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  • Epoxy Toughening via Formation of Polyisoprene Nanophases with Amphiphilic Diblock Copolymer
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-21
    Yixin Xiang, Sen Xu, Sixun Zheng

    In this contribution, we reported the investigation of epoxy toughening via the formation of nanostructures by the use of poly(ε-caprolactone)-block-polyisoprene (PCL-b-PI) diblock copolymer. The novel diblock copolymer was synthesized via the combination of ring-opening polymerization and reversible addition-fragmentation chain transfer polymerizations. This diblock copolymer can be successfully used to access the nanostructures of epoxy thermosets. Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) showed that the nanostructured thermosets were successfully obtained. In the nanostructured thermosets, the spherical or vesicular polyisoprene microdomains were dispersed in continuous epoxy matrix. It is the formation of the PI nanophases that endowed the thermosets with significantly improved fracture toughness.

    更新日期:2017-11-21
  • Electric field distribution and initial jet motion induced by spinneret configuration for molecular orientation in electrospun fibers
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-20
    Xiang Li, Jinyou Lin, Yongchun Zeng

    Understanding the molecular orientation of electrospun fibers is a key challenge for tailoring fiber properties. The studies of electric field distribution, and the motion of the initial portion of the polymer jet, are of interest for clarifying molecular orientation in fibers during electrospinning. In this work, we study the impact of electric field distribution and the initial jet motion induced by two kinds of spinneret configurations, referred to as a needle configuration and a hole configuration, on molecular orientation in electrospun PEO fibers. Using FE-SEM, FTIR and WAXD techniques, the fiber diameter and molecular orientation of the fibers prepared with the needle electrospinning system and the hole electrospinning system are characterized. To explore jet stretching and chain orientation during the spinning process, electric field simulation and high-speed photography are performed to obtain the electric field characteristics and to measure the initial jet velocities for the needle and the hole systems. Our results reveal the higher electric field strength around the spinneret and the larger initial jet velocities, which depend on the spinneret configuration, result in the higher degree of molecular orientation in fibers.

    更新日期:2017-11-20
  • Time resolved characterization of the solid-state reaction between polycarbonate and primary amine
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-20
    Cordelia Zimmerer, Lisa Ziegler, Gert Heinrich, Gerald Steiner

    Polycarbonate can be functionalized with specific moieties such as amino groups. A novel approach for functionalization is based on a process integrated surface modification, e.g. during the injection molding process. However, the solid-state reaction routes are complex, not well investigated and difficult to control. In this study the solid state reaction of polycarbonate with octadecylamine was studied by using infrared spectroscopy and 2D correlation analysis. The infrared spectrum taken after 20 minutes reaction time shows the formation of urethane as an interfacial linker between polycarbonate and octadecylamine. Furthermore, bisphenol-A, also formed initially, indicates a degradation of polycarbonate. The solid-state reaction during 360 minutes processing time was investigated by 2D correlation analysis. The 2D correlation maps indicate a progress in the degradation of polycarbonate and the formation of biuret and urea. No more urethane is formed during longer processing time. This study demonstrates that a surface modification of polycarbonate with octadecylamine requires a very short reaction time in order to ensure an optimized interfacial link and to minimize the degradation of the materials.

    更新日期:2017-11-20
  • Electron-induced reactive processing of polyamide 6/polypropylene blends: Morphology and properties
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-20
    Shib Shankar Banerjee, Andreas Janke, Uwe Gohs, Gert Heinrich

    Electron-induced reactive processing (EIReP) recently has appeared as an advanced processing technology to modify several polymer compounds at melt state by its spatial and temporal precise energy input. In the present work, an attempt was made to prepare a compatible blend from polar polyamide 6 (PA6) and non-polar polypropylene (PP) using EIReP without any chemical crosslinking and chemical additives. EIReP modified blends were prepared at different doses (5, 10 and 20 kGy) and dose per revolutions (3, 6 and 12 kGy/rev) while keeping constant the values of mass ratio (50/50 w/w), electron energy (1.5 MeV), rotor speed (60 rpm) and temperature (230 °C). EIReP process parameters-morphology-property relationship of this blend was studied. Interestingly, co-continuous morphology of the blend was converted to droplet-matrix morphology after EIReP whether PA6 was continuous phase. Influence of dose on the DMT modulus (Derjaguin-Muller-Toporov) at different phases of the blends was also measured and analyzed using advanced PeakForce Quantitative Nanomechanical Mapping atomic force microscopy (AFM) technique. Improved nano- and macroscopic properties of EIReP modified blends were originated from the properties of the continuous matrix phase, electron-induced branching and also from the reduction of domain size of PP phase with increased dose.

    更新日期:2017-11-20
  • Mechanical properties and thermal characteristics of poly(lactic acid) and paraffin wax blends prepared by conventional melt compounding and sub-critical gas-assisted processing (SGAP)
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-20
    Yann-Jiun Chen, An Huang, Thomas Ellingham, Chunhui Chung, Lih-Sheng Turng

    In this study, poly(lactic acid) (PLA)/paraffin wax (PW) blends containing different amounts of PW were investigated. The blends were prepared by a twin-screw extruder using two different methods: conventional melt compounding extrusion and sub-critical gas-assisted processing (SGAP). Then, the blends and neat PLA were injection molded into ASTM 638 Type V tensile bars for evaluation. To observe the effects of the different melt compounding processes and the effects of paraffin wax added to the blends, the rheological properties, crystallization behavior, and thermal stability of the extruded blends, as well as the phase morphology and tensile properties of the injection molded tensile bars, were characterized. The results showed that the addition of paraffin wax yielded tremendous improvements in elongation compared to neat PLA. In addition, samples made by the sub-critical gas-assisted processing (SGAP) extrusion method exhibited more homogeneous phase morphologies and paraffin wax dispersion, better tensile properties and thermal stability, and more consistent material properties as compared to their conventionally compounded counterparts.

    更新日期:2017-11-20
  • Water-actuated shape-memory and mechanically-adaptive poly(ethylene vinyl acetate) achieved by adding hydrophilic poly (vinyl alcohol)
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-20
    Zhi-xing Zhang, Xiao-dong Qi, Song-tai Li, Jing-hui Yang, Nan Zhang, Ting Huang, Yong Wang

    Water-actuated shape memory polymers (SMPs) have great potential applications in many fields. Although many strategies have been developed to endow polymers with water-active shape memory effect (SME), so far it is still challenging to prepare the water-actuated SMPs with a highly sensitive SME in a method as facile as possible. In this work, poly(vinyl alcohol) (PVA) was incorporated into poly(ethylene vinyl acetate) (EVA) through the simple solution compounding processing. The blends exhibited good interfacial interaction on one hand. On the other hand, PVA exhibited excellent reinforcement effect, leading to the great enhancement of modulus and strength. Further results showed that the samples had excellent water uptake and dehydration abilities, and the presence of water resulted in the dramatic decrease of modulus and large increase of tensile ductility, which endowed the materials with great potential to realize complicated deformation at gentle force. The water-active SME was evaluated through cycling measurements, i.e. wetting-stretching-drying processes. The results showed that the water-active SME of the blends was greatly dependent upon the blend compositions. After several cycling measurements, the water-active SME of samples became stable. Specifically, for the sample containing 35 wt% PVA, the shape fixity and shape recovery ratios were increased up to 98.7% and 99.5%, respectively. The mechanisms for the excellent water-active SME were then discussed.

    更新日期:2017-11-20
  • Improved Antiviral Properties of Chain End Lipophilic Fucoidan-Mimetic Glycopolymers Synthesized by RAFT Polymerization
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-20
    Mattias Tengdelius, Cheung Kwan Yee, May Griffith, Peter Påhlsson, Peter Konradsson

    Sulfated polysaccharides and synthetic glycopolymers are promising candidates as antiviral drugs but have failed in clinical trials most likely due to lack of virucidal activity. However, studies have shown that incorporation of lipophilic end groups to oligosaccharide chains is a mean to gain the desired virucidal properties. Here, we describe the introduction of lipophilic end groups to sulfated α-L-fucoside-pendant polymethacrylamides, also known as fucoidan-mimetic glycopolymers, by RAFT polymerization. RAFT agents bearing octadecyl, dioctadecyl and cholesteryl groups were used to synthesize lipoglycopolymers of different chain lengths. Short lipoglycopolymers bearing lipophilic end groups showed an improved ability to block viral entry and infection of cells compared to glycopolymers without lipophilic end groups. Short lipoglycopolymers bearing octadecyl or dioctadecyl end groups, also completely stopped the spreading of the viral infection. However, these lipoglycopolymers did not show actual virucidal properties. Nevertheless, we have described a first step towards obtaining virucidal synthetic glycopolymers for clinical use.

    更新日期:2017-11-20
  • Structure and performances changes during tensile of aromatic copolysulfonamide fibers under different thermal temperatures via in-situ Synchrotron SAXS/WAXS
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-17
    Xiaoyun Li, Jinchao Yu, Jianning Wang, Kang Chen, Xiuhong Li, Yumei Zhang, Fenggang Bian, Jie Wang

    In situ studies of structure and performance changes in aromatic copolysulfonamide (co-PSA) fibers during stretching at different thermal exposure temperature range from room temperature to 300°C were carried out using synchrotron small angle X-ray scattering and wide angle X-ray scattering techniques. Results showed that the optimum microstructure and mechanical property of co-PSA fibers were achieved when stretched at 200°C, the fibril length, fibril misorientation, crystal sizes L002 reached minimum, the long period became maximum at the same strain indicating that lamella and fibrils aligned perfectly, fiber structure compactness at 200°C. During stretching at RT to 200°C, at low strain, fibril length, crystal size L002 increased, fibrils oriented along stretching direction, the long period was enlarged; the opposite trend evolution of structure appeared under high strain. But stretching at 300°C, L002 increased, fibril orientation became poor, the lamellae destroyed easily resulting in the decreasing strength. It can be concluded that co-PSA fibers remain good property under thermal at 200°C, external force use environment.

    更新日期:2017-11-20
  • Amino acid-cured bio-based epoxy resins and their biocomposites with chitin- and chitosan-nanofibers
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-15
    Mitsuhiro Shibata, Junya Fujigasaki, Motohiro Enjoji, Ayaka Shibita, Naozumi Teramoto, Shinsuke Ifuku

    Sorbitol polyglycidyl ether (SPE), which is a bio-based water-soluble epoxy resin, was cured with lysine (Lys) and arginine (Arg) as basic amino acids and with cysteine (Cys) as an acidic amino acid. Furthermore, biocomposites of the Lys- and Arg-cured SPE (SPE-Lys and SPE-Arg) and Cys-cured SPE (SPE-Cys) with chitin nanofiber (ChNF) not higher than 10 wt% were successfully prepared by compression molding and casting methods, respectively. Also, SPE-Cys biocomposites with chitosan nanofiber (CsNF) not higher than 2 wt% were successfully prepared by the casting method. The FT-IR spectral analysis of the cured resins suggested that the ε-amino and carboxy groups of Lys, α-amino and carboxy groups of Arg, thiol group of Cys mainly reacted with epoxy groups of SPE. The FT-IR spectral analysis of the ChNF biocomposites suggested that a side reaction of SPE with acetic acid which was contained in ChNF suspension occurred. The dynamic mechanical analysis revealed that a higher order of the loss modulus peak temperature (Tα) was SPE-Lys (39 °C) > SPE-Arg (33 °C) > SPE-Cys (21 °C). Although Tαs of ChNF biocomposites were lower than those of the corresponding cured resins, Tαs of SPE-Cys/CsNF biocomposites were higher than that of SPE-Cys by the action of CsNF as a basic catalyst. The storage moduli over the range of 50∼100 °C for SPE-Lys/ChNF, SPE-Cys/ChNF and SPE-Cys/CsNF biocomposites were much higher than those for the corresponding cured resins. SPE-Lys/ChNF and SPE-Cys/CsNF biocomposites exhibited higher tensile strengths and moduli than SPE-Lys and SPE-Cys did, respectively.

    更新日期:2017-11-17
  • Structurally diverse polymers from norbornene and thiolactone containing building blocks
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-14
    Daniel Frank, Pieter Espeel, Nezha Badi, Filip Du Prez

    A wide set of norbornene-derived polymers with a diversity in backbone and side chain structures has been prepared based on norbornene building blocks that also include a thiolactone group. For this purpose, two thiolactone monomers with differently substituted norbornene moieties were synthesized and their reactivity compared using three different polymerization strategies. First, their potential for amine-thiol-ene polymerization was evaluated using different amines, solvents and initiator concentrations in order to screen their influence on the molecular weight and glass transition temperature. Free radical (co-)polymerization and ring-opening metathesis polymerization were also applied and the obtained polymers were submitted to post-polymerization modification. The results showed that only the monomer 5-norbornenemethyl thiolactone carbamate results in polymer formation under the tested conditions. The obtained compounds were characterized by SEC, TGA, DSC and NMR.

    更新日期:2017-11-15
  • Macroporous scaffolds: Molecular brushes based on oligo(lactic acid)–amino acid–indomethacin conjugated poly(norbornene)s
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-13
    Sutthira Sutthasupa, Fumio Sanda

    Leucine-derived norbornene monomer (1), oligo(lactic acid)-derived norborne macromonomer (2) and indomethacin-conjugated norbornene (3) were synthesized and polymerized using the Grubbs ruthenium complex as a catalyst. Macromonomer 2 was synthesized by the ring-opening polymerization of lactide using 5-norbornene-2,3-exo,exo-dimethanol as an initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst. The corresponding polymers, poly(1), poly(2), poly(3) and copolymers with number-average molecular weights (Mn) ranging from 14 000 to 360 000 were obtained in 73–95% yields. Poly(2) formed scaffolds by simply drying under reduced pressure presumably due to the brush-like structure causing entanglement of the polymer chains. The compressive strength of poly(2) scaffold increased as increasing the polylactide chain length. The compressive strength of the scaffolds obtained from the copolymers ranged from 0.222 to 0.587 MPa in accordance with the monomer unit ratios. SEM revealed the presence of pores around 5–10 µm diameters, together with larger pores dispersed in the range of 50–300 µm diameters. TEM demonstrated the presence of polymer networks. The conjugated indomethacin was gradually released by incubation under acidic condition (pH 5.7) at 37 °C. The results of % cell viability, release of LDH activity and cell morphology assays revealed that the obtained scaffolds did not exhibit cytotoxicity toward HEK 293 cells.

    更新日期:2017-11-14
  • Synergistic effect of liquid crystal and polyhedral oligomeric silsesquioxane to prepare molecularly imprinted polymer for paclitaxel delivery
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-13
    Li-Ping Zhang, Shi-Hui Tang, Chun-E Mo, Chao Wang, Yan-Ping Huang, Zhao-Sheng Liu

    A strategy based on the synergistic effect of polyhedral oligomeric silsesquioxane (POSS) and liquid crystal (LC) was described to prepare molecularly imprinted polymers (MIPs). A typical polymerization system was composed of 4-methyl phenyl dicyclohexyl ethylene (MPDE)(LC monomer), methacryllsobutyl POSS (POSS monomer), methacrylic acid, as well as ethylene glycol dimethacrylate (EDMA). The cooperative effect of LC and POSS was demonstrated by comparing the adsoption amount and imprinting factor of the LC POSS MIPs with that of other MIPs prepared using only LC or POSS monomer, as well as MIP made without LC and POSS. The influence of the content of POSS, the ratio of the template to functional monomer as well as the types of LC monomer on imprinting performance was investigated. A detailed morphology study of the MIPs displayed that the simultaneous use of LC and POSS monomer to prepare MIPs also produced the changes in pore structure different from the use of LC or POSS monomer independently. The reinforced imprinted effect of LC POSS MIPs against paclitaxel (PTX) was also approved by superior controlled release characteristics through analyzing the PTX release kinetics. The cytotoxicity of each polymer was lower than the drug-loaded polymer, which was measured by using the MTT assay with human breast cancer cell (MCF-7 cell). Compared with pure PTX, LC POSS MIPs displayed a higher relative bioavailability of 242.5 %, while the LC POSS-free control MIPs and POSS LC-free control MIPs only 127.4 and 63.2%, respectively.

    更新日期:2017-11-14
  • Effect of the Charge Interactions on the Composition Behavior of Acrylamide/Acrylic Acid Copolymerization in Aqueous Medium
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-13
    Eric J. Fischer, Danilo Cuccato, Giuseppe Storti, Massimo Morbidelli

    Acrylamide and sodium acrylate are copolymerized in aqueous solution to study the influence of monomer concentration and ionic strength onto the reactivity ratios using in-situ 1H NMR. Increasing the monomer content leads to larger reactivity of the ionized monomer. At low monomer concentration, this effect was reproduced by adding NaCl to increase the ionic strength, indicating that the reaction kinetics is largely governed by charge interactions. On the contrary, this was not observed at higher monomer content, suggesting that non-electrostatic effects are mainly responsible of the monomer concentration dependence at these conditions. A comprehensive mathematical model was developed to predict copolymer composition as a function of monomer concentration and ionic strength. It is based on a previously-proposed rate law of propagation for ionized monomers, which has been expanded to cover any ionization degree of acrylic acid. The model is capable to reproduce composition data from different sources obtained in a wide range of reaction conditions.

    更新日期:2017-11-14
  • Synthesis and Properties of Semi-crystalline Poly(decamethylene terephthalamide) Thermosets from Reactive Side-group Copolyamides
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-12
    Ming Li, Johan Bijleveld, Theo J. Dingemans

    We have prepared semi-crystalline polyamide (PA) thermosets using reactive side-group functionalized copolyamides as precursors. Reactive meta- and para-based phenylethynyl diacid chlorides (IPE and TPE) were synthesized and incorporated in poly(decamethylene terephthalamide) (PA 10T) using a low temperature solution polymerization method. The phenylethynyl-based comonomers disrupt crystallization of the final copolyamides and lower the onset of melting. Copolyamides containing 5, 10 and 15 mol% of the reactive comonomer could be cured at 350 °C into freestanding PA thermoset films. All thermoset films are stable up to 400 °C, as confirmed by DMTA, which is the result of network formation. The thermosets exhibit both a crystalline phase and a crosslinked amorphous phase. Depending on the concentration of the side-groups, the degree of crystallinity of the final thermosets can be controlled and suppressed by 52-76% compared to the PA 10T reference polymer. Most notable is the fact that the IPE-15 thermoset film exhibits outstanding stress–strain behavior, i.e. elongation at break (∼17%) and toughness (766 MJ·m-3).

    更新日期:2017-11-13
  • Highly Photoluminescent N-Isopropylacrylamide (NIPAAM) passivated Carbon Dots for Multicolor Bioimaging Applications
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-12
    Min Cheol Kim, Kwang Sik Yu, Seung Yun Han, Jwa-Jin Kim, Jae Won Lee, Nam Seob Lee, Yeong Gil Jeong, Do Kyung Kim

    We report a highly luminescent Carbon Dots passivated by nitrogen rich molecules, i.e. N-isopropylacrylamide (NIPAAM), with a QY as high as ca. 94%, which is the highest yield until now. NIPAMM@C-Dots are synthesized directly from the precursors composed of CA, EDA and NIPAAM by hydrothermal reaction. The optical properties of in situ synthesized NIPAAM@C-Dots showed EX-dependent EM at high concentration and EX-independent EM at low concentration. In most cations and anions except Fe3+ and Bi3+ added to the aqueous solution, NIPAAM@C-Dots exhibit an extremely stable inert behavior. In addition, in order to verify its usefulness as a fluorescent marker, C6 glioblastoma cells and NIPAAM@C-Dots were cultured together and then applied by both confocal bioimaging and flow cytometry analysis. The role of NIPAAM present on or around the C-Dots surface can improve QY values and stability, resulting in reduced cytotoxicity and can be a strong candidate as an alternative to organic dyes.

    更新日期:2017-11-13
  • WATER-DRIVEN SEGMENTAL COOPERATIVITY IN POLYVINYL BUTYRAL
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-10
    Giovanni Carini Jr, Antonio Bartolotta, Giuseppe Carini, Giovanna D'Angelo, Mauro Federico, Gaetano Di Marco

    Measurements of thermogravimetry, dynamic mechanical and dielectric analysis, and infrared absorption have been performed in polyvinyl butyral (PVB) to investigate the effect of absorbed water on relaxation dynamics. Increasing water content plasticizes PVB, also causing a growing intermolecular cooperativity mainly for the secondary relaxation motions. Mechanical and dielectric β-relaxations for dry- and wet-PVB fit onto the same Arrhenius plots showing the very close nature of underlying mechanisms. In particular, the sub-glass mechanical β-relaxation in wet-PVB exhibits a frequency factor which increases up to 1016 s-1, disclosing an activation entropy as high as about 59 J/Kmol. It is suggested the existence of cooperative transitions of relaxing side units in adjacent chains, mainly driven by bridges formed through water molecules between the hydroxyl groups of vinyl alcohol segments. Below the glass transition temperature Tg, the bridges are mechanically stable and give rise to an increase of the elastic modulus by more than a factor 2 when compared to that of a fully dry-PVB.

    更新日期:2017-11-10
  • Microwave-assisted rapid synthesis of Fe3O4/Poly(styrene-divinylbenzene-acrylic acid) polymeric magnetic composites and investigation of their structural and magnetic properties
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-09
    Krishna Kumar Jaiswal, Manikandan Dhamodaran, Murugan Ramaswamy, Arun Prasath Ramaswamy

    We report a facile method for rapid synthesis of highly crystalline superparamagnetic Fe3O4 nanoparticles with crystallite size in the range of 25-33 nm via microwave synthesizer. The Fe3O4 stabilized with PVP was used to synthesize strong magnetized spherical polymeric magnetic composites (PMCs) in the range 0.3–1.5 µm via microwave irradiated emulsion polymerization using vinyl monomers. The influence of reaction time and the amount of reactive reagents on the structure, morphology, thermal stability and magnetic property of synthesized PMCs were examined. HR-TEM revealed the incorporation of superparamagnetic Fe3O4 nanoparticles in the cross-linked polymeric matrix of poly(styrene-divinylbenzene-acrylic acid). The synthesized Fe3O4 nanoparticles exhibit superparamagnetic behavior at 300 K with a high saturation magnetization 67.5 emu/g for MNP-3. Interestingly, the as-synthesized magnetically responsive PMCs [Fe3O4/P(St-DVB-AA)] exhibit ferromagnetic properties with enhanced saturation magnetization in the measured time interval of 10 K – 350 K, which is in contrast with the superparamagnetic behavior of synthesized Fe3O4 nanoparticles. An excellent saturation magnetization 22.5 emu/g was noted for the composite PMC-10 loaded with ∼24% magnetic nanoparticles. Further, the as-synthesized Fe3O4 nanoparticles and polymer magnetic composites exhibit the charge ordering (Verwey transition) at low temperature in the range 30 K – 41 K and 23 K – 25 K, respectively.

    更新日期:2017-11-10
  • Multi-faced investigation for pH-sensitivity and solvent polarity in highly charged thermo-responsive hydro- and cryogels with strongly dissociated groups: A comparative evaluation of physico-chemical properties
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-08
    Talin Boyaci, Nermin Orakdogen

    Different series of strong polyelectrolyte poly(N -isopropylacrylamide-co-sodium acrylate) P(NIPA-co-NaA) hydrogels and cryogels were prepared in aqueous solution. With changing the ionic comonomer NaA ratio in reaction mixture, the resulting physico-chemical and swelling properties varied significantly. The findings elucidated that ionic P(NIPA-co-NaA) gels exhibited multi-stimuli performances with pH-, temperature-, solvent-, surfactant- and salt-responsivity, showing more sensitivity than non-ionic PNIPA. Their swollen/collapsed behaviors were strongly dependent on various synthesis/external parameters, including the content of ionic comonomer, temperature and solvent polarity. The effects produced by non-solvents were qualitatively compared considering the aspects related to co-nonsolvency phenomenon and re-entrant swelling transition on the basis of weakening of PNIPA-water interactions. Measurements of the elastic properties and swelling degree of samples having different NaA content were treated by combining Flory-Rehner theory and rubber elasticity to interpret the experimental observations. The polymer-solvent interaction parameter χχ of hydrogels was calculated from the swelling studies in water at different temperatures and was related to the composition and temperature. The ionic strength-reversibility and on-off switching kinetics of hydrogels and cryogels were studied in 10-5 M and 1.0 M of NaBr solutions. Diffusion kinetics showed that the swelling of ionic hydrogels is of non-Fickian-type transportation, however, non-ionic PNIPA hydrogels and P(NIPA-co-NaA) cryogels showed pseudo-Fickian diffusion. The resulting hydrogels and cryogels containing both temperature and pH-sensitive units are able to interact with oppositely charged groups via hydrophobic and electrostatic interactions.

    更新日期:2017-11-10
  • Viologen-Bridged Polyaniline based Multifunctional Heterofilms for All-Solid-State Supercapacitors and Memory Devices
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-08
    Luxin Wang, Sai Sun, Yafei He, Nan He, Fan Zhang, Yefeng Yao, Bin Zhang, Xiaodong Zhuang, Yu Chen

    Both the viologen and polyaniline (PANI) have shown high electrochemical redox activity that can be used to fabricate optoelectronic, electronic and energy storage devices as well as sensors. However, it still remains great challenge for integrating these two fascinating materials together via covalent linkage to avoid phase separation in physical mixtures. In this work, a novel viologen-bridged polyaniline film (hereafter called as VBP) onto the indium-tin-oxide (ITO) glass was prepared by one-step electropolymerization approach, and then the in-situ synthesized golden nanoparticles (AuNPs) were sandwiched between the VBP films to produce the heterofilms (VBP|Au|VBP) as active materials. The VBP|Au|VBP-based electronic memory device and all-solid-state supercapacitor, which exhibited bistable nonvolatile rewritable memory performance with high ON/OFF current ratio of 105 and high volumetric capacitance up to 6.22 Fcm-3, respectively, were fabricated through simple layer-by-layer method. This work not only offers a new and easy strategy for synthesizing viologen-bridged PANI materials through covalent bonding, but also paves the way for the development of high-efficient sandwich-type resistive random access memory (RRAM) devices and the all-solid-state supercapacitors based on rational designed heterofilms.

    更新日期:2017-11-10
  • Self-assembly of Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) Triblock Terpolymers
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-08
    Valentina Musteata, Burhannudin Sutisna, Georgios Polymeropoulos, Apostolos Avgeropoulos, Florian Meneau, Klaus-Viktor Peinemann, Nikos Hadjichristidis, Suzana P. Nunes

    Polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) terpolymer is a versatile polymer to form isoporous films and membranes, due to the possibility of self-assembly control and the properties of the different blocks, such as the P2VP ability of complexation, and H-bond formation, and the PEO biocompatibility. Copolymers with different block ratios and sizes were synthesized. The correlation between their equilibrium bulk morphology, the self-assembly in dilute and semi-dilute solutions and the non-equilibrium porous structures of membranes, obtained by non-solvent induced phase separation, was investigated and discussed in detail. The characterization was performed by small-angle X-ray scattering (SAXS), scanning (SEM) and transmission electron microscopy (TEM). Hexagonal, cubic and lamellar arrangements were observed. The preparation conditions were optimized and a regular, isoporous morphology, suitable for membrane application, was successfully obtained with PS80.5k-b-P2VP64.4k-b-PEO16.1k.

    更新日期:2017-11-10
  • A Simplistic Designing of Molecularly Imprinted Polymers for Derivative of Nerve Agents Marker using 31P{1H}NMR
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-07
    Kanchan Sinha Roy, Avik Mazumder, D. Raghavender Goud, Devendra Kumar Dubey

    The performance of MIP is related with the thermodynamic stability of the pre-polymerization complex. The stability of pre-polymerization complex is influenced by functional monomer, cross-linker, and porogen. These factors in conjugation with the microenvironment polarity determine the binding behaviours of MIP. Methylphosphonic acid (MPA), the ultimate degradation product and persistent environmental marker of nerve agents, was selected as target. In present work, 31P{1H}NMR was employed to optimize imprinting conditions of derivative of MPA. This approach comprised of screening of functional monomer, cross-linker, porogen and stability of pre-polymerization complex before and during polymerization and the MIP was synthesized accordingly. Sorption properties of MIP were elucidated by batch rebinding studies. The selectivity of MIP towards the template was confirmed by comparing its binding with structural analogues of phosphonate esters. These results indicate that 31P{1H}NMR is a simple and effective method for the rational design of MIP for phosphorus containing environmental contaminants.

    更新日期:2017-11-10
  • Encapsulation and release of zafirlukast from electrospun polyisobutylene-based thermoplastic elastomeric fiber mat
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-06
    Judit E. Puskas, Aditya Jindal, Kyle Nedic, Matthew T. Luebbers, James R. Baker Jr., Andrew McClain, Bruno Paiva dos Santos, Melissa Camassola, Wayne Jennings, Richard L. Einsporn, Nic D. Leipzig

    This paper reports the discovery that free-standing rubbery fiber mats can be electrospun from polyisobutylene-based thermoplastic elastomer/poly(ethylene glycol) mixtures from a THF-toluene solution. Direct contact and elution cytotoxic assays of these mats showed no cytotoxic response. Electrospinning the polymers mixed with Zafirlukast (ZAF), an anti-inflammatory drug, resulted in complete encapsulation of ZAF into the fibers, without the need of coaxial spinning. Release profiles followed close to a Fickian diffusion model. Significantly, ZAF-eluting fiber mats successfully inhibited the target cysteinyl leukotriene receptors in vitro, known to reduce inflammation. Local application of these mats could have the potential to reduce capsular contracture, the major complication reported for silicone rubber breast prostheses due to inflammatory response. A recent study using a poly(lactic-co-glycolic acid) polymer coating with a similar drug demonstrated capsule thickness reduction in vivo, but suggested that higher doses and slower release rates would be more effective. We believe our slower releasing mats with higher loading could be better at mitigating capsular contracture.

    更新日期:2017-11-10
  • Recent advances in plant-based vinyl ester resins and reactive diluents
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-04
    Santosh K. Yadav, Kevin M. Schmalbach, Emre Kinaci, Joseph F. Stanzione III, Giuseppe R. Palmese

    Vinyl ester resins (VERs) are used in a variety of applications. However, alternative feedstocks and molecular structures have been recently investigated due to dwindling petroleum reserves and risks associated with bisphenol A (BPA), a leading petroleum-derived precursor for VERs, as well as environmental hazards directly related to the use of petroleum-derived and classified hazardous air pollutant and volatile organic compound reactive diluents (RDs). Plant feedstocks are very common and based on their building blocks, the feedstocks can be categorized into plant oils, cellulose, and lignin. Considerable amount of work has been done on vinyl ester cross-linkers and diluents derived from plant oils, especially those prepared from soybean oil. Carbohydrate biomass-based building blocks, especially isosorbide and furan-based monomers, have a very high potential for use in commercial VERs due to the availability of raw materials and performance of building blocks. Lignin-based vinyl esters have also shown a lot of the potential to compete with their petrochemical counterparts in both cost and performance. This review covers both the topics of bio-based cross-linkers as well as RDs with emphasis on the preparation of monomers and polymers as well as the processing and properties of these materials.

    更新日期:2017-11-10
  • Polyhydroxyalkanoates (PHA) production by photoheterotrophic microbial consortia: Effect of culture conditions over microbial population and biopolymer yield and composition.
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-04
    P. Guerra-Blanco, O. Cortes, T. Poznyak, I. Chairez, E.I. García-Peña

    Three microbial consortia (C2, C4, C5) grown under photoheterotrophic conditions assimilate acetate and butyrate, as individual and mixed substrates. By controlling the culture conditions, it was possible to manipulate the microbial population composition and thus the yield of polyhydroxyalkanoates (PHA) accumulation. Under limited ammonium conditions, pH control, and a sequential two-step process, C2 and C4 produced PHA. C4 showed the highest production of 44% of the cell dry mass (CDM), close to the theoretical value calculated with a stoichiometric balance. Analysis of the confocal microscopy images confirm the accumulated biopolymer percentages produced by each consortium, and it was in close correlation with microbial distribution and substrate consumption pattern. 1H, 13C, NMR, and MALDI-TOF spectra identified the primary structure of the obtained biopolymers as copolymers of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV). This composition allows for better mechanical properties compared to the PHB homopolymer. Microbial characterization showed a similar microbial population with different proportions for C2 and C4. The highest PHA production in C4 was associated with higher abundances of PHA producers, including Clostridium (29%), Pseudomonas (8%) and Rhodopseudomonas (5%). Both microbial consortia showed that a portion of their microbial populations were able to perform syntrophic reactions (Dysgonomonas and Clostridium).

    更新日期:2017-11-10
  • Effect of the blend ratio on the shape memory and self-healing behaviour of ionomer-polycyclooctene crosslinked polymer blends
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-11-04
    Nuria García-Huete, Wouter Post, José Manuel Laza, José Luis Vilas, Luis Manuel León, Santiago J. García

    This work reports on the development of a novel polymer blend with thermally triggered shape memory and self-healing properties. Blends were prepared by mixing a self-healing ionomer (Surlyn 9520) and polycyclooctene (with and without crosslinking agent) in different ratios. The regions of thermal activation were determined by thermogravimetric analysis, differential scanning calorimetry and oscillatory shear rheology. Consecutively, the shape memory and self-healing behaviour were investigated by a torsion procedure and tensile testing respectively. It was found that ionomer/crosslinked polycyclooctene blends of 70/30 wt.% lead to polymers showing partial macroscopic healing and repeatable shape memory characteristics. The new polymer system shows both dual and triple shape memory behaviour and a near to 100% stiffness recovery after healing of crosscuts at standard ionomer healing conditions. Furthermore, the relation between terminal relaxation and self-healing in blends is shown. This study introduces a triple shape memory polymer with self-healing properties by a blending strategy thereby clearing the path for more durable materials based on shape memory properties.

    更新日期:2017-11-10
  • Analysis of microstructure and mechanical performance of polymeric cellular structures designed using stereolithography
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-28
    Sofiane Guessasma, Liu Tao, Sofiane Belhabib, Jihong Zhu, Weihong Zhang, Hedi Nouri
    更新日期:2017-10-28
  • Coupling of poly(lactic acid) with a polyurethane elastomer by reactive processing
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-27
    Dániel Bedő, Balázs Imre, Attila Domján, Peter Schön, G. Julius Vancso, Béla Pukánszky
    更新日期:2017-10-28
  • Fabrication of 3D printed objects with controlled surface chemistry and topography
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-27
    Nelson Vargas-Alfredo, Helmut Reinecke, Alberto Gallardo, Adolfo del Campo, Juan Rodríguez-Hernández
    更新日期:2017-10-28
  • Water-soluble polythiophenes as efficient charge-transport layers for the improvement of photovoltaic performance in Bulk Heterojunction polymeric solar cells
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-27
    Massimiliano Lanzi, Elisabetta Salatelli, Loris Giorgini, Adele Mucci, Filippo Pierini, Francesco Paolo Di-Nicola
    更新日期:2017-10-28
  • Application of a multi-phase multi-morphology crystallization model to isotactic polypropylenes with different molecular weight distributions
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-24
    E.M. Troisi, S.A.J.J. Arntz, P.C. Roozemond, A.H. Tsou, G.W.M. Peters
    更新日期:2017-10-25
  • Synthesis of methacrylate pendant polyelectrolyte as water-soluble multifunctional cross-linker
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-24
    Mustafa Akar, Okan Sirkecioglu, Niyazi Bicak
    更新日期:2017-10-25
  • Cellulose Nanocrystal in Poly (Lactic acid)/Polyamide11 Blends: Preparation, Morphology and Co-continuity
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-24
    Vahid Heshmati, Musa R. Kamal, Basil D. Favis
    更新日期:2017-10-25
  • 更新日期:2017-10-23
  • Synthesis and characterization of polyurethane foams derived of fully renewable polyester polyols from sorbitol
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-20
    Pierre Furtwengler, Rémi Perrin, Andreas Redl, Luc Avérous
    更新日期:2017-10-20
  • Mechanical, rheological and degradation properties of PBAT nanocomposites reinforced by functionalized cellulose nanocrystals
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-20
    I.F. Pinheiro, F.V. Ferreira, D.H.S. Souza, R.F. Gouveia, L.M.F. Lona, A.R. Morales, L.H.I. Mei
    更新日期:2017-10-20
  • 更新日期:2017-10-18
  • Absolute Characteristics and Conformation of Cationic Polymers by Hydrodynamic Approaches: Poly(AEMA-co-MAEMA-co-DMAEMA)stat Copolymers
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-18
    Igor Perevyazko, Anne-K. Trützschler, Alexander Gubarev, Elena Lebedeva, Anja Traeger, Nikolay Tsvetkov, Ulrich S. Schubert
    更新日期:2017-10-18
  • Crystallization Behavior of Precision Polymers Containing Azobenzene Defects
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-17
    Clement Appiah, Georg Woltersdorf, Ricardo A. Pérez-Camargo, Alejandro J. Müller, Wolfgang H. Binder
    更新日期:2017-10-17
  • Crosslinked poly(norbornene-dicarboximide)s as electro-optic chromophore hosts
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-16
    Andrew M. Spring, Feng Qiu, Jianxun Hong, Alisa Bannaron, Tsubasa Kashino, Takamasa Kikuchi, Masaaki Ozawa, Hideyuki Nawata, Keisuke Odoi, Shiyoshi Yokoyama
    更新日期:2017-10-17
  • Rapid preparation of all-cellulose composites by solvent welding based the use of aqueous solvent
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-16
    Juho Antti Sirviö, Miikka Visanko, Nils C. Hildebrandt
    更新日期:2017-10-16
  • Synthesis, characterization and physical properties of rigid polyurethane foams prepared with poly(propylene oxide) polyols containing graphene oxide
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-13
    Mercedes Santiago-Calvo, Victoria Blasco, Carolina Ruiz, Rodrigo París, Fernando Villafañe, Miguel-Ángel Rodríguez-Pérez
    更新日期:2017-10-13
  • Stretching temperature dependence of the critical strain in the tensile deformation of polyethylene copolymer
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-12
    Tao Liao, Zhiyong Jiang, Rui Li, Yuxin Gao, Yongfeng Men
    更新日期:2017-10-12
  • Understanding cyclic by-products and ether linkage formation pathways in the transesterification synthesis of aliphatic polycarbonates
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-12
    Qiang He, Qing Zhang, Shurui Liao, Changsheng Zhao, Xingyi Xie
    更新日期:2017-10-12
  • Thermally-triggered free-standing shape-memory actuators
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-12
    Alberto Belmonte, Giuseppe C. Lama, Gennaro Gentile, Pierfrancesco Cerruti, Veronica Ambrogi, Xavier Fernández-Francos, Silvia De la Flor
    更新日期:2017-10-12
  • Crystallization of Hard Segments in MDI/BD-based Polyurethanes Deformed at Elevated Temperature and Their Dependence on the MDI/BD Content
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-12
    Xuke Li, Ying Lu, Hai Wang, Elmar Pöselt, Berend Eling, Yongfeng Men
    更新日期:2017-10-12
  • Photocrosslinkable Electrospun Fiber Meshes for Tissue Engineering Applications
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-12
    Paula Ferreira, Patrícia Santos, Patrícia Alves, Marco P. Carvalho, Kevin D. de Sá, Sónia P. Miguel, Ilídio J. Correia, Patrícia Coimbra
    更新日期:2017-10-12
  • 更新日期:2017-10-10
  • Effect of sepiolite organomodification on the performance of PCL/sepiolite nanocomposites
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-10
    Marija S. Nikolic, Rada Petrovic, Djordje Veljovic, Vladan Cosovic, Nadezda Stankovic, Jasna Djonlagic
    更新日期:2017-10-10
  • Ionomer Solution to Film Solidification Dependence upon Solvent Type and Its Impact Upon Morphology and Ion Transport
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-10
    Donghui Wang, YanFang Fan, Mingqiang Zhang, Robert B. Moore, Chris J. Cornelius
    更新日期:2017-10-10
  • Tuning Charge Transport across Junctions of Ferrocene-Containing Polymer Brushes on ITO by Controlling the Brush Thickness and the Tether Lengths
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-10
    Lu Gan, C.S. Suchand Sangeeth, Yuan Li, Dominik Jańczewski, Jing Song, Christian A. Nijhuis
    更新日期:2017-10-10
  • Synthesis and temperature-induced self-assembly of a positively charged symmetrical pentablock terpolymer in aqueous solutions
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-09
    Erfan Dashtimoghadam, Hamed Salimi-Kenari, Vahid Forooqi Motlaq, Mohammad Mahdi Hasani-Sadrabadi, Hamid Mirzadeh, Kaizheng Zhu, Kenneth D. Knudsen, Bo Nyström
    更新日期:2017-10-10
  • Magnetoresponsive Polymer Networks as Adsorbents for the Removal of U(VI) Ions from Aqueous Media
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-07
    Rafaella Ilia, Ioanna Liatsou, Ioanna Savva, Eugenia Vasile, Ladislau Vekas, Oana Marinica, Fotios Mpekris, Ioannis Pashalidis, Theodora Krasia-Christoforou
    更新日期:2017-10-08
  • CO2-responsive polyacrylamide copolymer vesicles with acid-sensitive morpholine moieties and large hydrophobic RAFT end-group
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-07
    Benjamin A. Chalmers, Christopher Magee, David L. Cheung, Per B. Zetterlund, Fawaz Aldabbagh
    更新日期:2017-10-08
  • 更新日期:2017-10-08
  • Dielectric response of vulcanized natural rubber containing BaTiO3 filler: The role of particle functionalization
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-05
    Neudys González, Maria dels Àngels Custal, Georgia N. Tomara, Georgios C. Psarras, Jordi-Roger Riba, Elaine Armelin
    更新日期:2017-10-05
  • Bronsted acidic ionic liquids: New transesterification agents for the compatibilization of Polylactide/Ethylene-co-vinyl acetate blends
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-05
    Elaine C. Lopes Pereira, Juliana M. Farias da Silva, Rayan B. Jesus, Bluma G. Soares, Sebastien Livi
    更新日期:2017-10-05
  • Templated polycondensation of aminopropyltrimethoxysilane on DNA
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-04
    N. Jarroux, M.J. Clément, M. Gervais, S. Moriau, O. Maciejak, P.A. Curmi, H. Cheradame
    更新日期:2017-10-04
  • 更新日期:2017-10-04
  • 更新日期:2017-10-04
  • Fibrous Polymeric Buccal Film Formulation, Engineering and Bio-Interface Assessment
    Eur. Polym. J. (IF 3.531) Pub Date : 2017-10-03
    Kazem Nazari, Eleni Kontogiannidou, Rita Haj Ahmad, Dimitrios Andreadis, Manoochehr Rasekh, Nikolaos Bouropoulos, Marisa van Der Merwe, Ming-Wei Chang, Dimitrios G Fatouros, Zeeshan Ahmad
    更新日期:2017-10-03
Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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