羧基功能化聚苯乙烯荧光微球的制备及表征

以苯乙烯、丙烯酸为单体,引入疏水性荧光染料罗丹明6G(Rh6G),采用微乳聚合法制备羧基聚苯乙烯荧光微球,并分析了表面活性剂、引发剂、丙烯酸用量对产物粒径分布的影响,考察了羧基聚苯乙烯荧光微球的浓度对荧光强度的影响。通过粒度分析仪、扫描电子显微镜、红外光谱仪、紫外吸收光谱以及荧光光谱仪对样品的纳米特性、形貌、结构和荧光性能进行了表征。结果表明,用微乳聚合法制备出50~250nm的羧基聚苯乙烯荧光微球,粒径均一且呈单分散性。紫外光谱图测试表明,在533nm左右有吸收峰。荧光光谱测试表明,羧基功能化的荧光聚苯乙烯微球浓度≤0.01%,其荧光最大激发峰为527nm,最大发射峰在555nm处;浓度高于0.01%时,荧光光谱出现红移,且荧光强度减弱。     

Influence of poly(acrylic acid) molar mass on the fracture properties of glass polyalkenoate cements based on waste gasifier slags

The failure behaviour of glass polyalkenoate cements was investigated using a linear elastic fracture mechanics (LEFM) approach. Cements were based on Drayton gasifier slag and four poly(acrylic acid)s with number average molar masses ranging from 3.03 × 10³ to 6.44 × 10⁴. Cement properties were studied at time intervals of one, seven and twenty eight days. Compressive and flexural strengths of the cements increased with increasing molar mass of the poly(acrylic acid)s and time. The Young's modulii increased with time and were independent of poly(acrylic acid) molar mass. Fracture toughness increased with increasing molar mass of the poly(acrylic acid)s. Fracture toughness increases over an ageing time of one week and subsequently decreased over one month. Toughness increased with poly(acrylic acid) molar mass, these increases being most pronounced at higher molar mass. The toughness values decreased with time for the higher molar mass cements, which is consistent with increased crosslinking of the poly(acrylic acid) chains and reducing molecular flow at the crack tip. Plastic zone size increased with poly(acrylic acid) molar mass and decreased with time for lower molar mass cements, remained constant for intermediate molar mass cements and increased with high molar mass cements.     

高含量丙烯酸膨润土/聚丙烯酸钠高吸水性复合材料的研究Ⅰ:制备工艺与形貌

通过特殊工艺将丙烯酸膨润土(简称ABT)和丙烯酸钠单体采用溶液聚合法制备出高含量丙烯酸膨润土/聚丙烯酸钠高吸水性复合材料(简称HABT/PAA).SEM考察材料的形貌得知,ABT以20～30nm的尺寸较均匀、无序地分散在聚合物基体中,且与聚合物有很好的相容性.对合成工艺进行了优化得到较优的工艺:ABT用量为单体质量的30％(质量分数),交联剂用量为单体质量的0.3％(质量分数),引发剂用量为单体质量的1.1％(质量分数),体系总水量为单体质量的340％(质量分数),中和度为64％,在此条件下,材料吸附去离子水的能力为1103g/g.同时,HABT/PAA的保水性能较聚丙烯酸钠(PAA)好.     

Poly(ethylene glycol) Vesicles: Self-Assembled Site for Luminescence Generation

Fluorescence in poly(ethylene glycol) (PEGs 400-12000) solutions is reported here for the first time. PEG solutions form a vesicular organization with the hydrophilic groups attached at both ends which arrange themselves beyond a particular concentration and offer electron-dense regions at the center of the vesicle. These vesicles provide an inherent site for fluorescence generation in PEG solutions. Fluorescence emission was observed at ～380 nm with an excitation wavelength of 300 nm. PEG of molecular weight 6000 was found to show maximum emission intensity at a particular concentration. The formation of PEG vesicles (～1 nm size) was confirmed by dynamic light scattering (DLS) and confocal laser microscopy. On addition of metal ions the polymeric vesicle breaks up to monomeric PEG, and hence, the fluorescence intensity decreases with a red shift. Fluorescence lifetime measurements indicate the nature of complexation of the metals with PEG. Since PEGs are used as one of the phases in aqueous biphasic systems (ABS) of liquid-liquid extractions, the nature of the fluorescence emission spectrum of the PEG phase after extraction was studied. Metal extraction in the PEG-rich phase of an ABS leads to quenching of fluorescence in PEG.     

Transparent and high gas barrier films based on poly(vinyl alcohol)/graphene oxide composites

Composites of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were synthesized by a modified Hummers method and a solution-mixing method. GO was fully exfoliated in the PVA/GO composites. GO did not affect the crystallization of PVA during solvent evaporation. GO is itself an excellent gas barrier without any chemical reduction. The oxygen permeability of the PVA/GO (0.3 wt.%) composite coated film was 17 times lower than that of the pure poly(ethylene terephthalate) (PET) film, with 92% light transmittance at 550 nm. Composites of PVA and reduced graphene oxide (RGO) were synthesized by performing chemical reduction using hydrazine monohydrate. The oxygen permeability of the PVA/RGO (0.3 wt.%) composite coated film was 86 times lower than that of the pure PET film, with 73% light transmittance at 550 nm. The reduction of oxygen permeability was mainly attributed to the reduced oxygen solubility in the PVA/GO composite film, while it was attributed to both the reduced oxygen diffusivity and solubility in the PVA/RGO composite film.     

聚丙烯酸接枝聚氧乙烯共聚物的合成、表征及分散性能

以壬基酚聚氧乙烯醚(NPEO)和甲基丙烯酰氯(MAC)反应合成了壬基酚聚氧乙烯大单体(NPEO-MA),将其与丙烯酸沉淀共聚得到了一系列的聚丙烯酸接枝共聚物PAA-g-NPEO。用红外光谱(IR)、紫外光谱(UV)、凝胶渗透色谱(GPC)、核磁共振(^1H-NMR)等方法对产物进行了表征,探讨了所设计结构的接枝共聚物在丙烯酰胺分散聚合体系中的稳定机理。     

壳聚糖/聚氧乙烯复合纺丝液性能对静电纺丝的影响

为了研究壳聚糖/聚氧乙烯复合纺丝液性能对静电纺丝的影响,利用质量分数为3％的壳聚糖(CS)与聚氧乙烯(PEO)以不同的质量比溶解在浓度为50％的冰乙酸水溶液中制备了CS/PEO复合纺丝液,采用静电纺丝技术制备了CS/PEO复合纳米纤维.用扫描电子显微镜(SEM)对制备出的CS/PEO复合纳米纤维进行表征,并测试了CS/PEO复合纺丝液的溶液性能.从复合纺丝液性能对静电纺纤维成型的影响机理角度对实验结果进行了分析.分析结果表明,在其他静电纺丝参数一定时,纺丝液黏度影响射流的稳定性,从而影响纤维的形貌和直径.只要纺丝液电导率在合适的范围内,对静电纺的影响不大.从泰勒的临界公式中得出了纺丝液临界电压与纺丝液表面张力最佳值的一一对应关系,并与本实验中的实验数据相吻合.     

Poly(vinyl alcohol)/poly(acrylic acid)/TiO2/graphene oxide nanocomposite hydrogels for pH-sensitive photocatalytic degradation of organic pollutants

Poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂ nanocomposite hydrogels. Both TiO₂ and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO₂ and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water.     

Stretchable Light‐Emitting Diodes with Organometal‐Halide‐Perovskite–Polymer Composite Emitters

Intrinsically stretchable light‐emitting diodes (LEDs) are demonstrated using organometal‐halide‐perovskite/polymer composite emitters. The polymer matrix serves as a microscale elastic connector for the rigid and brittle perovskite and induces stretchability to the composite emissive layers. The stretchable LEDs consist of poly(ethylene oxide)‐modified poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate as a transparent and stretchable anode, a perovskite/polymer composite emissive layer, and eutectic indium–gallium as the cathode. The devices exhibit a turn‐on voltage of 2.4 V, and a maximum luminance intensity of 15 960 cd m^?2 at 8.5 V. Such performance far exceeds all reported intrinsically stretchable LEDs based on electroluminescent polymers. The stretchable perovskite LEDs are mechanically robust and can be reversibly stretched up to 40% strain for 100 cycles without failure.     

Effect of temperature in synthesis of silver nanoparticles in triblock copolymer micellar solution

Knowing that poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) in aqueous solution is thermoresponsive, the effect of temperature on formation and stabilisation of silver nanoparticles has been investigated systematically. Synthesis of silver nanoparticles was achieved from silver ammonia complex [Ag(NH₃)₂]⁺ in aqueous solution of hydroxyl terminated PEO–PPO–PEO at four different temperatures. A non-Arrhenius behaviour for the rate of silver reduction with temperature was observed. The hydrodynamic diameter of the composite coils suddenly increased at certain intermediate time indicating sudden agglomeration of individual micelles to form bigger network structures. The size and the distribution of the nanoparticles show a bimodal distribution at the lowest temperature. At intermediate temperature, particles of the smallest size with a narrow distribution was achieved. At the highest temperature, a bunch-like particle morphology was found. Chemical changes in polymer properties were observed at higher temperatures. The results suggest that at a lower temperature, a change in polymer morphology play an important role in controlling the particle size and their distribution, whereas at a higher temperature, this role is shifted to the chemical change of the polymer. At an intermediate temperature, a balance between the two effects provides the optimum condition for formation of silver nanoparticles of small size and narrow distribution.     

In-situ polymerization approach for preparation of rare earth fluoride phosphors coated with PAA

Up-conversion nanoparticles (UCNPs), which can convert a radiation from a longer wavelength to a shorter wavelength, have great potential uses as bio-labels in biological detection. However, these NPs usually cannot be used directly unless their surfaces are further modified. In this paper, NaYF4:Yb, Er nanoparticles (NPs) were coated with poly(acrylic acid) (PAA) by in situ polymerization for the first time. Accordingly, NaYF4:Yb, Er/NaYF4 NPs were synthesized before PAA coating to avoid the decay of optical intensity. The resulting UCNPs were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and up-conversion photoluminescence spectrometry. The XRD results indicated that the resultant UCNPs exhibited a pure hexagonal phase. The FT-IR spectra and TGA curves revealed that these NPs were coated successfully with PAA. Meanwhile, the TEM results showed that well-dispersed UCNPs with the best morphology and an average size of about 90 nm were obtained with 8.0 wt% acrylic acid content (the content percentage in the whole reaction system) at 0 degrees C within 130 min. Fluorescence tests showed that the UCNPs had a strong UC fluorescence intensity. Settlement tests revealed that PAA-coated NaYF4 UCNPs had more favorable dispersion stability than uncoated UCNPs in an aqueous system. These functionalized nanocomposites could be used for further bio-conjugation.     

Preparation of poly(acrylic)/SiO2/EuL3 x 2H2O, hybrid thin films from monodispersed colloidal silica

In this study, poly(acrylic)/SiO2/EuL3 x 2H2O hybrid thin films were prepared from various acrylic monomers (MMA and EDMA/TMPTA), lanthanide metal complexes (EuL3 x 2H2O, L = pyridine carboxylic acid), and monodispersed colloidal silica with a coupling agent, 3-(trimethoxysilyl)propyl methacrylate (MSMA). It is a combination of the sol-gel reaction, thermal polymerization, and spin coating. The silica content in the hybrid thin films is fixed at 20 wt%, and the EuL3 x 2H2O content is varied from 0.01 g to 0.07 g. FTIR and EA analysis confirms the chemical structure of the prepared EuL3 x 2H2O and poly(acrylic)/SiO2/EuL3 x 2H2O hybrid thin films. UV-Vis spectra and n&k analysis shows that the hybrid thin film has good transparency in visible light. The refractive index of hybrid thin films can be effectively controlled through the EuL3 x 2H2O content. The PL spectra shows that the strongest emission peak occurs at 615 nm and the emission intensity increases to the peak maximum at an EuL3 x 2H2O content of 0.05 g. Both TGA and PL analysis show that the prepared hybrid thin films from the crosslinked acrylic polymer moiety have much better film uniformity, thermal stability, and fluorescence properties. The TEM diagram shows that the MSMA/SiO2/EuL3 x 2H2O particles with a size 15-20 nm are well dispersed in the reaction solution. The SEM diagram shows that the particle distribution in the prepared hybrid thin films is uniform and no phase separation is observed. Finally, AFM analysis indicates that the prepared hybrid thin films have an excellent surface planarity.     

Development of nitroxide radicals–containing polymer for scavenging reactive oxygen species from cigarette smoke

We developed a nitroxide radicals–containing polymer (NRP), which is composed of poly(4-methylstyrene) possessing nitroxide radicals as a side chain via amine linkage, to scavenge reactive oxygen species (ROS) from cigarette smoke. In this study, the NRP was coated onto cigarette filters and its ROS-scavenging activity from streaming cigarette smoke was evaluated. The intensity of electron spin resonance signals of the NRP in the filter decreased after exposure to cigarette smoke, indicating consumption of nitroxide radicals. To evaluate the ROS-scavenging activity of the NRP-coated filter, the amount of peroxy radicals in an extract of cigarette smoke was measured using UV–visible spectrophotometry and 1,1-diphenyl-2-picrylhydrazyl (DPPH). The absorbance of DPPH at 517 nm decreased with exposure to cigarette smoke. When NRP-coated filters were used, the decrease in the absorbance of DPPH was prevented. In contrast, both poly[4-(cyclohexylamino)methylstyrene]- and poly(acrylic acid)-coated filters, which have no nitroxide radical, did not show any effect, indicating that the nitroxide radicals in the NRP scavenge the ROS in cigarette smoke. As a result, the extract of cigarette smoke passed through the NRP-coated filter has a lower cellular toxicity than smoke passed through poly[4-(cyclohexylamino)methylstyrene]- and poly(acrylic acid)-coated filters. Accordingly, NRP is a promising material for ROS scavenging from cigarette smoke.     

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double‐Emulsion Drops

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer‐graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double‐emulsion drops by osmotic‐pressure‐driven water pumping, PVA‐tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol–gel transition. Therefore, the PVA–GO composite remains undissolved when it is directly exposed to water by oil‐shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel‐forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.     

Specialized channels to control the kinetics of ion release in hydrophobic resin

Fluoride, as a model ion, has been clinically used to inhibit the development of secondary carious lesions at the interfaces of restored teeth and demineralization. Controlling of its release kinetic is important in the dental restorative composites with respect to enhance biological activities without side effects. To introduce the channels into composites as specialized channels for continuous and controllable fluoride release, this paper suggests the one-dimensional structure with controllable functions. This specialized structure is generated by the novel development of a coaxially aligned tri-nozzle electrospinning technique. The fluoride source, comminuted sodium fluoride nanoparticles, was encapsulated in poly(methyl methacrylate) sheath. Tuned fluoride release was achieved by hydrophilic poly(acrylic acid) incorporated with the NaF nanosuspension with a hollow structure introduced using an inner fluid (ethylene glycol) in the tri-nozzle system. The structures of the multi-functionalized channels were preserved during UV curing of the polymeric dental restorative composites. The resulting composite resins show long-term release profiles controllable by both poly(acrylic acid) content and the hollow structures, which are based on fluoride diffusion and water ingress. Therefore, the functionalized channel can be applied to control the long-term release of ions in hydrophobic matrix at desirable kinetic.     

丁氧基封端聚醚高效减水剂的合成及性能

通过酯交换合成了不同分子量的丁氧基聚氧乙烯甲基丙烯酸酯(BPEGMA),并通过水溶液调节共聚合方法制备了丁氧基聚氧乙烯甲基丙烯酸酯/丙烯酸/甲基丙烯酸/2-丙烯酰胺基-2-甲基丙磺酸(BPEGMA/AA/MAA/AMPS)多元共聚物。用红外光谱(FT-IR)表征了共聚物的分子结构,详细研究了聚乙二醇(PEG)支链长度、BPEGMA用量、AMPS用量和AA/MAA摩尔比等因素对其分散性能的影响。研究表明,该共聚物对水泥具有良好的分散性及分散保持性能,掺量为0.3%,水灰比为0.29时,水泥净浆流动度可达335mm,120min内坍落度基本不变。     

PSS resin-fortified polythiophene nanoparticles for highly transparent conducting films

Polythiophene/poly(sodium 4-styrene sulfonate) (PT/PSS) composite nanoparticles having different particle size were prepared by Fe(3+)-catalyzed oxidative polymerization in aqueous medium. This facile method includes a FeCl3/H2O2 (catalyst/oxidant) combination system, which guarantees a high conversion (more than 95%) of thiophene monomers in various concentration of poly(styrene sulfonate) (PSS) with only a trace of FeCl3. Particle size of PT/PSS composite nanoparticles decreased from 134 nm to 26 nm as the concentration of PSS and H2O2 increased, and which was confirmed by SEM and CHDF analyses. The poly(ethylene terephthalate) (PET) film coated with PT/PSS was transparent and showed a high conductivity in a dried state. The sheet resistivity decreased as the ratio of PT to PSS increased. Photoluminescence property of the PT/PSS composite nanoparticles was also investigated.     

Mesoporous silica beads embedded with semiconductor quantum dots and iron oxide nanocrystals: dual-function microcarriers for optical encoding and magnetic separation

Mesoporous beads are promising materials for embedding functional nanoparticles because of their nanometer-sized pores and large surface areas. Here we report the development of silica microbeads embedded with both semiconductor quantum dots (QD) and iron oxide (Fe3O4) nanocrystals as a new class of dual-function carriers for optical encoding and magnetic separation. The embedding (doping) process is carried out by either simultaneous or sequential addition of quantum dots and iron oxide (Fe3O4) nanocrystals in solution. The doping process is fast and quantitative, but the incorporated iron oxide strongly attenuates the signal intensity of QD fluorescence. We find that this attenuation is not due to conventional fluorescence quenching but is caused by the broad optical absorption spectrum of mixed-valence Fe3O4. For improved biocompatibility and reduced nonspecific binding, the encoded beads are further coated with amphiphilic polymers such as octylamine poly(acrylic acid). The results indicate that the polymer-coated beads are well suited for target capturing and enrichment, yielding magnetic separation efficiencies higher than 99%. By combining the multiplexing capability of QDs with the superparamagnetic properties of iron oxide nanocrystals, this class of encoded beads is expected to find broad applications in high-throughput and multiplexed biomolecular assays.     

辉光放电电解等离子体法制备蛭石/聚丙烯酸高吸水性复合材料及其溶胀性能

在水溶液中,以丙烯酸（AA）和蛭石（VMT）为原料,N,N’-亚甲基双丙烯酰胺（MBA）为交联剂,用辉光放电电解等离子体（GDEP）技术引发一步制备蛭石/聚丙烯酸高吸水性复合材料。采用FTIR、XRD对蛭石/聚丙烯酸的结构进行了表征,探讨了GDEP引发聚合和溶胀动力学行为的机制,研究了pH值和盐浓度对蛭石/聚丙烯酸平衡溶胀率的影响。结果表明,蛭石/聚丙烯酸高吸水性复合材料在蒸馏水中2 h达溶胀平衡,溶胀过程遵循拟二级动力学模型;该复合材料具有pH敏感性、盐敏感性和可逆溶胀-消溶胀开关行为,其在单价阳离子溶液中的平衡溶胀率比二价阳离子溶液中的更高。     

Polymer microspheres with active carboxyl groups: preparation, structure and hydrophilicity

A quantitative research of microspheres, poly(ethylene glycol dimethacrylate-co-acrylic acid) (P(EGDMA-co-AA)) and poly(divinvlbenzene-80-co-acrylic acid) (P(DVB-co-AA)), with active carboxyl groups on surface prepared by distillation-precipitation polymerization was presented in this paper. The loading capacity of active carboxyl group on microspheres which was investigated by titration technique would be increased and the contact angle was decreased following the increase of the feed ratio of acrylic acid (AA) monomer. This phenomenon indicated that the hydrophilicity of particles was mainly determined by the feed ration of hydrophilic AA monomer. However, when the AA fraction was at a fixed level, a slight difference of the loading capacity of carboxyl groups on microsphere surfaces with different crosslinkers existed. The microspheres with EGDMA as crosslinker had a higher loading capacity of carboxyl groups and lower contact angle than those of P(DVB-co-AA) microspheres, which indicated that P(EGDMA-co-AA) microspheres were more hydrophilic than P(DVB-co-AA) microspheres.