Properties of magnetic poly(glycidyl methacrylate) and poly(N-isopropylacrylamide) microspheres

Iron oxide colloids were prepared by coprecipitation of Fe(II) and Fe(III) salts in alkaline media and stabilized by perchloric acid, oleic acid, or poly(acrylic acid). In an attempt to obtain magnetic polymer microspheres differing in size, dispersion polymerization of glycidyl methacrylate (GMA) in ethanol containing HClO₄-stabilized magnetite, dispersion copolymerization of GMA and 2-hydroxyethyl methacrylate (HEMA) in toluene/2-methylpropan-1-ol mixture in the presence of oleic acid-coated magnetite, and inverse suspension copolymerization of N-isopropylacrylamide (NIPAAm) and N,N′-methylenebisacrylamide (MBAAm) in cyclohexane in the presence of poly(acrylic acid)-coated maghemite were compared. The microspheres were characterized by morphology, size, polydispersity, and some magnetic properties.     

Poly(glycidyl methacrylate-acrylonitrile)-based polymeric electrolytes for dye-sensitized solar cell applications

Poly(glycidyl methacrylate-acrylonitrile) P(GMA-AN) copolymer was synthesized and used as a polymer electrolyte in dye-sensitized solar cells (DSSCs). P(GMA-AN)-based polymer electrolyte is obtained by adding 1-methyl-3-propylimidazolium iodide (PMII) as a room temperature ionic liquid (RTIL), tetrabutylammonium iodide (TBAI), iodide (I2) as the source of redox couple (I3(-)/I(-)) in order to improve the power conversion efficiency (PCE) by addition of optimized plasticizer contents such as ethylene carbonate (EC) and propylene carbonate (PC) in an acetonitrile solvent. These polymer electrolyte results revealed that more stable photovoltaic performance such as PCE of 4.97% with enhanced short-circuit current density (J(SC), 10.42 mA/cm2) and open circuit voltage (V(OC), 0.75 V) and fill factor (FF) of 0.63 under standard light intensity of 100 mW/cm2, irradiation of AM 1.5 sunlight. It is expected that these polymer electrolyte is an attractive alternative to liquid electrolytes for the fabrication of the long term stable DSSCs.     

Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) beads for heavy metal removal

Poly(ethylene glycol dimethacrylate-n-vinyl imidazole) [poly(EGDMA-VIM)] hydrogel (average diameter 150-200 microm) was prepared by copolymerizing ethylene glycol dimethacrylate (EGDMA) with n-vinyl imidazole (VIM). The copolymer hydrogel bead composition was characterized by elemental analysis and found to contain 5 EGDMA monomer units each VIM monomer unit. Poly(EGDMA-VIM) beads had a specific surface area of 59.8 m2/g. Poly(EGDMA-VIM) beads were characterized by swelling studies and scanning electron microscopy (SEM). These poly(EGDMA-VIM) beads with a swelling ratio of 78% were used for the heavy metal removal studies. Chelation capacity of the beads for the selected metal ions, i.e., Cd(II), Hg(II) and Pb(II) were investigated in aqueous media containing different amounts of these ions (10-750 mg/l) and at different pH values (3.0-7.0). Chelation rate was very fast. The maximum chelation capacities of the poly(EGDMA-VIM) beads were 69.4 mg/g for Cd(II), 114.8 mg/g for Pb(II) and 163.5 mg/g for Hg(II). The affinity order on molar basis was observed as follows: Hg(II) > Cd(II) > Pb(II). Chelation behavior of heavy metal ions could be modelled using both the Langmuir and Freundlich isotherms. pH significantly affected the chelation capacity of VIM incorporated beads. Chelation of heavy metal ions from synthetic wastewater was also studied. The chelation capacities are 45.6 mg/g for Cd(II), 74.2 mg/g for Hg(II) and 92.5 mg/g for Pb(II) at 0.5 mmol/l initial metal concentration. Regeneration of the chelating-beads was easily performed with 0.1 M HNO3. These features make poly(EGDMA-VIM) beads potential candidate adsorbent for heavy metal removal.     

Large-scale initiated chemical vapor deposition of poly(glycidyl methacrylate) thin films

The initiated chemical vapor deposition (iCVD) of poly(glycidyl methacrylate) (PGMA) was scaled up using dimensionless analysis. In the first stage, PGMA was deposited onto a large stationary substrate and a deposition rate as high as 85 nm/min was achieved. It was found that the deposition rate increases with increasing filament temperature, whereas the deposition rate and the number-average molecular weight decrease with increasing substrate temperature. In the second stage, PGMA was deposited onto a moving substrate. At speeds between 20 mm/min and 60 mm/min, the deposition rate on the moving substrate was found to be equal to the deposition rate on the stationary substrate. Fourier transform infrared spectroscopy showed that the epoxide functionality of the PGMA films was retained during the iCVD process. Since the iCVD polymerization of different vinyl monomers all use similar parameters, this scale up can be applied to the scale up of other vinyl monomers such as 2-hydroxyethyl methacrylate and perfluoroalkyl ethyl methacrylate.     

聚偏氟乙烯/聚甲基丙烯酸甲酯交替多层材料的热稳定性

利用微层共挤出技术制得不同层数(2,16,64层)的聚偏氟乙烯(PVDF)/聚甲基丙烯酸甲酯(PMMA)交替多层材料,通过偏光显微镜、垂直燃烧测试、热失重分析、红外光谱分析、微型量热测试研究了层数的变化对体系热分解和热释放行为的影响。结果表明,PVDF层与PMMA层沿层状样品的厚度方向交替排列,层结构明显,层界面清晰,随着层数的增加,层界面数增加,材料的垂直燃烧行为几乎不变,但表现出更高的热稳定性;高层数样品中热稳定性优异的PVDF层对易热解的PMMA层保护作用增强,且在热释放过程中,更多的层界面为PVDF炭层的形成提供了更丰富的空间,使材料的热释放速率减小,总热释放降低。     

Myoglobin adsorption onto poly(glycidyl methacrylate) microbeads with surface functionalized iminodiacetic acid

In this study, poly(glycidyl methacrylate) [PGMA] microbeads with surface modified iminodiacetic acid (IDA) were used for myoglobin (Mb) adsorption from buffer solutions at different pHs and ionic strengths in a packed-bed column. Attenuated Total Reflectance Fourier Transformed Infrared (ATR-FTIR) spectroscopy and scanning electron microscopy (SEM) measurements before and after the adsorption process confirmed the structural stability of adsorbed Mb. The effects of initial concentration, flow-rate, pH and ionic strength on the adsorption were investigated. The results showed that the maximum amount of protein was adsorbed at a pH 7.0, which is the protein isoelectric point. The adsorption is rationalized in terms of local electrostatic forces acting between the protein and the IDA modified PGMA surface as well as hydrophobic interactions close to the protein isoelectric point, whereas at low pH the global changes give rise to protein–protein repulsion and at high pH protein-support material repulsion.     

Poly(hydroxyethyl methacrylate) nanobeads containing imidazole groups for removal of Cu(II) ions

Poly(hydroxyethyl methacrylate) (PHEMA) nanobeads with an average size of 300 nm in diameter and with a polydispersity index of 1.156 were produced by a surfactant free emulsion polymerization. Specific surface area of the PHEMA nanobeads was found to be 996 m²/g. Imidazole containing 3-(2-imidazoline-1-yl)propyl(triethoxysilane) (IMEO) was used as a metal-chelating ligand. IMEO was covalently attached to the nanobeads. PHEMA-IMEO nanobeads were used for the removal of copper(II) ions from aqueous solutions. To evaluate the degree of IMEO loading, the PHEMA nanobeads were subjected to Si analysis by using flame atomizer atomic absorption spectrometer and it was estimated as 973 µmol IMEO/g of polymer. The PHEMA nanobeads were characterized by transmission electron microscopy and fourier transform infrared spectroscopy. Adsorption equilibrium was achieved in about 8 min. The adsorption of Cu²⁺ ions onto the PHEMA nanobeads was negligible (0.2 mg/g). The IMEO attachment into the PHEMA nanobeads significantly increased the Cu²⁺ adsorption capacity (58 mg/g). Adsorption capacity of the PHEMA-IMEO nanobeads increased significantly with increasing concentration. The adsorption of Cu²⁺ ions increased with increasing pH and reached a plateau value at around pH 5.0. Competitive heavy metal adsorption from aqueous solutions containing Cu⁺, Cd²⁺, Pb²⁺ and Hg²⁺ was also investigated. The adsorption capacities are 61.4 mg/g (966.9 µmol/g) for Cu²⁺; 180.5 mg/g (899.8 µmol/g) for Hg²⁺; 34.9 mg/g (310.5 µmol/g) for Cd²⁺ and 14.3 mg/g (69 µmol/g) for Pb²⁺. The affinity order in molar basis is observed as Cu²⁺ > Hg²⁺ > Cd²⁺ > Pb²⁺. These results may be considered as an indication of higher specificity of the PHEMA-IMEO nanobeads for the Cu²⁺ comparing to other ions. Consecutive adsorption and elution operations showed the feasibility of repeated use for PHEMA-IMEO nanobeads.     

Poly(styrene-block-vinylpyrrolidone) beads as a versatile material for simple fabrication of optical nanosensors

A versatile platform for designing optical nanosensors is proposed. The "sensing chemistries" are entrapped into the poly(styrene-block-vinylpyrrolidone) nanobeads having the average size of 245 nm in aqueous media. Addressable staining into the core or the shell of the beads results in nanosensors for essential analytes such as dissolved oxygen, temperature, pH, chloride, and copper ions. Two immobilization procedures are developed: staining in the polystyrene core is performed from a tetrahydrofuran/water mixture (50:50 v/v) and staining in the poly(vinylpyrrolidone) shell is achieved by using the ethanol/water mixture (70:30 v/v). The oxygen and temperature indicators should be preferably immobilized into the core, whereas nanosensors for ions are manufactured by staining into the shell. In the case of the lipophilic pH indicators both procedures result in similar pKa values. The unique properties of the beads make them promising for sensing and imaging even in very complex media, multianalyte sensing, and monitoring of very fast processes.     

Dynamic fracture behavior of single and contacting Poly(methyl methacrylate) particles

Fracture behaviors of single, two, and multiple contacting spherical Poly(methyl methacrylate) (PMMA) particles were recorded using high speed synchrotron X-ray phase contrast imaging. A miniaturized Kolsky bar setup was used to apply dynamic compressive loading on the PMMA particles. In both single and two particle experiments, cracking initiated near the center of the particles and propagated towards the contacts. The crack bifurcated near the contact points for single particle experiments, thus forming conical fragments. The crack bifurcation and subsequent conical fragment formation was observed only at the particle-particle contact for two particle experiments. The particles were observed to fracture in hemispherical fragments normal to the contact plane in the multi-particle experiments. The observed failure mechanisms strongly suggest that the maximum tensile stress near the center of the particle is the critical parameter governing fracture of the particles. Furthermore, the compressive stress under the contact areas led to the bifurcation and subsequent conical fragment formation.     

Preparation and Compaction Behaviour of Poly(methyl methacrylate) Coated Iron Microparticles

The poly(methyl methacrylate)(PMMA) coatings onto surface of iron particles were electrochemically prepared and the effect on both surface structure and internal structure of the resulted material after compaction was carried out.The electrochemical polymerization treatment was performed in a fluidized bed electrolyzer using sulphuric acid solution containing potassium persulphate and methyl methacrylate(MMA).The surface topography and the microstructure of the samples were observed by scanning electron mic...     

Poly(vinyl pyridine-poly ethylene glycol methacrylate-ethylene glycol dimethacrylate) beads for heavy metal removal

Poly(vinyl pyridine-poly ethylene glycol methacrylate-ethylene glycol dimethacrylate) [poly(VP-PEGMA-EGDMA)] beads with an average size of 30–100 μm were prepared by suspension polymerization. Poly(VP-PEGMA-EGDMA) beads were characterized by swelling studies, scanning electron microscopy (SEM), elemental analysis, Fourier Transform Infrared Spectroscopy (FTIR). The beads with a swelling ratio of 65% were used for the heavy metal removal studies. Chelation capacity of the beads for the selected metal ions, i.e., Pb(II), Cd(II), Cr(III) and Cu(II) were investigated in aqueous media containing different amounts of these ions (5–80 mg/l) and at different pH values (2.0–10.0). The maximum chelation capacities of the poly(VP-PEGMA-EGDMA) beads were 18.23 mg/g for Pb(II), 16.50 mg/g for Cd(II), 17.38 mg/g for Cr(III) and 18.25 mg/g for Cu(II). The affinity order on mass basis was observed as follows: Cu(II) > Pb(II) > Cr(III) > Cd(II). pH significantly affected the chelation capacity of VP incorporated beads. Heavy metal adsorption on the poly(PEGMA-EGDMA) control microspheres was negligible. Regeneration of the chelating beads was easily performed with 0.1 M HNO₃. It was shown that these beads can be used effectively for heavy metal removal from aqueous solutions with repeatedly adsorption–desorption operations. These features show that poly(VP-PEGMA-EGDMA) beads are potential candidate sorbent for heavy metal removal.     

Poly(N,N-dimethylaminoethyl methacrylate) modification of activated carbon for copper ions removal

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) functionalization of rice husk-based activated carbon was prepared and its application in the removal of copper ions was investigated. The structural properties of the resulting composite material were characterized by means of N₂ adsorption/desorption, Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA). The obtained composite is observed to hold a relatively large pore diameter of 3.8 nm and high surface area of 789 m² g^?1 with 12 wt% of PDMAEMA coated, which is significant for its use as adsorbent. The ability of the composite material for removing Cu²⁺ from aqueous solution was studied by batch experiments. The adsorption data obeyed the Langmuir isotherms, which revealed that 1 g of the prepared material could adsorb 31.46 mg of Cu²⁺ from its aqueous solution. The PDMAEMA functionalized activated carbon is expected to be used as an efficient adsorbent for removing other heavy metal ions and dyes in water.     

A smart microfluidic affinity chromatography matrix composed of poly(N-isopropylacrylamide)-coated beads

The efficient upstream processing of complex biological or environmental samples for subsequent biochemical analysis remains a challenge in many analytical systems. New microfluidic platforms that provide multidiagnostic capabilities on single chips face a similar challenge in getting specific analytes purified or contaminants removed in different fluid streams. Here, stimuli-responsive polymers have been used to construct "smart" beads that can be reversibly immobilized on microfluidic channel walls to capture and release targets. The 100-nm latex beads were surface-modified with the temperature-sensitive polymer poly(N-isopropylacrylamide) (PNIPAAm). At room temperature, a suspension of these beads flows through a microfluidic channel constructed of poly(ethylene terephthalate). However, when the temperature in the channel is raised above the lower critical solution temperature (LCST) of PNIPAAm, the beads aggregate and adhere to the walls of the channel. The adhered beads are stable for long durations on the channel walls (demonstrated up to 70 min) in the presence of flow. The beads were further modified with the affinity moiety biotin, which tightly binds streptavidin. The dual-modified beads were adhered to the channel walls and functioned as a chromatographic affinity separation matrix, capable of binding streptavidin that was flowed through the microfluidic channel. Upon the reverse thermal stimulation to below the PNIPAAm LCST, the beads and captured streptavidin were observed to quickly dissolve and elute from the channel walls. This temperature-responsive affinity chromatography matrix can thus be flowed into a column and aggregated via temperature change, followed by the controlled release of affinity-captured targets back into the microfluidic flow stream.     

Preparation,characterization of chitosan/bamboo charcoal/poly(methacrylate) composite beads

Preparation and characterization of a low-cost, novel steam-activated bamboo charcoal (BC) and poly(methacrylate) (PMAA) bound with chitosan (CTS) to form chitosan/bamboo charcoal/poly(methacrylate) (CTS/BC/PMAA) composite beads is reported for the first time in this paper. The characteristics are revealed by techniques such as X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), scanning electron microscopy (SEM), Brunauer Emmett Teller (BET), solution pH and pH at point of zero charge \((\hbox {pH}_{\mathrm {pzc}})\). The composite beads possessed a dominant acidic surface group of 0.663 mmol \(\hbox {g}^{\mathrm {-1}}\), as revealed by Boehm titration method. This acidity was confirmed by its solution pH of 6.46; \(\hbox {pH}_{\mathrm {pzc}}\) of 6.70 and increase in oxygen surface via XPS analysis. \(\hbox {N}_{\mathrm {2}}\) adsorption–desorption isotherms at 77 K of the beads revealed high BET surface area (SA) of 681.15 \(\hbox {m}^{\mathrm {2}}\hbox {g}^{\mathrm {-1}}\). Langmuir model affords a SA of 773.34 \(\hbox {m}^{\mathrm {2}}\hbox {g}^{\mathrm {-1}}\). SEM showed the microporous nature of the composite beads. The properties of CTS/BC/PMAA composite beads were compared to CTS/BC and neat BC. Thermal stability and successful coating of 5.1 wt% of PMAA and 6.8 wt% of CTS to CTS/BC/PMAA beads were shown by DSC and TGA analyses. The composite beads showed low carbon particle released at pH 7.4 and 6.8. Furthermore, dynamic adsorption revealed that CTS/BC/PMAA composite beads can be used to capture a polar substance, such as creatinine.     

聚甲基丙烯酸甲酯/二氧化硅复合材料的热性能

聚甲基丙烯酸甲酯/二氧化硅(PMMA/Si O_2)复合材料可以通过简便的单体浇铸、本体聚合方法制备,二氧化硅用硅烷偶联剂3-(异丁烯酰氧)丙基三甲氧基硅烷(γ-MPS)进行表面修饰,并用红外光谱表征其甲苯抽提后的组成。当加入量为11.76%时,PMMA/Si O_2复合材料的导热率达到0.23 W/(m·K),比基体PMMA提高了27.78%。用PMMA红外光谱的侧甲基弯曲振动峰(δCH3)与羰基(νC=O)的伸缩振动峰比值可以表示PMMA大分子的偶合终止与歧化终止的比例,随着二氧化硅含量的增加,歧化终止比例升高,从而使PMMA/Si O_2复合材料的热稳定性提高,与热重分析结果一致。     

Poly(hydroxyethyl methacrylate) based magnetic nanoparticles for plasmid DNA purification from Escherichia coli lysate

The aim of this study is to prepare poly(hydroxyethyl methacrylate-N-methacryloyl-(L)-histidine) [PHEMAH] magnetic nanoparticles for plasmid DNA (pDNA) purification from Escherichia coli (E. coli) cell lysate. Magnetic nanoparticles were produced by surfactant free emulsion polymerization. mPHEMAH nanoparticles were characterized by elemental analysis, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), vibrating sample magnetometer (VSM), electron spin resonance (ESR), thermogravimetric analyses (TGA) and transmission electron microscopy (TEM). Surface area, average particle size and size distribution were also performed. Specific surface area of the mPHEMAH nanoparticles was found to be 1180 m²/g. Elemental analysis of MAH for nitrogen was estimated as 0.18 mmol/g polymer. The amount of pDNA adsorbed onto the mPHEMAH nanoparticles first increased and then reached a saturation value at around 1.0 mg/mL of pDNA concentration. Compared with the mPHEMA nanoparticles (50 μg/g polymer), the pDNA adsorption capacity of the mPHEMAH nanoparticles (154 mg/g polymer) was improved significantly due to the MAH incorporation into the polymeric matrix. The maximum pDNA adsorption was achieved at 25 °C. The overall recovery of pDNA was calculated as 92%. The mPHEMAH nanoparticles could be used six times without decreasing the pDNA adsorption capacity significantly. The results indicate that the PHEMAH nanoparticles promise high selectivity for pDNA.     

Near-Field Mapping of Plasmonic Antennas by Multiphoton Absorption in Poly(methyl methacrylate)

Mapping the optical near-field response around nanoantennas is a challenging yet indispensable task to engineer light-matter interaction at the nanometer scale. Recently, photosensitive molecular probes, which undergo morphological or chemical changes induced by the local optical response of the nanostructures, have been proposed as a handy alternative to more cumbersome optical and electron-based techniques. Here, we report four-photon absorption in poly(methyl methacrylate) (PMMA) as a very promising tool for nanoimaging the optical near-field around nanostructures over a broad range of near-infrared optical wavelengths. The high performance of our approach is demonstrated on single-rod antennas and coupled gap antennas by comparing experimental maps with 3D numerical simulations of the electric near-field intensity.