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1.
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   

2.
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   

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.
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   

5.
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.  相似文献   

6.
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   

7.
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   

8.
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  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.
The first synthesis of porous, optically active, magnetic Fe3O4@poly(N‐acryloyl‐leucine) inverse core/shell composite microspheres is reported, in which the core is constructed of chiral polymer and the shell is constructed of Fe3O4 NPs. The microspheres integrate three significant concepts, “porosity”, “chirality”, and “magneticity”, in one single microspheric entity. The microspheres consist of Fe3O4 nanoparticles and porous optically active microspheres, and thus combine the advantages of both magnetic nanoparticles and porous optically active microspheres. The pore size and specific surface area of the microspheres are characterized by N2 adsorption, from which it is found that the composite microspheres possess a desirable porous structure. Circular dichroism and UV‐vis absorption spectroscopy measurements demonstrate that the microspheres exhibit the expected optical activity. The microspheres also have high saturation magnetization of 14.7 emu g–1 and rapid magnetic responsivity. After further optimization, these novel microspheres may potentially find applications in areas such as asymmetric catalysis, chiral adsorption, etc.

  相似文献   


11.
Summary: The synthesis of core‐shell particles with a poly(ε‐caprolactone) (PCL) shell and magnetite (Fe3O4) contents of between 10 wt.‐% and 41 wt.‐% proceeds by surface‐initiated ring‐opening polymerization of ε‐caprolactone to give surface‐immobilized oligomers with between 1 400 g · mol−1 and 11 500 g · mol−1. The particles are dispersable in good solvents for the PCL shell. Magnetization experiments on the resulting superparamagnetic ferrofluids give a core‐size distribution with an average diameter, dv, of about 9.7 nm.

TEM image of Fe3O4/PCL core‐shell particles cast from CHCl3 dispersion.  相似文献   


12.
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%.  相似文献   

13.
Octakis[3‐(3‐aminopropyltriethoxysilane)propyl]octasilsesquioxane (APTPOSS) as a polyhedral oligomeric silsesquioxane derivative was prepared and used as a pioneer reagent to obtain a novel core–shell composite using magnetic iron oxide nanoparticles as the core and the inorganic–organic hybrid polyhedral oligomeric silsesquioxane as the shell. Fe3O4@SiO2/APTPOSS were confirmed using Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, dynamic light scattering, thermogravimetric analysis, X‐ray diffraction and vibrating sample magnetometry. The inorganic–organic hybrid polyhedral oligomeric silsesquioxane magnetic nanoparticles were used as an efficient new heterogeneous catalyst for the one‐pot three‐component synthesis of 1,3‐thiazolidin‐4‐ones under solvent‐free conditions. Moreover, these nanoparticles could be easily separated using an external magnet and then reused several times without significant loss of catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

14.
Magnetic silica‐coated magnetite (Fe3O4) sub‐microspheres with immobilized metal‐affinity ligands are prepared for protein adsorption. First, magnetite sub‐microspheres were synthesized by a hydrothermal method. Then silica was coated on the surface of Fe3O4 particles using a sol–gel method to obtain magnetic silica sub‐microspheres with core‐shell morphology. Next, the trichloro(4‐chloromethylphenyl) silane was immobilized on them, reacted with iminodiacetic acid (IDA), and charged with Cu2+. The obtained magnetic silica sub‐microspheres with immobilized Cu2+ were applied for the absorption of bovine hemoglobin (BHb) and the removal of BHb from bovine blood. The size, morphology, and magnetic properties of the resulting magnetic micro(nano) spheres were investigated by using scanning microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD), and a vibrating sample magnetometer (VSM). The measurements showed that the magnetic sub‐microspheres are spherical in shape, very uniform in size with a core‐shell, and are almost superparamagnetic. The saturation magnetization of silica‐coated magnetite (Fe3O4) sub‐microspheres reached about 33 emu g?1. Protein adsorption results showed that the sub‐microspheres had a high adsorption capacity for BHb (418.6 mg g?1), low nonspecific adsorption, and good removal of BHb from bovine blood. This opens a novel route for future applications in removing abundant proteins in proteomic analysis.  相似文献   

15.
Facile strategy was developed for the fabrication of the monodisperse superparamagnetic pH‐sensitive single‐layer chitosan (CS) hollow microspheres with controllable structure. The carboxyl group‐functionalized polystyrene microspheres prepared by soap‐free emulsion polymerization were used as the templates. After the Fe3O4 nanoparticles were in situ formed onto the surface of the templates, the single‐layer CS was self‐assembled and cross‐linked with glutaraldehyde subsequently. Then, the magnetic single‐layer CS hollow microspheres were obtained after the templates were removed. It was found that the feeding ratio of the monomer acrylic acid in the soap‐free emulsion polymerization had played an important role on the particle size and surface carboxyl group content of the templates, which determined the particle size and shell thickness of the magnetic single‐layer CS hollow microspheres in the proposed strategy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010  相似文献   

16.
免疫磁性纳米微球的制备与表征   总被引:1,自引:0,他引:1  
王斌 《化学通报》2015,78(9):847-850
成功制备了Fe3O4磁性纳米颗粒及二甲基丙烯酸乙二醇酯-甲基丙烯酸(EGDMA-MAA)共聚物包覆的Fe3O4磁性复合微球。将吲哚美辛抗体固定在复合微球表面,形成了Fe3O4(核)/聚合物-抗体(壳)的复合免疫磁性颗粒。XRD结果表明,制备的Fe3O4的晶型为反立方尖晶石型且纯度较高;TEM表征表明Fe3O4粒径较为均匀,平均粒径为12nm;磁性复合微球的平均直径为460nm。制备的Fe3O4磁性纳米颗粒和磁性复合微球有较强的磁响应强度,其饱和磁化率分别为49.16和8.38emu/g,能够满足磁性分离的要求。FT IR验证了磁性复合微球中羧基特征峰的存在,表明羧基成功连接在磁性微球上面。通过碳二亚胺/N-羟基琥珀酰亚胺(EDC/NHS)活化法将微球表面羧基活化并成功与抗吲哚美辛抗体交联。  相似文献   

17.
Three‐dimensional (3D) flowerlike hierarchical Fe3O4@Bi2O3 core–shell architectures were synthesized by a simple and direct solvothermal route without any linker shell. The results indicated that the size of the 3D flowerlike hierarchical microspheres was about 420 nm and the shell was composed of several nanosheets with a thickness of 4–10 nm and a width of 100–140 nm. The saturation magnetization of the superparamagnetic composite microspheres was about 41 emu g?1 at room temperature. Moreover, the Fe3O4@Bi2O3 composite microspheres showed much higher (7–10 times) photocatalytic activity than commercial Bi2O3 particles under visible‐light irradiation. The possible formation mechanism was proposed for Ostwald ripening and the self‐assembled process. This novel composite material may have potential applications in water treatment, degradation of dye pollutants, and environmental cleaning, for example.  相似文献   

18.
Magnetic poly(N‐propargylacrylamide) (PPRAAm) microspheres were prepared by the precipitation polymerization of N‐propargylacrylamide (PRAAm) in a toluene/propan‐2‐ol medium in the presence of magnetic nanoparticles (oleic acid‐coated Fe3O4). The effects of several polymerization parameters, including the polarity of the medium, polymerization temperature, the concentration of monomer, and the amount of magnetite (Fe3O4) in the polymerization feed, were examined. The microspheres were characterized in terms of their morphology, size, particle‐size distribution, and iron content using transmission and scanning electron microscopies (TEM and SEM) and atomic absorption spectroscopy (AAS). A medium polarity was identified in which magnetic particles with a narrow size distribution were formed. As expected, oleic acid‐coated Fe3O4 nanoparticles contributed to the stabilization of the polymerized magnetic microspheres. Alkyne groups in magnetic PPRAAm microspheres were detected by infrared spectroscopy. Magnetic PPRAAm microspheres were successfully used as the anchor to enable a “click” reaction with an azido‐end‐functionalized model peptide (radiolabeled azidopentanoyl‐GGGRGDSGGGY(125I)‐NH2) and 4‐azidophenylalanine using a Cu(I)‐catalyzed 1,3‐dipolar azide‐alkyne cycloaddition reaction in water. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.  相似文献   

19.
Magnetic composite nanospheres (MCS) were first prepared via mini‐emulsion polymerization. Subsequently, the hybrid core–shell nanospheres were used as carriers to support gold nanoparticles. The as‐prepared gold‐loading magnetic composite nanospheres (Au‐MCS) had a hydrophobic core embed with γ‐Fe3O4 and a hydrophilic shell loaded by gold nanoparticles. Both the content of γ‐Fe3O4 and the size of gold nanoparticles could be controlled in our experiments, which resulted in fabricating various materials. On one hand, the Au‐MCS could be used as a T2 contrast agent with a relaxivity coefficient of 362 mg?1 ml S?1 for magnetic resonance imaging. On the other hand, the Au‐MCS exhibited tunable optical‐absorption property over a wavelength range from 530 nm to 800 nm, which attributed to a secondary growth of gold nanoparticles. In addition, dynamic light scattering results of particle sizing and Zeta potential measurements revealed that Au‐MCS had a good stability in an aqueous solution, which would be helpful for further applications. Finally, it showed that the Au‐MCS were efficient catalysts for reductions of hydrophobic nitrobenzene and hydrophilic 4‐nitrophenol that could be reused by a magnetic separation process. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

20.
In this work, Fe3O4/polystyrene/poly(N‐isopropylacryl amide‐co‐methylacrylate acid) (Fe3O4/PS/P(NIPAAM‐co‐MAA)) magnetic composite latex was synthesized by the method of two stage emulsion polymerization. In this reaction system, 2,2′‐azobis(2‐methyl propionamidine) dihydrochloride (AIBA) was used as initiator to initiate the first stage reaction and second stage reaction. The Fe3O4 particles were prepared by a traditional coprecipitation method. Fe3O4 particles were surface treated by either PAA oligomer or lauric acid to form the stable ferrofluid. The first stage for the synthesis of magnetic composite latex was to synthesize PS in the presence of ferrofluid by soapless emulsion polymerization to form the Fe3O4/PS composite latex particles. Following the first stage of reaction, the second stage of polymerization was carried out by the method of soapless emulsion polymerization with NIPAAM and MAA as monomers and Fe3O4/PS latex as seeds. The magnetic composite particles, Fe3O4/PS/P(NIPAAM‐co‐MAA), were thus obtained. The mechanism of the first stage reaction and second stage reaction were investigated. Moreover, the effects of PAA and lauric acid on the reaction kinetics, morphology, and particle size distribution were studied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3912–3921, 2007  相似文献   

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