The removal of arsenic from (ground)-water by adsorbent loaded in polymeric microspheres

Arsenic is a natural tasteless and odourless element,existing in the earth's crust at average levels of between two and five thousands micrograms per liter (parts per million) . Arsenic is highly toxic to humans, who are exposed to it primarily from air,food and water. The occurrence of arsenic in groundwater is due to geological composition of soil. High concentrations of arsenic in water are the result of dissolution or desorption of ferric oxides and the oxidation of mineral arsenopyrites. Arsenic in drinking water has an important impact on the human health,especially in the less developed countries. Different methods exist to remove arsenic from aquatic media,and one of them is by adsorption. In this work,the adsorption of both As(III) and As(V) by means of novel microspheres has been investigated. In particular,TiO2 has been embedded into polymeric microspheres PES (PolyEtherSulphone) and PEEK-WC (PolyEtherEther-Ketone) . The main advantages of this encapsulation adsorption material are: no loss of adsorbents into the water stream,easy to be used and scaled-up.

An efficient preparation of porous polymeric microspheres by solvent evaporation in foam phase

This paper reports an efficient method of preparing porous polymeric microspheres by solvent evaporation in foam phase,in which phase separation between polymer and porogen occurs in foam phase instead of that in water phase by using the traditional solvent eva poration method.The method provides outstanding features,including being time-saving,of high-yield and able for continuous production,in which formation of porous polymeric microspheres finished within 3 min with a high production yield up to approximate 95 wt% and the process was able to be developed into a continuous process for production of porous polymeric microspheres.It was also universal to non-crosslinked polymers since the method is a development on the traditional emulsion solvent evaporation method.The new method is efficient and can be used potentially on the industrial scale for continuous production of porous polymeric microsphere s.

Performance and enhanced oil recovery efficiency of an acid-resistant polymer microspheres of anti-CO_(2) channeling in low-permeability reservoirs

CO_(2) flooding is a vital development method for enhanced oil recovery in low-permeability reservoirs,However,micro-fractures are developed in low-permeability reservoirs,which are essential oil flow channels but can also cause severe CO_(2) gas channeling problems.Therefore,anti-gas channeling is a necessary measure to improve the effect of CO_(2) flooding.The kind of anti-gas channeling refers to the plugging of fractures in the deep formation to prevent CO_(2) gas channeling,which is different from the wellbore leakage.Polymer microspheres have the characteristics of controllable deep plugging,which can achieve the profile control of low-permeability fractured reservoirs.In acidic environments with supercritical CO_(2),traditional polymer microspheres have poor expandability and plugging properties.Based on previous work,a systematic evaluation of the expansion performance,dispersion rheological properties,stability,deep migration,anti-CO_(2) channeling and enhanced oil recovery ability of a novel acid-resistant polymer microsphere(DCNPM-A)was carried out under CQ oilifield conditions(salinity of85,000 mg/L,80℃,pH=3).The results show that the DCNPM-A microsphere had a better expansion performance than the traditional microsphere,with a swelling rate of 13.5.The microsphere dispersion with a concentration of 0.1%-0.5%had the advantages of low viscosity,high dispersion and good injectability in the low permeability fractured core.In the acidic environment of supercritical CO_(2),DCNPM-A microspheres showed excellent stability and could maintain strength for over 60 d with less loss.In core experiments,DCNPM-A microspheres exhibited delayed swelling characteristics and could effectively plug deep formations.With a plugging rate of 95%,the subsequent enhanced oil recovery of CO_(2) flooding could reach 21.03%.The experimental results can provide a theoretical basis for anti-CO_(2)channeling and enhanced oil recovery in low-permeability fractured reservoirs.

Polymeric microsphere injection in large pore-size porous media

High water-cut has become a worldwide challenge for oil production.It requires extensive efforts to process and dispose.This entails expanding water handling facilities and incurring high power consumption costs.Polymeric microsphere injection is a cost-effective way to deal with excessive water production from subterranean formations.This study reports a laboratory investigation on polymeric microsphere injection in a large volume to identify its in-depth fluid diversion capacity in a porous media with large pore/particle size ratio.The performance of polymeric microsphere injection was evaluated using etched glass micromodels based on the pore network of a natural carbonate rock,which were treated as water-wet or oil-wet micromodels.Waterflooding was conducted to displace oil at reservoir temperature of 95°C,followed by one pore volume of polymeric microsphere injection.Three polymeric microsphere samples with median particle size of 0.05,0.3,and 20μm were used to investigate the impact of particle size of the polymeric microspheres on incremental oil production capacity.Although the polymeric microspheres were much smaller than the pores,additional oil production was observed.The incremental oil production increased with increasing polymeric microsphere concentration and particle size.As a comparison,polymeric microsphere solutions were injected into oil-wet and water-wet micromodels after waterflooding.It was observed that the oil production in oil-wet micromodel was much higher than that in water-wet micromodel.The wettability of micromodels affected the distribution patterns of the remaining oil after waterflooding and further dominated the performance of the microsphere injection.The study supports the applicability of microsphere injection in oil-wet heterogeneous carbonates.

Immobilization of penicillin G acylase on paramagnetic polymer microspheres with epoxy groups

Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated Fe3O4nanoparticles using N,N’‐methylene‐bis(acrylamide)as across‐linking agent.Penicillin G acylase(PGA)was covalently immobilized on the surface of theparamagnetic microspheres by reacting the amino groups of the PGA molecules with the epoxygroups of the paramagnetic polymer microspheres.The effect of the SiO2coating and the amount ofparamagnetic Fe3O4nanoparticles on the initial activity and the operational stability of the immobilizedPGA was investigated.The results indicated that SiO2played an important role in the polymerization process and paramagnetic polymer microspheres with a SiO2‐coated Fe3O4nanoparticles mass content of7.5%are an optimal support material for PGA immobilization.Immobilized PGA on the paramagnetic polymer microspheres shows a high initial activity of430U/g(wet)and retains99%of its initial activity after recycling10times.Furthermore,immobilized PGA exhibits high thermal stability,pH stability and excellent reusability,which can be rapidly recycled by the aid of magnet.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Preparation and Characterization of Non-porous Superparamagnetic Microspheres with Epoxy Groups by Dispersion Polymerization

Non-porous superparamagnetic polymer microspheres with epoxy groups were prepared by dispersion polymerization of glycidyl methacrylate (GMA) in the presence of magnetic iron oxide (Fe3O4) nanoparticles coated with oleic acid. The polymerization was carried out in the ethanol/water medium using polyvinylpyrrolidone (PVP) and 2,2’-azobisisobutyronitrile (AIBN) as stabilizer and initiator, respectively. The magnetic microspheres obtained were characterized with scanning electron microscopy (SEM), vibrating sample magnetometry (VSM) and Fourier transform infrared spectroscopy (FTIR). The results showed that the magnetic microspheres had an average size of-1μm with superparamagnetic characteristics. The saturation magnetization was found to be 4.5emu.g-1. There was abundance of epoxy groups with density of 0.028 mmol·g^-1 in microspheres. The magnetic PGMA microspheres have extensive potential uses in magnetic bioseparation and biotechnology.

SYNTHESIS OF MONODISPERSE HOLLOW POLYMER MICROSPHERES WITH FUNCTIONAL GROUPS BY DISTILLATION PRECIPITATION POLYMERIZATION

Monodisperse hollow polymer microspheres having various functional groups on the shell-layer, such as carboxylic acid, pyridyl and amide, were prepared by two-stage distillation precipitation polymerization in neat acetonitrile in the absence of any stabilizer or additive, during which monodisperse poly（methacrylic acid） （PMAA） afforded from the first-stage polymerization was utilized as the seeds for the second-stage polymerization. The shell layer with different functional groups was formed during the second-stage copolymerization of either divinylbenzene （DVB） or ethyleneglycol dimethacrylate （EGDMA） as crosslinker and the functional comonomers, in which the hydrogen-bonding interaction between the carboxylic acid group of PMAA core and the functional groups of the corresponding comonomers, including carboxylic acid, amide and pyridyl, played an essential role for the formation of monodisperse core-shell functional microspheres. The hollow polymer microspheres were then developed after the subsequent removal of PMAA cores by dissolution in ethanol under basic condition. Transmission electron microscopy （TEM） and scanning electron microscopy （SEM） were used to determine the morphology of the resultant PMAA core, functional core-shell microspheres and the corresponding hollow polymer microspheres with different functional groups. FT-IR spectra confirmed the successful incorporation of the various functional groups on the shell layer of the hollow polymer microspheres.

A review of recent progress in preparation of hollow polymer microspheres

The preparation methods of hollow polymer microspheres both at home and abroad are summarized, and their preparation mechanisms and developmental states are presented. These methods include the liquid droplet method, dried-gel droplet method, self-assembly method, microencapsulation method, emulsion polymerization method and the template method. Hollow polystyrene microspheres are the most extensively studied in the research of hollow polymer microspheres. Through comparison of the advantages and disadvantages of different preparation methods, it is concluded that microencapsulation method is most suitable for preparing polystyrene hollow microspheres.

Preparation of Dysprosium Ferrite/Polyacrylamide Magnetic Composite Microsphere and Its Characterization

Using the technique of microemulsion polymerization with nano-reactor, dysprosium ferrite/polyacrylamide magnetic composite microsphere was prepared by one-step method in a single inverse microemulsion. The structure, average particle size, morphology of composite microsphere were characterized by FTIR, XRD, TEM and TGA. The magnetic responsibility of composite microsphere was also investigated. The results indicate that the magnetic composite microsphere possess high magnetic responsibility and suspension stability.

PREPARATION OF MONODISPERSE CROSSLINKED POLYMER MICROSPHERES HAVING CHLOROMETHYL GROUP BY DISTILLATIONPRECIPITATION POLYMERIZATION

Monodisperse crosslinked poly(chloromethylstyrene-co-divinylbenzene)(poly(CMSt-co-DVB))microsphereswere prepared by distillation-precipitation copolymerization of chloromethylstyrene(CMSt)and divinylbenzene(DVB)inneat acetonitrile.The polymer particles had clean surfaces due to the absence of any added stabilizer.The size of the particlesranges from 2.59 μm to 3.19 μm and with mono-dispersity around 1.002-1.014.The effects of monomer feed incopolymerization on the microsphere formation were described.The polymer microspheres were characterized by SEM andchlorinity elemental analysis.

PREPARATION OF POLYMER MICROSPHERES WITH PYRIDYL GROUP AND THEIR STABILIZED GOLD METALLIC COLLOIDS

Narrow disperse poly（ethyleneglycol dimethacrylate-co-4-vinylpyridine） （poly（EGDMA-co-4-VPy）） microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate （EGDMA） and 4-vinylpyridine （4-VPy） with 2,2＇-azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile. The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm, which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles. The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.

Preparation and performance of fluorescent polyacrylamide microspheres as a profile control and tracer agent

Polyacrylamide microspheres have been suc- cessfully used to reduce water production in reservoirs, but it is impossible to distinguish polyacrylamide microspheres from polyacrylamide that is used to enhance oil recovery and is already present in production fluids. In order to detect polyacrylamide microspheres in the reservoir pro- duced fluid, fluorescent polyacrylamide microspheres P（AM-BA-AMCO）, which fluoresce under ultraviolet irradiation, were synthesized via an inverse suspension polymerization. In order to keep the particle size distribu- tion in a narrow range, the synthesis conditions of the polymerization were studied, including the stirring speed and the concentrations of initiator, NaaCO3, and dispersant. The bonding characteristics of microspheres were deter- mined by Fourier transform infrared spectroscopy. The surface morphology of these microspheres was observed under ultraviolet irradiation with an inverse fluorescence microscope. A laboratory evaluation test showed that the fluorescent polymer microspheres had good water swelling capability, thus they had the ability to plug and migrate in a sand pack. The plugging rate was 99.8 % and the residual resistance coefficient was 800 after microsphere treatment in the sand pack. Furthermore, the fluorescent microspheres and their fragments were accurately detected under ultra- violet irradiation in the produced fluid, even though theyhad experienced extrusion and deformation in the sand pack.

Local immunotherapy with interleukin - 2 delivered from biodegradable polymer microspheres combined with interstitial chemotherapy: a novel treatment for experimental malignant glioma.

OBJECTIVE:Local delivery of carmustine(BCNU)from biodegradablepolymers prolongs survival against experi-mental brain tumors.Moreover,paracrine administration of interleukin-2(IL-2)has been shown to elicit apotent antitumor immune response and to improve survival in animal brain tumor models.We report the use of anovel polymeric microsphere delivery vehicle to release IL-2.We demonstrate both in vitro release of cytokinefrom the microspheres and histological evidence of the inflammatory response elicited by IL-2 released from themicrospheres in the rat brain.Thees microspheres are used to deliver IL-2,and biodegradable polymer wafers

From the microspheres to scaffolds:advances in polymer microsphere scaffolds for bone regeneration applications

The treatment and repair of bone tissue damage and loss due to infection,tumours,and trauma are major challenges in clinical practice.Artificial bone scaffolds offer a safer,simpler,and more feasible alternative to bone transplantation,serving to fill bone defects and promote bone tissue regeneration.Ideally,these scaffolds should possess osteoconductive,osteoinductive,and osseointegrative properties.However,the current first-generation implants,represented by titanium alloys,have shown poor bone-implant integration performance and cannot meet the requirements for bone tissue repair.This has led to increased research on second and third generation artificial bone scaffolds,which focus on loading bioactive molecules and cells.Polymer microspheres,known for their high specific surface areas at the micro-and nanoscale,exhibit excellent cell and drug delivery behaviours.Additionally,with their unique rigid structure,microsphere scaffolds can be constructed using methods such as thermal sintering,injection,and microsphere encapsulation.These scaffolds not only ensure the excellent cell drug loading performance of microspheres but also exhibit spatial modulation behaviour,aiding in bone repair within a three-dimensional network structure.This article provides a summary and discussion of the use of polymer microsphere scaffolds for bone repair,focusing on the mechanisms of bone tissue repair and the current status of clinical bone grafts,aimed at advancing research in bone repair.

An efficient synthesis of ampicillin on magnetically separable immobilized penicillin G acylase

Penicillin G acylase(PGA) was immobilized on the magnetic hydrophilic polymer microspheres with average pore size of 17.1 nm,specific surface area of 128.2 m2/g and saturate magnetization of 6.4 emu/g.The 96.7%ampicillin yield with 1.60 of the synthesis/hydrolysis(S/H) ratio from 6-aminopenicillanic acid(6-APA) and D-(-)-alpha-phenylglycine methyl ester(D-PGME) can be achieved using the resultant magnetic biocatalyst in ethylene glycol,where only 82.1%yield with 1.40 of the S/H ratio was obtained using the free PGA under the identical reaction conditions.The immobilized PGA can be separated magnetically and recycled for five times without obvious loss of its catalytic activity.

Photo-induced fusion of monodisperse polymer microspheres:A novel strategy for constructing topological microsphere clusters with improved stability

The preparation of monodisperse azobenzene(Azo)polymer microspheres by dispersion polymerization was reported.The photo-induced fusion of Azo polymer microspheres was successfully achieved during the process of reversible trans-cistrans photoisomerization of Azo units,and induced various unique“microsphere molecular”clusters or“microsphere polymers”.Encouraged by this interesting phenomenon,microsphere clusters of different topological structures were stabilized by the in situ acetal cross-linking chemistry.The photo-induced fusion polymerization of monodisperse polymer microspheres provides a new strategy for designing photo-responsive clusters and allows for control over the mechanical properties of microspheres with high spatiotemporal resolution.

Influence of surface modification of SrFe12O19 particles with oleic acid on magnetic microsphere preparation

Oleic acid was used as surface modification agent to improve the hydrophobicity of magnetic strontium hexaferrite particles. The structure and properties of treated magnetic particles were characterized by scanning electronic microscopy （SEM）, Fourier transform infrared spectra （FTIR）, powder X-ray diffraction （XRD） and magnetic property measurement system （MPMS）. The results show that oleic acid is chemically enwrapped on the surface of SrFe12O19 particles. Magnetic particles modified by oleic acid are highly dispersible and strongly responsive to magnetism but with slight decrease in saturated magnetization. The affinity between magnetic particles and monomers is improved by surface modification, resulting in increased particle incorporation in magnetic polymeric microspheres. The surface modification mechanism of magnetic particles by oleic acid is addressed in this work.

MAGNETIC POLYMER MICROSPHERE STABILIZED GOLD NANOCOLLOIDS AS A FACILELY RECOVERABLE CATALYST

Magnetically responsive hierarchical magnetite/silica/poly（ethyleneglycol dimethacrylate-co-4-vinylpyridine） （Fe3O4/SiO2/P（EGDMA-co-VPy）） tri-layer microspheres were used as stabilizers for gold metallic nanoeolloids as a facilely recoverable catalyst with the reduction of 4-nitrophenol to 4-aminophenol as a model reaction. The magnetic microsphere stabilized gold metallic nanocolloids were prepared by in situ reduction of gold chloride trihydrate with borohydride as reductant via the stabilization effect of the pyridyl groups to gold nanoparticles on the surface of the outer shell-layer of the inorganic/polymer tri-layer microspheres.

Preparation and Properties of Magnetic-fluorescent Microporous Polymer Microspheres

Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by incorporating Fe304 nanoparticles and CdSe/ZnS quantum dots（QDs） into hyper-crosslinked microporous polymer micro- spheres（HCMPs） via the in situ coprecipitation method and swelling-diffusion. The HCMPs predominantly have mi- cropores, and their specific surface area is as high as 703.4 m2/g. The magnetic-fluorescent microspheres maintain the superparamagnetic behavior of Fe304, and the saturation magnetization reaches 38.6 A.m2/kg. Moreover, the composite microspheres exhibit an intense emission peak at 530 nm and achieve good fluorescence.

Whispering-gallery mode lasing from polymer microsphere for humidity sensing

Microlasers based on high quality （Q） whispering-gallery mode （WGM） resonance are pronfising low threshold laser sources for bio-sensing and imaging applications. In this Letter, dye-doped polymer microspheres were fabricated by a controlling emulsion solvent evaporation method. WGM lasing with low threshold and high Q factors was realized in an individual microsphere under femtosecond laser pumping. The slight change of environmental relative humidity （RH） can be monitored by measuring the shift of the lasing modes at tile ex- posure of water molecules, which dcmonstrates the sensitivity is as high as 6 pm/RH%. The results would offer an insight into employing microlasers as sensors.