reactions, a novel semi‐heterogeneous support was developed based on hyperbranched poly(ethylene glycol)‐block ‐poly(citric acid)‐functionalized Fe3O4 magnetic nanoparticles (Fe3O4@PCA‐b ‐PEG). Because of the surface modification of the Fe3O4 nanoparticles with amphiphilic and hyperbranched polymers (PCA‐b ‐PEG), these hybrid materials are not only soluble in a wide range of solvents (e.g. water, ethanol and dimethylformamide) but also are able to trap Pd2+ ions via complex formation of free carboxyl groups of the PCA dendrimer with metal ions. The reduction of trapped palladium ions in the dendritic shell of Fe3O4@PCA‐b ‐PEG leads to immobilized palladium nanoparticles. The morphology and structural features of the catalyst were characterized using various microscopic and spectroscopic techniques. The catalyst was effectively used in the palladium‐catalysed Mizoroki–Heck coupling reaction in water as a green solvent. In addition, the catalyst can be easily recovered from the reaction mixture by applying an external magnetic field and reused for more than ten consecutive cycles without much loss in activity, exhibiting an example of a sustainable and green methodology.  相似文献   

19.
A reversible addition‐fragmentation chain transfer (RAFT) agent was directly anchored onto superparamagnetic Fe3O4 nanoparticles (SPNPs) in a simple procedure using a ligand exchange reaction of 2‐[(dodecylsulfanylcarbonylthiolsulfanyl) propionic acid] (DCPA) with oleic acid initially present on the surface of Fe3O4 nanoparticles. The DCPA‐modified SPNPs were then used for the surface‐mediated RAFT polymerization of di(ethylene glycol) ethyl ether acrylate and (oligoethylene glycol) methyl ether acrylate to fabricate structurally well‐defined hybrid SPNPs with temperature‐responsive poly[di(ethylene glycol) ethyl ether acrylate‐co‐(oligoethylene glycol) methyl ether acrylate] shell and magnetic Fe3O4 core. Evidence of a well‐controlled surface‐mediated RAFT polymerization was gained from a linear increase of number‐average molecular weight with overall monomer conversions and relatively narrow polydispersity indices of the copolymers grown from the SPNPs. The resultant hybrid nanoparticles exhibited superparamagnetic property with a saturation magnetization of 55.1–19.4 emu/g and showed a temperature‐responsive phenomenon as the temperature changed between 25 and 40 °C. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3420–3428  相似文献   

20.
Thiourea dioxide was immobilized on γ‐Fe2O3@Cu3Al‐LDH magnetic nanoparticles to prepare the γ‐Fe2O3@Cu3Al‐LDH‐TUD MNPs. The structure and properties of these magnetic nanoparticles were established by FT‐IR, EDX, SEM, XRD, and hystogram of particle size analytical methods. The results obtained from these analytical methods confirmed the successful immobilization of the thiourea dioxide onto the magnetic support. The synthesized magnetic nanoparticles (MNPs) exhibited high catalytic activity in one‐pot three‐component reactions under mild and solvent‐free conditions for the synthesis of diverse ranges of dihydropyrano[3,2‐c]pyrazoles and dihydropyrano[3,2‐c]chromens. All the reactions proceeded smoothly to furnish the respective products in excellent yields. Simple isolation of the products, avoidance of harmful organic solvents, versatility of the catalyst and its easy magnetic separation and reusability with no significant loss of activity are the main advantages of the present method.  相似文献   

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