Preparation of Micron-size Functional Fluorescent Microspheres

As a kind of special functional microspheres, fluorescent polymer microspheres could be used in cell label and separation, blood flow assay, flow cytometer marking, chemical reaction assay,and in analyst of the transform and diffusion of particles in soil 1. However, one of the most important applications of fluorescent microspheres is in the high-throughput screening of drugs (HTS) 2. Through affinity interaction, radioactive ligands (latent drugs) are bound to fluorescent microspheres covered by receptor, and luminescence is produced by radioactivity, so ligands can be assayed and screened.In this study, we developed a technique for preparing micron-size fluorescent microspheres with different functional groups. The methods included the synthesis of micron-size polystyrene microspheres through the dispersion polymerization of styrene in different media such as ethanol,ethanol-water, and isopropanol; the functional polystyrene microspheres were prepared by introduction of functional monomers into the reaction system of styrene; the functional fluorescent microspheres were obtained by the way of dying functional microspheres in the fluorescent material's ethanol solvent.The average diameter of microspheres was in the range of 1～10 μm, and the distribution was normal distribution. The functional groups included -OH, -CHO, -COOH, -CONH2, and SO3H. The absorbing spectrum and exciting spectrum were tested, the results showed that the maximal absorbance of fluorescent microsphere was near 306.5 nm, and its maximal excitation was near 362 nm. The excitation spectrum of fluorescent material (DPO) and fluorescent microspheres were shown in figure 1, and it indicated that the developed fluorescent microspheres showed the same excitation behavior like DPO, which related to the fluorescent microspheres had stable luminescence property.     

Surface-modified hemispherical polystyrene/polybutyl methacrylate composite particles

Micrometer-sized polystyrene/poly(n-butyl methacrylate) composite particles of hemisphere morphology and narrow size distribution were prepared by a process of single-step swelling of uniform polystyrene template microspheres with emulsion droplets of the monomer n-butyl methacrylate containing the initiator benzoyl peroxide in the presence, or absence, of the co-swelling agent toluene. Butyl methacrylate was then polymerized at 73 degrees C within the template microspheres. Surface and bulk characterization of the particles were performed by methods such as FTIR, elemental analysis, XPS, advancing contact angle, light microscope, SEM, and cross-sectional TEM. Selective surface functionalization of the poly(n-butyl methacrylate) phase of the composite particles was performed by carrying out a similar swelling and polymerization process in the presence of a water-soluble vinylic monomer such as acrylamide.     

Interfacial synthesis of hollow TiO2 microspheres in ionic liquids

An interfacial sol-gel synthesis of inorganic hollow microspheres in room-temperature ionic liquids is newly developed. When metal alkoxides such as titanium tetrabutoxide, Ti(OBu)4, are dissolved in anhydrous toluene and injected into 1-buthyl-3-methylimidazolium hexafluorophosphate ([C4mim]PF6) under vigorous stirring, hollow titania microspheres are formed. The present technique is widely applicable to the reactive metal alkoxides such as Zr(OBu)4, Hf(OBu)4, Nb(OBu)4, and InSn3(OR)x, giving a general route to the metal oxide microspheres. When gold nanoparicles and carboxylate-containing dyes such as fluorescein isothiocyanate (FITC) are dissolved in the toluene microdroplets, they are stably immobilized in the microsphere shells. Calcination of the titania gel microspheres gives anatase TiO2 microspheres. The present method provides the first example of inorganic hollow microspheres formed in ionic liquids, and the ability to modify microspheres with metal nanoparticles or functional organic molecules would be widely applied to the design of smart organic/inorganic hybrid materials.     

Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres

~~Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres~~     

Preparation and characterization of porous polymeric microspheres obtained from multifunctional methacrylate monomers

Synthesis and properties of the new difunctional methacrylate monomer 2‐hydroxy‐3‐methacryloyloxypropoxybenzene are presented. This monomer was applied for the synthesis of porous microspheres. It was copolymerized with trimethylolpropane trimethacrylate in the presence of two pairs of pore‐forming diluents dodecane and toluene, and n‐decanol and toluene. Influence of diluents composition on their porous structures was studied. Thermal resistance and tendency to swell in different organic diluents for a chosen sample were also determined. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6165–6174, 2008     

Effects of the reaction parameters on the properties of thermosensitive poly(N‐isopropylacrylamide) microspheres prepared by precipitation and dispersion polymerization

Poly(N‐isopropylacrylamide) (PNIPAAm)‐based microspheres were prepared by precipitation and dispersion polymerization. The effects of several reaction parameters, such as the type and concentration of the crosslinker (N,N′‐methylenebisacrylamide or ethylene dimethacrylate), medium polarity, concentration of the monomer and initiator, and polymerization temperature, on the properties were examined. The hydrogel microspheres were characterized in terms of their chemical structure, size and size distribution, and morphological and temperature‐induced swelling properties. A decrease in the particle size was observed with increasing polarity of the reaction medium or increasing concentration of poly(N‐vinylpyrrolidone) as a stabilizer in the dispersion polymerization. The higher the content was of the crosslinking agent, the lower the swelling ratio was. Too much crosslinker gave unstable dispersions. Although the solvency of the precipitation polymerization mixture controlled the PNIPAAm microsphere size in the range of 0.2–1 μm, a micrometer range was obtained in the Shellvis 50 and Kraton G 1650 stabilized dispersion polymerizations of N‐isopropylacrylamide in toluene/heptane. Typically, the particles had fairly narrow size distributions. Copolymerization with the functional glycidyl methacrylate monomer afforded microspheres with reactive oxirane groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 968–982, 2006     

Further insight into the mechanism of poly(styrene‐co‐methyl methacrylate) microsphere formation

Polymeric microspheres have been used in a broad range of applications from chromatographic separation techniques to analysis of air flow over aerodynamic surfaces. The preparation of microspheres from many polymer families has consequently been extensively studied using a variety of synthetic approaches. Although there are a myriad of polymeric microsphere synthesis methods, free‐radical initiated emulsion polymerization is one of the most common techniques. In this work, poly(styrene‐co‐methyl methacrylate) microspheres were synthesized via surfactant‐free emulsion polymerization. The effects of co‐monomer composition and addition time on particle size distribution, particle formation, and particle morphology were investigated. Particles were characterized using dynamic light scattering and scanning electron microscopy to gain further insight into particle size and size distributions. Reaction kinetics were analyzed through consideration of characterization results. A particle formation mechanism for poly(styrene‐co‐methyl methacrylate) microspheres was proposed based on characterization results and known reaction kinetics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2249–2259     

Synthesis and characteristics of snowman-like fluorescent PMMA microbeads

This paper reports the fabrication of fluorescent snowman-like poly(methyl methacrylate) (PMMA) colloidal microbeads using a two-step method. The fluorescent cross-linked PMMA seeds were first synthesized by dispersion polymerization and then swelled in a monomer solution containing the methyl methacrylate monomer, a secondary cross-linker and initiator, followed by heat-induced polymerization. Scanning electron microscopy, confocal laser scanning microscopy, and Fourier transform infrared spectroscopy confirmed the synthesis of fluorescent snowman-like particles.     

Preparation of microspheres by radiation-induced polymerization. II. Mechanism of microsphere growth

The effects of the monomer concentration were investigated on the preparation of diethylene glycol dimethacrylate (2G) microspheres by radiation-induced polymerization. The monomer concentration strongly affected the conversion and the shape of the microspheres. The particles were obtained in the range from 2 to 24 vol % of 2G monomer. The effective concentration for the preparation of monodisperse microspheres is around 10 vol %. Higher monomer concentrations up to 24 vol % gave rough surface particles. Considering the effects on the number of microspheres in the solution, the authors introduced the inhibiting region, where one microsphere disturbs the existence of another microsphere, and tried to explain the mechanism of the microsphere growth. The competition between the propagation and the crosslinking reactions is balanced to give the microspheres.     

Preparation and characterization of a novel fluorinated acrylate resin

The novel fluorinated acrylate resin was successfully prepared by solution polymerization of 2-(perfluoro-(1,1-bis-isopropyl)-2-propenyl)oxyethyl methacrylate (POMA) with butyl acrylate (BA), methyl methacrylate (MMA) and methacrylic acid (MAA) initiated by AIBN in the co-solvents of ethyl acetate, butyl alcohol and toluene. POMA was synthesized from the intermediate perfluoro nonene and 2-hydroxyethyl methacrylate as the staring reactants. Films of the novel fluorinated acrylate resin were prepared by coating the resin directly on the clean glass sheet and allowed to dry at room temperature. The characteristics of the film such as hydrophobicity, glass transition temperature and thermal stability were characterized with the contact angle, differential scanning calorimetry and thermo-gravimetric analysis respectively. The structure of the novel fluorinated acrylate resin was investigated by Fourier transform infrared (FTIR) spectrometry. The influences of the fluorine content on the performance of the acrylate resin were studied. Results show that the hydrophobicity, chemical resistance, glass transition temperature and thermal stability of the acrylate resin are improved when the fluorinated monomer is introduced to copolymerize with other monomers. However, the hydrophobicity of the fluorinated acrylate resin is improved slightly via annealing.     

Preparation of copolymer microspheres of diethylene glycol dimethacrylate

Preparation of copolymer microspheres of diethylene glycol dimethacrylate (2G) with several comonomers by radiation-induced radical polymerization is described. Ethyl methacrylate (EMA), acrylamide, maleic anhydride, and styrene gave microspheres successively. The copolymerization resulted in gelation more easily than the 2G homopolymerization. The allowed ratio of copolymerization is up to about 0.4 as the mole fraction of comonomer for the solution containing 10 vol % 2G monomer. Copolymerization affected the size of microspheres by keeping its narrow distribution. The size of microspheres was increased by the copolymerization with EMA and styrene and, was decreased with acrylamide. The formation of microsphere strongly depends on the crosslinking ability of monomers. The crosslinking ability and reactivity in the copolymerization cause the change of the size of the microspheres. © 1992 John Wiley & Sons, Inc.     

Synthesis and Reactions of Hydrophilic Functional Microspheres for Immunological Studies

There is a need for hydrophilic polymeric microspheres with functional groups on their surface which can be reacted efficiently with proteins. These microspheres with antibodies (immunoglobulins) covalently bound to their surfaces constitute valuable immunoreagents capable of marking specific receptors (antigens) on cell surface membranes. The main requirements of the microspheres for the above applications are: insolubility in aqueous or organic media, absence of aggregation and of nonspecific interaction with cells and presence of suitable functional groups for covalent binding with antibodies. Hydrophobic polystyrene or poly(methyl methacrylate) latices do not meet these requirements. Copolymerization of hydrophilic monomers under suitable experimental conditions yielded microspheres with the required characteristics. Emulsion polymerization and ionizing radiation were found to constitute convenient techniques for the synthesis of hydrophilic and crosslinked (and therefore insoluble) functional microspheres ranging in diameter from 0.01 to 8 μm. By choosing suitable comonomers, it was possible to incorporate hydroxyl, carboxyl, amido, and dimethylamino functional groups into the particles. Copolymerization with isomeric vinylpyridines or dimethylamino methacrylate yielded weakly or strongly basic groups, respectively, capable of binding with acids. The experimental conditions suitable for obtaining desired particle sizes, in a relatively narrow distribution, were determined. It was found that the particle size depended to a large extent on the water solubility of the monomers, the presence or absence of stabilizer, the concentration of a surfactant, and the monomer concentration. The preferred technique to bind antibodies to the microsphere surface consisted of reacting amino groups with glutaraldehyde followed by the reaction with proteins. The use of polyglutaraldehyde instead of glutaraldehyde was also investigated. For this purpose the rate of polymerization of glutaraldehyde as a function of concentration and pH was first studied, followed by a study of the reactivity of polyglutaraldehyde micro-spheres with immunoglobulins. A recent new development of importance for cell separation is the synthesis of functional microspheres containing magnetic iron oxide. Preliminary investigations show that red blood cells and lymphocytes labeled with magnetic immunomicrospheres can be efficiently separated by means of permanent magnet. Separation of labeled from unlabeled human red blood cells was also achieved by means of a free-flow electrophoretic instrument.     

Preparation and Adsorption Ability of Molecularly Imprinted Polymer Microspheres for Malachite Green

Molecularly imprinted polymer (MIP) microspheres were synthesized through precipitation polymerization using malachite green (MG) as template, methacrylic acid (MAA) as monomer, and trimethylolpropane trimethacrylate (TRIM) as cross-linker. The microsphere structure of MIP was characterized by IR spectroscopy and SEM. The influence of preparation conditions such as monomer and cross-linker dosages on the polymer absorption of MG in acetonitrile solution was also explored. Under the optimum synthesis conditions (0.25 mmol MG, 1.5 mmol MAA, 2.5 mmol TRIM, 40 mL acetonitrile), the prepared MIP microspheres have a binding capacity as high as 2000 µg g^?1 of MG with an imprinting factor of above 4.0. The result suggests that the prepared MIP microspheres are promising material for the selective extraction of MG in complicated matrix solutions.     

Multifunctional nanoparticles/silica microsphere assemblies using polyglycidyl methacrylate shells as supports

A general method to prepare functional (or multifunctional) nanoparticles/silica microsphere assemblies is reported in this article. A thin shell of polyglycidyl methacrylate is grafted on the surface of silica through surface-initiated atom transfer radical polymerization technique. And then, various types of nanoparticles, including water-soluble CdTe quantum dots, Au nanoparticles and oil-soluble Fe₃O₄ nanoparticles are assembled on silica microspheres, respectively, or simultaneously. The properties of the assembled nanoparticles are well retained in the nanocomposite assemblies, and the controllable integration of magnetic and fluorescent properties can be achieved through varying the proportion of different nanoparticles assembled on nanoparticle/silica microsphere.     

Preparation of fluorescent polystyrene microspheres by gradual solvent evaporation method

Highly cross-linked polystyrene beads of 9.2 μm were synthesized by seed polymerization with styrene as monomer and divinylbenzene as cross linker. Other sized monodisperse PS microspheres were also prepared by varying seed particle diameter and proportion of swelling agents. Furthermore, the polystyrene beads were stained by gradual solvent evaporation method using dyes such as rhodamine 101 and acridine orange. Gradual solvent evaporation method facilitates a high concentration of fluorescent dyes on beads. This is the key to obtain fluorescent beads with high intensity. The results showed that the fabricated fluorescent microspheres could be excited to various wavelengths (such as yellow, green, red and scarlet). Our synthesized microspheres offer high fluorescence emission efficiency compared to commercial fluorescent microspheres in the mean time have other properties in common.     

粒径可控的聚乙烯醇交联微球VA/DVB的制备

以醋酸乙烯酯(VAc)为主单体,二乙烯基苯(DVB)为交联剂,聚乙烯醇(PVA)为分散剂,采用悬浮聚合法制备了交联微球VAe/DVB.重点考察了分散剂用量、搅拌速率、油水两相比例、NaCl用量等因素对交联微球的形成及其粒度的影响.使用甲醇对微球VAc/DVB进行醇解反应,制得了聚乙烯醇交联微球VA/DVB.结果表明:交联微球VA/DVB的物理形态决定于前驱体微球VAc/DVB的形貌与粒径.在悬浮聚合体系中,分散剂用量、搅拌速率与油水两相比是影响交联微球制备的主要因素,当分散剂用量太少(<0.3%)、搅拌速率太慢(<200 r/min)与油水两相体积比太大(>l:4)时,共聚合体系中均不能发生成球过程.控制悬浮聚合的反应条件,可以制备出球形度好、粒径可调控的交联微球VA/DVB.影响醇解反应的主要因素是反应温度,适宜的温度是40℃,反应15 h醇解度可达92%.     

Polymeric microspheres by radiation copolymerization of acrolein and various monomers at low temperatures

The preparation of polymeric microspheres having aldehyde groups by radiation polymerization of acrolein solution containing various monomers at low temperatures was studied, in which the monomer solution was dispersed with polyvinyl alcohol in order to obtain monomeric microspheres and then irradiated. The particle size of the microspheres from acrolein — 2-hydroxyethyl methacrylate system varied with polymerization and dispersion condition, in which the particle size increase of the concentration of 2-hydroxy ethyl methacrylate and its particle size distribution was broadened. In acrolein — polyethyleneglycol dimethacrylate system, the effect of the molecular structure of monomers on the particle size was studied, and it was found that the particle size decreased with number of oxyethylene units in monomers.     

Seeded polymerization as a method for producing hollow monodisperse microspheres

Crosslinked hollow monodisperse microspheres with diameters of 1.9–5.9 μm and one- or two-layer shells, with the layers being based on polymers of different natures, are produced by one- and two-stage seeded copolymerization of styrene and/or methyl methacrylate with ethylene glycol dimethacrylate or allyl methacrylate as crosslinking agents. Factors determining the morphology and dispersity of the microspheres are revealed. It is shown that, when, at the final stage of the synthesis, the content of a crosslinking agent in the reaction mixture is at least 50 wt %, the produced microspheres retain their size and morphology after exposure in toluene and dimethylformamide.     

Amine‐Functionalized Polyglycidyl Methacrylate Microsphere as a Unified Template for the Synthesis of Gold Nanoparticles and Single‐Crystal Gold Plates

Polyglycidyl methacrylate (PGMA) microspheres, crosslinked and surface‐functionalized by amine, can be used as a solid‐state template for the synthesis of gold (Au) crystals in the forms of either nanoparticles (NPs) or plates. It is discovered that the polymer microsphere acts as an internal template to cultivate Au NPs inside the microsphere or an external template to generate the single‐crystal plates depending on the critical concentration (C_cr) of gold ions. The ion–dipole interaction and the structure‐dependent solubility of gold induce two distinct gold nanostructures in the presence of the functionalized polymer microspheres. The catalytic activity and long‐term storage of the developed gold nanostructures that can be easily scaled‐up for mass production through the developed novel methodology is demonstrated.     

胶带表面优异防覆冰性能

通过在普通胶带表面黏结聚甲基丙烯酸甲酯(PMMA)微米球,再通过水热法在微米球表面制备规则的ZnO纳米棒结构,经氟化处理后得到了具有柔性、大面积、低温超疏水和防冰性能的薄膜.低温环境中,液滴在这种复合的微纳米结构表面可以实现结冰延迟.经历结冰-融化循环后,液滴的界面未发生明显变化,证明了该结构的可靠性.这种抗结冰的薄膜是建立在胶带和PMMA基础之上的,在风电、高压线缆以及冰箱制造工业中具有良好的应用前景.