Covalent immobilization of albumin on micron‐sized magnetic poly(methyl methacrylate‐divinylbenzene‐glycidyl methacrylate) microspheres prepared by modified suspension polymerization

Micron‐sized magnetic poly(methyl methacrylate‐divinylbenzene‐glycidyl methacrylate) microspheres were prepared by a modified suspension polymerization in the presence of oleic acid‐coated magnetite nanoparticles. The magnetic microspheres were functionalized by reacting the epoxy groups with ammonia solution to provide amino groups. After activated with glutaraldehyde (GA), bovine serum albumin was covalently immobilized on these magnetic microspheres. The influence of initial protein concentration, pH and ionic strength of the protein solution on covalent immobilization was studied. Scanning electron micrographs showed that the magnetic microspheres had an average size of 6.4 µm and relative narrow size distribution. Magnetic measurement revealed the magnetic microspheres were superparamagetic with saturation magnetization of 7.32 emu/g. The successful amination of the magnetic microspheres was confirmed by Fourier transform infrared spectroscopy (FT‐IR). Copyright © 2005 John Wiley & Sons, Ltd.     

PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

 Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2,2-azobis(2-methylpropionamidine) dihydrochloride as an initiator. The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined. In addition, the optimum polymerization conditions of poly(styrene-co-glycidyl methacrylate) latex microspheres for immobilization of biomolecules were obtained.     

Multihollow structured poly(methyl methacrylate)/silver nanocomposite microspheres prepared by suspension polymerization in the presence of dual dispersion agents

Poly(methyl methacrylate) (PMMA)/silver nanocomposite microspheres with unique multihollow structures were prepared by suspension polymerization in the presence of dual dispersion agents. The addition of a lipophilic emulsifier, polyethylene glycol (30EO) dipolyhydroxystearate (Arlacel P135), not only stabilized water-in-oil (W/O) emulsion, but also converted silver nanoparticles from hydrophilic to lipophilic. When a suspension polymerization dispersion agent, poly(vinyl alcohol), was added to the above W/O emulsion system, a water-in-oil-in-water suspension was formed with silver nanoparticles dispersed in the oil phase. The suspension polymerization was carried out at low temperature with 2,2’-azobis(2,4-dimethylvaleronitrile) as the initiator. When modified silver nanoparticles were added, the rate of polymerization increased slightly. High monomer conversion (about 85%) was obtained in spite of low polymerization temperature of 30 °C. Under controlled conditions, PMMA/silver microspheres with various hollow structures were synthesized. The PMMA/silver microspheres with multihollow structure showed high antibacterial ability.     

Fabrication and functionalization of dendritic poly(amidoamine)-immobilized magnetic polymer composite microspheres

The synthesis of functionalized magnetic polymer microspheres was described by a process involving (1) preparation of the monodisperse magnetic seeds according to a two-step procedure including the preparation of bilayer-oleic acid-coated Fe3O4 nanoparticles followed by soap-free emulsion polymerization with methyl methacrylate (MMA) and divinyl benzene (a cross-linking agent, DVB); (2) seeded emulsion polymerization proceeding under the continuous addition of glycidyl methacrylate (GMA) monomers in the presence of the magnetic PMMA seeds; and (3) chemical modification of the PGMA shells with ethylenediamine (EDA) to yield amino groups. As such, the magnetic poly(MMA-DVB-GMA) microspheres were prepared possessing monodispersity, uniform magnetic properties, and abundant surface amino groups. Then, the dendritic poly(amidoamine) (PAMAM) shells were coated on the magnetic particles on the basis of the Michael addition of methyl acrylate and the amidation of the resulting ester with a large excess of EDA, which could achieve generational growth under such uniform stepwise reactions. For improving the luminescence properties of the composite particles, fluorescein isothiocyanate, which is a popular organic dye, was reacted with the terminal -NH2 groups from the dendritic PAMAM shells, resulting in the formation of multifunctional microspheres with excellent photoluminescence, superparamagnetic, and pH-sensitive properties. In this case, it can be expected that an extension of the functionalization of these microspheres is to immobilize other target molecules onto the PAMAM shells to introduce other desired functions for potential chemical and biological applications.     

PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2.2′- azobis(2-methylpropionamidine) dihydrochloride as an initiator.The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined.In addition,the optimum polymerization conditions of poly(styrene-co- glycidyl methacrylate) latex microspheres ...     

Monodispers and Multifunctional Magnetic Composite Core Shell Microspheres for Demulsification Applications

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.     

Synthesis of poly(vinyl acetate-methyl methacrylate) copolymer microspheres using suspension polymerization

Poly(vinyl acetate-methyl methacrylate) (VAc-MMA) copolymer microspheres were prepared using suspension polymerization at low temperature initiated with 2,2'-azobis(2,4-dimethyl valeronitrile) (ADMVN). The poly(VAc-MMA) copolymer microspheres can be used over a large area where homopolymers, polyvinyl acetate (PVAc) and methyl methacrylate (PMMA) microspheres are capable of being put to use. The prepared microspheres were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Obtained copolymer microspheres which have 200 μm average diameter and higher thermal stability than those of homopolymer.     

Polyaniline microsphere encapsulated by poly(methyl methacrylate) and investigation of its electrorheological properties

Microspheres consisting of a poly(methyl methacrylate) (PMMA) shell wrapping the conductive polyaniline (PANI) particle as a core were prepared by an in-situ suspension polymerization method and then adopted as an electrorheological (ER) material. The polymerization reaction and encapsulation were confirmed by Fourier transform infrared spectrum analysis. The rod-like PANI particles were synthesized via an emulsion polymerization protocol and observed by transmission electron microscopy. In addition, a spherical shape of encapsulated PANI/PMMA (core/shell) microspheres was observed by scanning electron microscopy. The thermal stability of PANI/PMMA particles was examined by use of thermogravimetric analysis. The PANI/PMMA particle-based suspension in silicone oil exhibited typical ER behavior. The conductivity of PANI/PMMA particles was much lower than that of the rod-like PANI.     

Poly(methyl methacrylate)/multiwalled carbon nanotube microspheres fabricated via in‐situ dispersion polymerization

Poly(methyl methacrylate)/multiwalled carbon nanotube (PMMA/MWCNT) microspheres were successfully prepared by in situ dispersion polymerization in an alcohol phase in which the acid‐treated MWCNTs were dispersed before polymerization. The PMMA and PMMA/MWCNT microspheres were monodisperse. The diameters of the microspheres decreased from about 11.6–6.0 μm as the MWCNT content was increased from 0 to 0.03 wt %. The morphology of the PMMA/MWCNT microspheres was investigated by scanning electron microscopy, atomic force microscopy, and transmission electron microscopy, and the experimental results showed that the MWCNTs were present both in the interior and on the surface of the microspheres. The synthesized PMMA/MWCNT microspheres were also characterized by electrical resistance measurements to analyze their electrical conductivity. They showed electrorheological (ER) fluid characteristics when they were dispersed in silicone oil. Their ER properties were confirmed by using optical microscopy to examine a suspension of the PMMA/MWCNT microspheres dispersed in insulating silicone oil to which an electric field of 2.5 kV/cm was applied. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 182–189, 2008     

Surface molecularly imprinted magnetic microspheres for the recognition of albumin

A new approach, combining metal coordination with the molecular imprinting technique, was developed to prepare affinity materials. Magnetic poly(glycidyl methacrylate) microspheres in monosize form were used for specific recognition toward the target protein. The magnetic poly(glycidyl methacrylate) microspheres were prepared by dispersion polymerization in the presence of magnetite nanopowder. Surface imprinted magnetic poly(glycidyl methacrylate) microspheres based on metal coordination were prepared and used for the selective recognition of human serum albumin. Iminodiacetic acid was used as the metal coordinating agent and human serum albumin was anchored by Cu²⁺ ions on the surface of magnetic poly(glycidyl methacrylate) microspheres by metal coordination. The magnetic poly(glycidyl methacrylate) microspheres were coated with a polymer formed by condensation of tetraethyl orthosilicate and 3‐aminopropyltrimethoxysilane. The human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres were characterized by scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy and particle size analysis. The maximum adsorption capacity of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres was 37.7 mg/g polymer at pH 6.0. The selectivity experiments of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres prepared with different concentrations in the presence of lysozyme, bovine serum albumin and cytochrome C were performed in order to determine the relative selectivity coefficients.     

Using electroless deposition for the preparation of micron sized polymer/metal core/shell particles and hollow metal spheres

Uniform and stable core-shell microspheres composed of a poly(methyl methacrylate) (PMMA) core and a thin metallic shell of nickel-phosphorus, cobalt-phosphorus, or mixed metal alloys (CoNiP, NiFeP, CoFeP) were prepared by dispersion polymerization of methyl methacrylate followed by electroless plating. The presence of the metallic shell around the particles was confirmed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and photoelectron spectroscopy. Transmission electron microscopy images of the cross-section of individual particles show that the thickness of the metal/alloy can be precisely tuned by adjusting the immersion time of the microspheres in the electroless bath. Depending on the deposited metallic material, various magnetic properties, from paramagnetic to ferromagnetic, are achieved. Finally, uniform hollow metallic spheres composed of nickel, cobalt, or nickel-cobalt alloy are obtained by dissolving the polymer core.     

Magnetic poly(glycidyl methacrylate)-based microspheres prepared by suspension polymerization in the presence of modified La0.75Sr0.25MnO3 nanoparticles

With the aim of preparing new magnetic poly(glycidyl methacrylate) (PGMA) microspheres suitable for magnetic separation, La_0.75Sr_0.25MnO₃ nanoparticles were selected as a core material. In order to improve their compatibility with PGMA, the surface of the nanoparticles was treated with penta(methylethylene glycol) phosphate methacrylate (PMGPMA) as a stabilizer. Subsequently, the nanoparticles were encapsulated by the suspension polymerization of glycidyl methacrylate (GMA) resulting in a relatively homogeneous distribution of La_0.75Sr_0.25MnO₃ nanoparticle aggregates inside the polymer microspheres. Microspheres in the size range of a hundred micrometers with a broad particle size distribution were obtained. PMGPMA can be considered to be an efficient compatibilizer between La_0.75Sr_0.25MnO₃ nanoparticles and PGMA. Both PMGPMA-coated La_0.75Sr_0.25MnO₃ nanoparticles and magnetic PGMA microspheres were characterized in terms of morphology, particle size, composition and magnetic properties by the appropriate methods, such as X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), light microscopy and SQUID magnetometry.     

Synthesis of Fe3O4@poly(methylmethacrylate-co-divinylbenzene) magnetic porous microspheres and their application in the separation of phenol from aqueous solutions

A simple strategy to fabricate magnetic porous microspheres of Fe(3)O(4)@poly(methylmethacrylate-co-divinylbenzene) was demonstrated. The magnetic microspheres, consisting of polymer-coated iron oxide nanoparticles, were synthesized by the modified suspension polymerization of methacrylate and divinylbenzene in the presence of a magnetic fluid. The morphology and the properties of the magnetic porous microspheres were examined by scanning electron microscopy, transmission electron microscopy, superconducting quantum interference device, Fourier transform infrared spectroscopy, thermogravimetry, and X-ray powder diffraction. The pore size distribution and the specific surface area of the microspheres were measured by nitrogen sorption and mercury porosimetry technique. As predicted from the previous knowledge, the magnetic porous microspheres possessed a high specific surface area using n-hexane as a porogen. It was further found that the amounts of divinylbenzene and methacrylate, the ratio of porogens, and the dosage of ferrofluids affect the specific surface area of the microspheres. Furthermore, the microspheres were applied to remove phenol from aqueous solutions. The results showed that the microspheres had a high adsorption capacity for phenol and a high separation efficiency due to their porous structure, polar groups, and superparamagnetic characteristic.     

超声悬浮共聚法制备聚合物微球及其形态

采用超声粉碎和悬浮聚合法,以甲基丙烯酸甲酯、苯乙烯为主单体,过氧化苯甲酰为引发剂,颜料黄74为着色剂,合成了彩色聚合物微球。光学显微镜以及扫描电镜的观察和分析表明：利用超声粉碎法可使聚合物微球的粒径从几百微米降低到几微米;热熔融后,聚合物微球内包覆了细小的颜料颗粒。     

Preparation of magnetic microspheres with thiol-containing polymer brushes and immobilization of gold nanoparticles in the brush layer

Narrow-disperse magnetic microspheres were prepared by alkaline coprecipitation of Fe²⁺ and Fe³⁺ ions within poly(acrylic acid–divinylbenzene) microspheres that were prepared by distillation–precipitation copolymerization. Magnetic microspheres with polymer brushes that contain epoxy groups were prepared by graft copolymerization of glycidyl methacrylate and glycerol monomethacrylate via atom transfer radical polymerization (ATRP) from the magnetic microsphere surfaces. Subsequently, magnetic microspheres with thiol-containing polymer brushes were prepared by treating the epoxy group-containing magnetic microspheres with sodium hydrosulfide. Gold nanoparticles were immobilized in the brush layer of the thiol-containing magnetic microspheres through Au–S coordination. The catalytic activity of the gold nanoparticle-immobilized magnetic microspheres was investigated using the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride as a model reaction. The catalyst could be reused for over 10 cycles without noticeable loss of catalytic activity.     

AMPS/MMA二元共聚微球的超声无皂乳液制备与表征

将超声辐射无皂乳液聚合作用于含有2-丙烯酰胺基-2-甲基丙磺酸（AMPS）和甲基丙烯酸甲酯（MMA）的水溶液中,在不加任何引发剂和乳化剂的条件下合成AMPS/MMA二元共聚高分子微球,考察了超声反应时间对单体转化率的影响,用FTIR、TGA-DSC、TEM和粒度分析仪等技术进行了表征,并初步探讨了聚合反应机理。结果表明,合成得到的高分子微球粒径在0.77μm左右,分散均匀,且具有较好的热稳定性     

Preparation and properties of thermoexpandable polymeric microspheres

In this paper,thermoexpandable polymeric microspheres were prepared by suspension polymerization with acrylonitrile(AN) and methyl methacrylate(MMA) as monomers and i-butane as a blowing agent.The micromorphology and thermal stability were researched by polarized microscopy and TGA.The diameter of the expandable microspheres increased from about 20 mm(unexpanded) to 40–80 mm(expanded) upon heating.The maximum expansion volume was higher than 22 times of the original volume and the density of the expanded microspheres was about 16.7 kg/m3.The blowing agent content in microspheres was about 20 wt% and To.e.,Tm.e.and To.s.were 80 8C,120–130 8C and 140–145 8C,respectively.     

在聚合物微球 GMA/MMA 表面同步合成与固载卟啉及固载化金属卟啉的催化氧化性能

 制备了甲基丙烯酸缩水甘油酯 (GMA) 与甲基丙烯酸甲酯 (MMA) 共聚微球 GMA/MMA, 并通过键合有对羟基苯甲醛 (HBA) 的改性微球 HBA-GMA/MMA 与苯甲醛 (或取代苯甲醛) 以及吡咯间的 Adler 反应, 实现了卟啉在共聚微球 GMA/MMA 表面的同步合成与固载, 制得了固载有苯基卟啉 (PP)、对氯苯基卟啉 (CPP)、对硝基苯基卟啉 (NPP) 的功能化微球 PP-GMA/MMA, CPP-GMA/MMA 和 NPP-GMA/MMA. 重点考察了影响卟啉同步合成与固载过程的因素. 制备了固载有钴卟啉的催化剂, 并以分子氧氧化乙苯为模型反应, 考察了催化剂的活性. 结果表明, 苯甲醛取代基的结构、催化剂的酸性和溶剂的极性对卟啉的同步合成与固载都有较大的影响; 钴卟啉催化剂对分子氧氧化乙苯反应具有较高的催化活性, 且当钴卟啉外环上含有强吸电子基团硝基时, 催化剂活性最高.     

含环氧基团的聚合物微球固载2,2,6,6-四甲基哌啶氮氧自由基催化剂的制备及其催化分子氧氧化苯甲醇

以甲基丙烯酸缩水甘油酯(GMA)为单体, 以乙二醇二甲基丙烯酸酯(EGDMA)为交联剂, 采用悬浮聚合法制得交联聚甲基丙烯酸缩水甘油酯(CPGMA)微球, 然后以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(4-OH-TEMPO)为试剂, 使CPGMA微球表面的环氧基团发生开环反应, 从而制得了TEMPO固载化微球TEMPO/CPGMA, 考察了制备条件对固载化反应的影响, 并采用多种方法对微球TEMPO/CPGMA进行了表征. 将微球TEMPO/CPGMA与CuCl组成共催化体系, 用于分子氧氧化苯甲醇, 考察了反应条件对催化体系性能的影响. 结果表明, 以含环氧基团的聚合物微球CPGMA为载体, 通过开环反应, 可成功地实现TEMPO的固载化, 开环反应属S_N2亲核取代反应, 适宜采用溶剂N,N''-二甲基甲酰胺和反应温度85℃. 非均相催化剂TEMPO/CPGMA与助催化剂CuCl构成共催化体系, 在室温、常压O₂条件下可高效地将苯甲醇氧化为苯甲醛, 产物选择性和产率分别为100%和90%. 主催化剂TEMPO与助催化剂CuCl适宜的摩尔比为1:1.2; 主催化剂适宜用量为0.90 g. 此外, TEMPO/CPGMA固体催化剂具有良好的循环使用性能.     

Synthesis of functional magnetic porous SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/P(St-DVB-MAA) microspheres by a novel suspension polymerization

In this study, a novel and effective suspension polymerization has been employed to prepare functional magnetic porous SrFe₁₂O₁₉/P(St-DVB-MAA) microspheres in the presence of bilayer surfactants (sodium dodecyl benzene sulfonate (SDBS) and oleic acid (OA)) coated on micro-size magnetic SrFe₁₂O₁₉. This was achieved by pre-polymerizing the organic phase, which contained co-monomers, porogens and treated magnetic particles, at 65°C for 0.5 h under ultrasound conditions. Aqueous solutions containing a dispersion agent were then added to effect suspension polymerization. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and magnetic property measurement system (MPMS) were used to characterize the functional magnetic porous microspheres. The results show that the microparticles are well shaped with a uniform size distribution of about 0.5 ∼ 0.7 mm and the surfaces of the microspheres have many micro-pores with an average diameter of 0.533 μm. There are carboxyl groups (−COOH) on the surface of the microspheres to the extent of 0.65 mmol g⁻¹, as determined by conductometric titration. According to the XRD spectra, iron oxide consists mainly of SrFe₁₂O₁₉ which reveals hexahedral structure. The content of magnetic SrFe₁₂O₁₉ reaches 17.81% (by mass), and the microspheres have good heat resistance. The magnetic porous microspheres are ferromagnetic with high residual magnetization and coercivity, 21.59 emu g⁻¹ and 4.13 kOe, respectively. The saturation magnetisation is around 42.85 emu g⁻¹.