Preparation and clinical application of immunomagnetic latex

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     

PREPARATION OF Fe3O4/PSt MAGNETIC PARTICLES IN THE PRESENCE OF MAGNETIC FLUID IN ETHANOL/WATER MIXTURE*

Fe_3O_4/Polystyrene(PSt) magnetic particles with core/shell structure have been prepared in thepresence of Fe_3O_4 magnetic fluid in ethanol/water medium by dispersion polymeriation of styrene. A Fe_3O_4particle formation mechanism was proposed. According to this mechanism, the size of particle nuclei isdetermined by the extent of aggregation of Fe_3O_4 /oligomer. Magnetic particles with diameter ranging from 5to 200 μm were prepared under different reaction conditions. Some polymerization parameters such as theconcentration of monomer, stabilizer, initiator, and ethanol which affect particle size and size distribution arediscussed and their effect on particle formation are explained by the proposed mechanism.     

Polystyrene‐Core–Silica‐Shell Hybrid Particles Containing Gold and Magnetic Nanoparticles

Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe₃O₄ nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors.     

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     

A microfluidics-dispensing-printing strategy for Janus photonic crystal microspheres towards smart patterned displays

From the implementation point of view, the printable magnetic Janus colloidal photonic crystals (CPCs) microspheres are highly desirable. Herein, we developed a dispensing-printing strategy for magnetic Janus CPCs display via a microfluidics-automatic printing system. Monodisperse core/shell colloidal particles and magnetic Fe₃O₄ nanoparticles precursor serve as inks. Based on the equilibrium of three-phase interfacial tensions, Janus structure is successfully formed, followed by UV irradiation and self-assembly of colloid particle to generate magnetic Janus CPCs microspheres. Notably, this method shows distinct superiority with highly uniform Janus CPCs structure, where the TMPTA/Fe₃O₄ hemisphere is in the bottom side while CPCs hemisphere is in the top side. Thus, by using Janus CPCs microspheres with two different structural colors as pixel points, a pattern with red flower and green leaf is achieved. Moreover, 1D linear Janus CPCs pattern encapsulated by hydrogel is also fabricated. Both the color and the shape can be changed under the traction of magnets, showing great potentials in flexible smart displays. We believe this work not only offers a new feasible pathway to construct magnetic Janus CPCs patterns by a dispensing-printable fashion, but also provides new opportunities for flexible and smart displays.     

空心结构磁性固体碱催化剂Fe3O4@LDO的制备与性能

基于水滑石类化合物的复合氧化物(LDO)是一类性能优异的固体碱催化剂,对其进行改性和功能化引起了越来越多的关注。本文将空心结构和Fe_3O_4引入到镁铝复合氧化物中,制备了一种空心结构磁性固体碱催化剂Fe_3O_4@LDO。这种空心结构磁性固体碱催化剂粒子具有以镁铝复合氧化物为壳层,空心Fe_3O_4为核的核壳结构。由于其独特的空心结构,Fe_3O_4@LDO粒子的悬浊液具有良好的稳定性,将其应用于催化Knoevenagel缩合反应,达到平衡后苯甲醛的转化率约为62%,显示出较好的催化性能。同时,Fe_3O_4@LDO粒子具有较强的磁性,非常方便分离与回收,是一种性能优良的磁性固体碱催化剂。     

Magnetic polystyrene nanocapsules with core-shell morphology obtained by emulsifier-free miniemulsion polymerization

Nanocapsules containing hexadecane and Fe₃O₄ magnetic nanoparticles as core materials and polystyrene as shell were produced in a new method through emulsifier-free miniemulsion polymerization using 2,2′-azobis(2-amidinopropane) dihydrochloride (V-50) as a water-soluble initiator. The effect of some parameters such as the amounts of Fe₃O₄ and initiator on morphology of resulting nanocapsules was studied. Transmission electron microscopy showed that the products had latex particles having a size range of about 300–1300 nanometer and both magnetic nanocapsules with core-shell morphology and solid particles. The phase transition temperature and phase transition heat of the produced capsules were determined by differential scanning calorimetric analyses. Thermal properties of the latex were compared with those of magneticparticles-free latex and with those of latex free of both magnetic particles and hexadecane. Thermogravimetric analysis was also used to confirm the encapsulation and to determine the amounts of hexadecane and Fe₃O₄ within the capsules.     

Selected-Control Synthesis of Monodisperse Fe3O4@C Core–Shell Spheres,Chains, and Rings as High-Performance Anode Materials for Lithium-Ion Batteries

A method is reported for the first time for the selected-control, large-scale synthesis of monodispersed Fe₃O₄@C core–shell spheres, chains, and rings with tunable magnetic properties based on structural evolution from eccentric Fe₂O₃@poly(acrylic acid) core–shell nanoparticles. The Fe₃O₄@C core–shell spheres, chains, and rings were investigated as anode materials for lithium-ion batteries. Furthermore, a possible formation mechanism of Fe₃O₄@C core–shell chains and rings has also been proposed.     

Fabrication of liquid crystal Fe3O4 composites and their magnetorheological properties

Some supramolecular polyacrylate-based liquid crystal polymers (PLCPs) were prepared by polyacrylic acid, a liquid crystal monomer and 3,5-pyridinedicarboxylic acid. Series of magnetic liquid crystal particles (Fe₃O₄@PLCPs) with core-shell structure were prepared by modifying surface of magnetic nanoparticles Fe₃O₄ by the PLCPs. The Fe₃O₄@PLCPs showed a saturation magnetization strength above 51.17 emu/g, which is similar to pure magnetic Fe₃O₄, indicating good magnetism and magnetic field dependence. Series of magnetorheological fluids were fabricated by Fe₃O₄@PLCPs (using as dispersed phase) and silicone oil (using as carrier liquid). The effects of mesogen, magnetic particle, and the polymer matrix on magnetorheological performance and settling stability were investigated. The magnetorheological fluid based on 10% Fe₃O₄@PLCP-1 showed the best performance at an applied magnetic field of 100 mT in this study. Furthermore, the magnetorheological fluids showed excellent settling stability because the density of Fe₃O₄@PLCPs was lower than that of Fe₃O₄. The Fe₃O₄@PLCPs-based fluids presented certain application potential in the field of magnetic fluid due to the excellent magnetorheological effect and settling stability.     

Preparation of composite particles with magnetic silica core and fluorescent polymer shell

Dual functions of magnetic and fluorescent properties were created in composite particles that incorporated magnetite (Fe₃O₄) nanoparticles in particle cores of silica and fluorescent pyrene in particle shells of polystyrene. The Fe₃O₄ nanoparticles were prepared with a conventional homogeneous precipitation method and surface modified with a coupling agent of carboxyethylsilanetriol. The silica particles incorporating Fe₃O₄ nanoparticles were synthesized with a modified Stöber method in which the Fe₃O₄ nanoparticles were added to a system of tetraethylorthosilicate (TEOS)/ammonia/water/ethanol. Then, the magnetite/silica composite particles were coated with the pyrene/polystyrene shell in a soap-free emulsion polymerization, which was conducted in the presence of pyrene in a mixed solvent of water/ethanol. The composite particles prepared in the mixed solvent had both magnetic and fluorescent properties. The fluorescent spectrum of the particles with Fe₃O₄ was very similar to that without Fe₃O₄, indicating that the magnetic component within the core particles scarcely interfered with the fluorescent emission from the polymer shell.     

可循环磁性Pt/Fe3O4-MCNT催化剂上的肉桂醛选择性加氢反应

采用多步法依次将制备的Fe₃O₄纳米颗粒和Pt纳米颗粒负载到多壁碳纳米管(MCNT)上得到Pt/Fe₃O₄-MCNT磁性催化剂,以X射线衍射(XRD)、透射电镜(TEM)、超导量子干涉磁强计(SQUID)和热重-差热分析(TG-DTA)对Pt/Fe₃O₄-MCNT磁性催化剂的结构和磁性质进行了表征。研究发现预制备的Fe₃O₄纳米颗粒与Pt纳米颗粒均匀地分散于MCNT上,新制备以及多次使用后的Pt/Fe₃O₄-MCNT室温下都具有良好的超顺磁性。研究了Pt/Fe₃O₄-MCNT磁性催化剂上的肉桂醛选择性加氢反应,结果显示催化剂具有良好的C=O加氢活性,肉桂醛转化率在50%左右时,肉桂醇选择性可达96%以上。尺寸均一的Pt粒子均匀的分散在催化剂上可能是催化剂具有良好的C=O加氢选择性的重要原因。在外加磁场作用下催化剂可以高效地从液相反应体系中分离,经多次循环使用后仍具有良好的催化性能。     

Stimulated aggregation, rotation, and deformation of magnetite-filled microcapsules in external magnetic fields

Microcapsules are nowadays applied in a wide range of products including food, pharmaceuticals, and cosmetic formulations. Because of their pronounced viscoelastic properties, polymer microcapsules are able to undergo mechanical deformations when they are stimulated by external signals. The elongation of capsule membranes, up to bursting processes, is important for the controlled release of active ingredients under well-defined conditions. Their application as quick and reliable control release systems affords a detailed knowledge of their rheological and mechanical properties. The aims of our work were to prepare new types of magnetic switchable microcapsules and to investigate their deformation behavior in externally imposed magnetic fields. The magnetic sensitivity was achieved by encapsulating magnetic magnetite (Fe₃O₄) particles within a polyorganosiloxane capsule. We investigated the dynamic response of those capsule suspensions and single capsules to external magnetic forces where aggregation processes, rotational movements, and field-induced deformations in static or rotating fields were observed.     

Selective extraction of morphine from biological fluids by magnetic molecularly imprinted polymers and determination using UHPLC with diode array detection

The determination of morphine concentration in the blood and urine is necessary for patients and recruitment purposes. Herein, a magnetic molecularly imprinted polymer for selective and efficient extraction of morphine from biological samples was synthesized by using a core–shell method. Fe₃O₄ nanoparticles were coated with SiO₂‐NH₂. The molecularly imprinted polymer was coated on the Fe₃O₄/SiO₂‐NH₂ surface by the copolymerization of methacrylic acid and ethylene glycol dimethacrylate in the presence of morphine as the template molecule. The morphological and magnetic properties of the polymer were investigated. Field‐emission scanning electron microscopy indicated that the prepared magnetic polymer is almost uniform. The saturation magnetization values of Fe₃O₄ nanoparticles, Fe₃O₄/SiO₂‐NH₂, and the magnetic polymer were 48.41, 31.69, and 13.02 emu/g, respectively, indicating that all the particles are superparamagnetic. Kinetics of the adsorption of morphine on magnetic polymer were well described by second‐order kinetic and adsorption processes and well fitted by the Langmuir adsorption isotherm, in which the maximum adsorption capacity was calculated as 28.40 mg/g. The recoveries from plasma and urine samples were in the range of 84.9–105.5 and 94.9–102.8%, respectively. By using the magnetic molecularly imprinted polymer, morphine can selectively, reliably, and in low concentration be determined in biological samples with high‐performance liquid chromatography and UV detection.     

Synthesis and morphology of an iron oxide/polystyrene/poly(isopropylacrylamide‐co‐methacrylic acid) thermosensitive magnetic composite latex with potassium persulfate as the initiator

In this work, an iron oxide (Fe₃O₄)/polystyrene (PS)/poly(N‐isopropylacryl amide‐co‐methacrylic acid) [P(NIPAAM–MAA)] thermosensitive magnetic composite latex was synthesized by the method of two‐stage emulsion polymerization. The Fe₃O₄ particles were prepared by a traditional coprecipitation method and then surface‐treated with either a PAA oligomer or lauric acid to form a stable ferrofluid. The first stage for the synthesis of the thermosensitive magnetic composite latex was to synthesize PS in the presence of a ferrofluid by emulsion polymerization to form Fe₃O₄/PS composite latex particles. Following the first stage of reaction, the second stage of polymerization was carried out with N‐isopropylacryl amide and methacrylic acid as monomers and with Fe₃O₄/PS latex as seeds. The Fe₃O₄/PS/[P(NIPAAM–MAA)] thermosensitive magnetic particles were thus obtained. The effects of the ferrofluids on the reaction kinetics, morphology, and particle size of the latex were discussed. A reaction mechanism was proposed in accordance with the morphology observation of the latex particles. The thermosensitive property of the thermosensitive magnetic composite latex was also studied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3062–3072, 2007     

Influence of DS of CMC on morphology and performance of magnetic microcapsules

In this paper, we present a reproducible method for the preparation of mixed colloidal nanoparticles, consisting of a magnetic Fe₃O₄ nanoparticle nucleus and a biocompatible self-assembly shell of substitution of sodium carboxy methyl cellulose and chitosan in different degree. The heterogeneous structure of the particles can confer them both the possibility of being used as drug delivery systems and the responsiveness to external magnetic fields, allowing a selective guidance of drug molecules to specific target tissues without a concurrent increase in its level in healthy tissues. The preparation method is based on a coordination and layers by layers self-assembly process. In order to specify that A complete physicochemical characterization of the composite particles is carried out, in order to use this preliminary investigation to show that the CMC/CS shell efficiently coating Fe₃O₄ nanoparticles, and leading to composite particles, the magnetic behavior of the core/shell particles is similar to that of bare magnetic Fe₃O₄ nanoparticles. It is observed that The magnetic microspheres with CMC DS 1.05 served as shell show the best dispersion, super paramagnetic, the range of magnetic field the particles can respond is an order of magnitude higher than others, and the specific saturation magnetization intensity is the highest. Thus we can indicate with the conclusion that if the DS of CMC becomes higher, the Fe₃O₄@CS/CMC would be more sensitive with the extant magnetic field. However, when the DS of CMC is higher than 1.1, the specific saturation magnetization intensity of magnetic microspheres would fall down again and the geometry becomes not well. Therefore, when the DS of CMC stay in 1.05, it would be a better material of magnetic microsphere.     

可循环磁性Pt/Fe_3O_4-MCNT催化剂上的肉桂醛选择性加氢反应

采用多步法依次将制备的Fe3O4纳米颗粒和Pt纳米颗粒负载到多壁碳纳米管(MCNT)上得到Pt/Fe3O4-MCNT磁性催化剂,以X射线衍射(XRD)、透射电镜(TEM)、超导量子干涉磁强计(SQUID)和热重-差热分析(TG-DTA)对Pt/Fe3O4-MCNT磁性催化剂的结构和磁性质进行了表征。研究发现预制备的Fe3O4纳米颗粒与Pt纳米颗粒均匀地分散于MCNT上,新制备以及多次使用后的Pt/Fe3O4-MCNT室温下都具有良好的超顺磁性。研究了Pt/Fe3O4-MCNT磁性催化剂上的肉桂醛选择性加氢反应,结果显示催化剂具有良好的C=O加氢活性,肉桂醛转化率在50%左右时,肉桂醇选择性可达96%以上。尺寸均一的Pt粒子均匀的分散在催化剂上可能是催化剂具有良好的C=O加氢选择性的重要原因。在外加磁场作用下催化剂可以高效地从液相反应体系中分离,经多次循环使用后仍具有良好的催化性能。     

Superparamagnetic Polymer Emulsion Particles from a Soap-Free Seeded Emulsion Polymerization and their Application for Lipase Immobilization

Using emulsion copolymer of styrene (St), glycidyl methacrylate (GMA) and 2-hydroxyethyl methacrylate (HEMA) as seed latexes, the superparamagnetic polymer emulsion particles were prepared by seeded emulsion copolymerization of butyl methacrylate (BMA), vinyl acetate (VAc) and ethylene glycol dimethacrylate in the presence of the seed latexes and superparamagnetic Fe₃O₄/SiOx nanoparticles (or Fe₃O₄-APTS nanoparticles) through a two-step process, without addition of any emulsifier. The magnetic emulsion particles named P(St-GMA-HEMA)/P(BMA-VAc) were characterized by transmission electron microscope and vibrating sample magnetometry. The results showed that the magnetic emulsion particles held a structure with a thinner shell (around 100 nm) and a bigger cavity (around 200 nm), and possessed a certain level of magnetic response. The resulting magnetic emulsion particles were employed in the immobilization of lipase by two strategies to immobilized lipase onto the resulting magnetic composites directly (S-1) or using glutaraldehyde as a coupling agent (S-2), thus, experimental data showed that the thermal stability and reusability of immobilized lipase based on S-2 were higher than that of S-1.     

A facile two-step modifying process for preparation of poly(SStNa)-grafted Fe3O4/SiO2 particles

This article reports the synthesis of the poly(sodium 4-styrenesulfonate)-grafted Fe₃O₄/SiO₂ particles via two steps. The first step involved magnetite nanoparticles (Fe₃O₄) homogeneously incorporated into silica spheres using the modified Stöber method. Second, the modified silica-coated Fe₃O₄ nanoparticles were covered with the outer shell of anionic polyelectrolyte by surface-initiated atom transfer radical polymerization. The resulted composites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive microscopy (EDS), Fourier transform-infrared (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and vibration sample magnetometer (VSM). The XRD results indicated that the surface modified Fe₃O₄ nanoparticles did not lead to phase change compared with the pure Fe₃O₄. TEM studies revealed nanoparticles remained monodisperse. The detection of sulfur and sodium signals was a convincing evidence that sodium 4-styrenesulfonate was grafted onto the surface of the magnetic silica in XPS analysis. Finally, super-paramagnetic properties of the composite particles, and the ease of modifying the surfaces may make the composites of important use in mild separation, enzyme immobilization, etc.     

Preparation of Fe3O4 magnetic fluid by one-step method with a microemulsion reactor

A W/O microemulsion was prepared with Span80-PS (petroleum sulfonate) as complex emulsifier, isopropanol as cosurfactant and kerosene as oil phase. The optimal constituents of microemulsion were found from pseudoternary phase diagrams: the mass ratio of Span80 to PS was 4:1 and complex surfactant to cosurfactant was 1:1. The Fe₃O₄ magnetic fluid was obtained by one-step method with the W/O microemulsion as microreactor to synthesize magnetic nanoparticles (reaction temperature was 30 °C and reaction time was 5 h) and kerosene as carrier liquid. The magnetic fluid was investigated by TEM, XRD and fluorescence microscope. The magnetism was determined by Gouy magnetic balance. The average particle size of Fe₃O₄ was 7.4 nm, and magnetic particles were well-dispersed. The stable Fe₃O₄ magnetic fluid with good magnetism may be produced by one-step method in the W/O microemulsion. Accordingly, the traditional preparation method of magnetic fluid can be simplified greatly. __________ Translated from Chinese Journal of Applied Chemistry, 2005, 22 (7) (in Chinese)     

免疫磁性纳米微球的制备与表征

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。