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Sample records for poly phthalazinone ether

  1. Synthesis and Characterization of Poly(phthalazinone Ether Nitrile) Copolymers with Hydrophobic Surface

    NASA Astrophysics Data System (ADS)

    Dong, L. M.; Liao, G. X.; Liu, C.; Yang, S. S.; Jian, X. G.

    Poly(phthalazinone ether nitrile) (PPEN) block copolymers containing polysiloxane were prepared so as to create a strongly hydrophobic polymer surface. The copolymers were synthesized from eugenol end-capped polydimethylsiloxane (PDMS) and fluoro-terminated PPEN oligomers by the aromatic nucleophilic substitution polycondensation in the presence of dimethyl sulfoxide/o-dichlorobenzene and K2CO3 as solvents and catalyst, respectively. The resultant copolymers were characterized by FTIR, 1H NMR, and gel permeation chromatography. XPS analysis results indicated that the copolymer film had a very rich PDMS segment surface. Atomic force microscopy further showed that there existed a continuous PDMS phase on the copolymer surface and PPEN as the dispersive particles was dispersed at diameters between 0.1 and 0.3 nm. The enrichment of PDMS in the copolymer surface could be responsible for an increase of surface water repellency (113.4°).

  2. Coupling hydrogen separation with butanone hydrogenation in an electrochemical hydrogen pump with sulfonated poly (phthalazinone ether sulfone ketone) membrane

    NASA Astrophysics Data System (ADS)

    Huang, Shiqi; Wang, Tao; Wu, Xuemei; Xiao, Wu; Yu, Miao; Chen, Wei; Zhang, Fengxiang; He, Gaohong

    2016-09-01

    This work reports the novel work of coupling H2/CO2 separation with biomass-derived butanone hydrogenation in non-fluorinated sulfonated poly (phthalazinone ether sulfone ketone) (SPPESK) electrochemical hydrogen pump (EHP) reactor. Due to higher resistance to swelling, SPPESK-based EHP reactor exhibits more excellent reaction rate in elevated temperature (60 °C) and higher butanone concentration (2 M) as 270, 260 nmol cm-2 s-1, respectively, higher than 240, 200 nmol cm-2 s-1of Nafion-based EHP reactors. Also, the SPPESK-based EHP reactor remains 90% of initial hydrogenation rate after 4 batches, better than that of Nafion-based EHP reactors, which is only 62%. The energy efficiency of EHP separator reaches 40% under H2/CO2 mixture feed mode, and electricity of about 0.3 kWh is consumed per Nm3 H2 product, being superior to energy consumption compared with alternative processes like PSA and electrolysis of water. In addition, SPPESK-based EHP exhibits better hydrogenation stability due to lower CO2 permeation than Nafion. With increasing CO2 content in H2 feed, hydrogenation rate almost keeps constant at around 210 nmol cm-2 s-1 in SPPESK-based EHP reactor while decreases fast to 50 nmol cm-2 s-1 in Nafion/PTFE-based EHP reactor. These results show integration of gas separation with hydrogenation reactor is feasible in SPPESK-based EHP reactor.

  3. Aligned electrospun nanofibers as proton conductive channels through thickness of sulfonated poly (phthalazinone ether sulfone ketone) proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Gong, Xue; He, Gaohong; Wu, Yao; Zhang, Shikai; Chen, Bo; Dai, Yan; Wu, Xuemei

    2017-08-01

    A novel approach is proposed to fabricate sulfonated poly (phthalazinone ether sulfone ketone) (SPPESK) proton exchange membranes with ordered through-plane electrospinning nanofibers, which provide nano-scale through-plane proton conductive channels along the thickness direction of the membranes, aiming to satisfy the challenging requirement of high through-plane proton conductivity in fuel cell operations. Induced by electrostatic attraction of strong electric field, the negatively charged sulfonic acid groups tend to aggregate towards surface of the electrospun fibers, which is evidenced by TEM and SAXS and further induces aggregation of the sulfonic acid groups in the SPPESK inferfiber voids filler along the surface of the nanofibers. The aligned electrospun nanofibers carries long-range ionic clusters along the thickness direction of the membrane and results in much higher total through-plane conductivity in the thickness aligned electrospun membranes, nearly twice as much as that of the cast SPPESK membrane. With smooth treatment, the thickness aligned electrospun SPPESK membranes exhibit higher single cell power density and tensile strength as compared with Nafion 115 (around 1.2 and 1.5 folds, respectively). Such a design of thickness aligned nano-size proton conductive channels provide feasibility for high performance non-fluorinated PEMs in fuel cell applications.

  4. Optimization and characterization of poly(phthalazinone ether ketone) (PPEK) heat-resistant porous fiberous mat by electrospinning

    NASA Astrophysics Data System (ADS)

    Shi, R.; Bin, Y. Z.; Yang, W. X.; Wang, D.; Wang, J. Y.; Jian, X. G.

    2016-08-01

    Poly(phthalazinone ether ketone) (PPEK) is noted for its outstanding heat-resistance property and mechanical strength. A one-step electrospinning method was conducted to produce PPEK micro-nano porous fibrous mat. We gave emphasis study on the spinnability, optimized conditions, fibers' morphology, surface science and fracture mechanism. The uniform electrospun fibrous mat resulted from PPEK/chloroform binary system indicated that PPEK would be a prospective material to be applied in electrospinning. Addition of a small amount of non-solvent (ethanol) turned out to be advantageous to the reduction of fiber diameter and the alleviation of choking during spinning process. Organic salt (benzyltrimethylammonium chloride) was employed to increase the conductivity of solution for the formation of thin fiber. After trials, PPEK/chloroform/ethanol system with salt and PPEK/NMP system were taken as two optimized systems. These two systems showed different pore fraction in N2 adsorption test, and displayed different mechanical behaviors in uniaxial tension test. The fibrous mat from PPEK/chloroform/ethanol system showed a feature of ductile fracture with relatively low fracture strength but long fracture deformation, while the fibrous mat from PPEK/NMP system showed a feature of brittle fracture with small deformation but quite large fracture strength of ca. 6 MPa. Finally thermogravimetric analysis indicated that the resultant PPEK fibrous mat did not decompose until the temperature reached 478 °C, which qualified the resultant fibrous mat as a promising material used under high-temperature condition.

  5. Low vanadium ion permeabilities of sulfonated poly(phthalazinone ether ketone)s provide high efficiency and stability for vanadium redox flow batteries

    NASA Astrophysics Data System (ADS)

    Chen, Liyun; Zhang, Shouhai; Chen, Yuning; Jian, Xigao

    2017-07-01

    A series of novel sulfonated poly(phthalazinone ether ketone)s containing pendant phenyl moieties (SPPEK-Ps) are synthesized and thoroughly characterized. The chemical structures of the polymers are confirmed by 1H NMR and FTIR analysis. The physicochemical properties and single cell performance of SPPEK-P membranes are systematically evaluated, revealing that the membranes are thermally, chemically and mechanically stable. The area resistances of SPPEK-P-90 and SPPEK-P-100 are 0.75 Ω cm2 and 0.34 Ω cm2, respectively. SPPEK-P membranes are impermeable to the bulky hydrated VO2+ ion and exhibited low V3+ ion permeability (SPPEK-P-90, 2.53 × 10-5 cm min-1) (Nafion 115 membrane: 9.0 × 10-4 cm min-1). Tests of SPPEK-P-90 in vanadium redox flow batteries (VRFBs) demonstrate a comparable columbic efficiency (CE) and energy efficiency (EE) to that of Nafion 115, where the CE is 98% and the EE is 83% at 60 mA cm-2. Moreover, the SPPEK-P-90 membrane exhibits stable performance in cell over 100 charge-discharge cycles (∼450 h).

  6. Preparation and characterization of thermally stable copoly(phthalazinone biphenyl ether sulfone) hollow fiber ultrafiltration membranes

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Zhang, Shouhai; Wang, Yutian; Lu, Yan; Jian, Xigao

    2015-04-01

    Novel thermally stable copoly(phthalazinone biphenyl ether sulfone) (PPBES) hollow fiber ultrafiltration (UF) membranes were successfully fabricated by the dry/wet phase inversion technique. The effects of polymer dope formulation (i.e., the PPBES concentration, different types and contents of additives) and fiber spinning conditions (i.e., air gap distance, coagulation bath temperature) on the morphologies and separation performance of PPBES hollow fiber UF membranes were investigated, respectively. It was found that the water flux of hollow fiber membrane decreased with the increase of PPBES concentration or EGME content in casting solution, while the rejection of PEG increased. However, the PPBES hollow fiber UF prepared with LiCl as inorganic small molecule additive exhibited different phenomena. In addition, the decrease of air gap distance or the increase of coagulation bath temperature could improve the water flux of UF membrane while reduce the rejection of PEG. Moreover, the thermal stability of the PPBES hollow fiber UF membranes was investigated. The water flux of PPBES membrane increased dramatically from 155 to 428 L m-2 h-1 without significant decrease of rejection when the temperature of feed solution increased from 20 °C to 95 °C.

  7. Effect of additives on the performance and morphology of sulfonated copoly (phthalazinone biphenyl ether sulfone) composite nanofiltration membranes☆

    NASA Astrophysics Data System (ADS)

    Guan, Shanshan; Zhang, Shouhai; Liu, Peng; Zhang, Guozhen; Jian, Xigao

    2014-03-01

    Sulfonated copoly (phthalazinone biphenyl ether sulfone) (SPPBES) composite nanofiltration membranes were fabricated by adding low molecular weight additives into SPPBES coating solutions during a dip coating process. Three selected additives: glycol, glycerol and hydroquinone were used in this work. The effect of additives on the membrane performance was studied and discussed in terms of rejection and permeation flux. Among all the composite membranes, the membrane prepared with glycol as an additive achieved the highest Na2SO4 rejection, and the membrane fabricated with glycerol as an additive exhibited the highest flux. The salts rejection of SPPBES composite membranes increased in the following order MgCl2 < NaCl ≤ MgSO4 < Na2SO4. The morphologies of the SPPBES composite membranes were characterized by SEM, it was found that the membrane prepared with hydroquinone showed a rough membrane surface. Composite membrane fabricated with glycol or glycerol as the additive showed very good chemical stability.

  8. Poly(arylene ether)s containing pendent ethynyl groups

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Jensen, Brian J. (Inventor)

    1996-01-01

    Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

  9. Promoting and Tuning Porosity of Flexible Ether-Linked Phthalazinone-Based Covalent Triazine Frameworks Utilizing Substitution Effect for Effective CO2 Capture.

    PubMed

    Yuan, Kuanyu; Liu, Cheng; Zong, Lishuai; Yu, Guipeng; Cheng, Shengli; Wang, Jinyan; Weng, Zhihuan; Jian, Xigao

    2017-04-10

    Five porous ether-linked phthalazinone-based covalent triazine frameworks (PHCTFs) were successfully constructed via ionothermal polymerizations from flexible dicyano monomers containing asymmetric, twisted, and N-heterocyclic phthalazinone structure. All the building blocks could be easily prepared by simple and low-cost aromatic nucleophilic substitution reactions, showing the large-scale application potential of thermal stable phthalazinone structure in constructing porous materials. Generally, the flexible building blocks are avoided to prevent the networks from collapsing in constructing high surface area porous materials. Our experimental results revealed that the introduction of the substituents can effectively decrease the probability of the network interpenetration from the longer struts and the intermolecular/intramolecular intercalation from the increased degree of conformation freedom in the flexible ether-linkage, the BET surface areas of PHCTFs increasing from 676 to 1270 m(2) g(-1). Meanwhile, the effects of introducing different sizes (methyl or phenyl group) and amounts (one or two) of substituents on the porosities of the target polymer networks were also investigated in detail. The high CO2 adsorption capacity of 10.3 wt % (273 K, 1 bar) can be ascribed to the strong affinity of the electron-rich N,O-containing networks with CO2. Excitingly, PHCTF-5 demonstrates the high CO2/N2 selectivity up to 138 (273 K, 1 bar), according to the ideal adsorbed solution theory (IAST) for the higher proportion of Vmicro accompanied the electron-rich heteroatoms characteristic. Such high CO2 adsorption capacity and good separation properties are superior to those of many other microporous organic polymers. These properties along with easily up-scalable synthesis make porous PHCTFs promising candidates applied in gas sorption and separation field.

  10. Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

    DOEpatents

    Hofmann, Michael A.

    2006-11-14

    The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

  11. Poly(arylene ether)s That Resist Atomic Oxygen

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Hergenrother, Paul; Smith, Joseph G., Jr.

    1994-01-01

    Novel poly(arylene ether)s containing phosphine oxide (PAEPO's) made via aromatic nucleophilic displacement reactions of activated aromatic dihalides (or, in some cases, activated aromatic dinitro compounds) with new bisphenol monomers containing phosphine oxide. Exhibited favorable combination of physical and mechanical properties and resistance to monatomic oxygen in oxygen plasma environment. Useful as adhesives, coatings, films, membranes, moldings, and composite matrices.

  12. A new alternative to expandable pedicle screws: Expandable poly-ether-ether-ketone shell.

    PubMed

    Demir, Teyfik

    2015-05-01

    Screw pullout is a very common problem in the fixation of sacrum with pedicle screws. The principal cause of this problem is that the cyclic micro motions in the fixation of sacrum are higher than the other regions of the vertebrae that limit the osteo-integration between bone and screw. In addition to that, the bone quality is very poor at sacrum region. This study investigated a possible solution to the pullout problem without the expandable screws' handicaps. Newly designed poly-ether-ether-ketone expandable shell and classical pedicle screws were biomechanically compared. Torsion test, pullout tests, fatigue tests, flexion/extension moment test, axial gripping capacity tests and torsional gripping capacity tests were conducted in accordance with ASTM F543, F1798 and F1717. Standard polyurethane foam and calf vertebrae were used as embedding medium for pullout tests. Classical pedicle screw pullout load on polyurethane foam was 564.8 N compared to the failure load for calf vertebrae's 1264 N. Under the same test conditions, expandable poly-ether-ether-ketone shell system's pullout loads from polyurethane foam and calf vertebrae were 1196.3 and 1890 N, respectively. The pullout values for expandable poly-ether-ether-ketone shell were 33% and 53% higher than classical pedicle screw on polyurethane foam and calf vertebrae, respectively. The expandable poly-ether-ether-ketone shell exhibited endurance on its 90% of yield load. Contrary to poly-ether-ether-ketone shell, classical pedicle screw exhibited endurance on 70% of its yield load. Expandable poly-ether-ether-ketone shell exhibited much higher pullout performance than classical pedicle screw. Fatigue performance of expandable poly-ether-ether-ketone shell is also higher than classical pedicle screw due to damping the micro motion capacity of the poly-ether-ether-ketone. Expandable poly-ether-ether-ketone shell is a safe alternative to all other expandable pedicle screw systems on mechanical perspective.

  13. Poly (Aryl Ether Ketones) Bearing Alkylated Side Chains

    NASA Technical Reports Server (NTRS)

    Cassidy, Patrick E. (Inventor); Fitch, John W., III (Inventor); Gronewald, Scott D. (Inventor); St.Clair, Ann K. (Inventor); Stoakley, Diane M. (Inventor)

    2002-01-01

    This invention relates generally to poly(aryl ether ketones) bearing alkylated side chains. It relates particularly to soluble, thermally stable. low dielectric poly(aryl ether ketones) with alkylated side chains and especially to films and coatings thereof. These poly(aryl ether ketones) have a structural formula wherein Y is selected from the group consisting of CF3 and CH3; and wherein R is C(sub n)H(sub (2n+1)) and n = 11-18.

  14. Phenylethynyl-Terminated Poly(Arylene Ethers)

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Bryant, Robert G.; Hergenrother, Paul M.

    1994-01-01

    Phenylethynyl-terminated poly(arylene ethers) synthesized in wide range of molecular weights by adjusting monomer ratios and adding appropriate amounts of 4-phenylethynyl-4'-fluorobenzophenone to monomers to end-cap oligomers during polymerization. Have low molecular weights and low melt viscosities, and are easily processed as adhesives, composites, and moldings. Thermally cured to provide materials that are crosslinked and insoluble in common organic solvents. Exhibit increased resistance to solvents, greater tensile moduli, and better high-temperature properties. Useful as adhesives, composite matrices, and moldings, especially in applications in which combination of toughness and resistance to solvents needed.

  15. Fluorinated Poly(Phenylene Ether Ketones)

    NASA Technical Reports Server (NTRS)

    St. Clair, Anne K.; Cassidy, Patrick E.; Tullos, Gordon L.

    1994-01-01

    Fluorinated poly(phenylene ether ketones) are colorless, transparent, low-dielectric-constant, highly thermally stable polymers. Particularly suitable for use as film and coating materials in electronic and thermal-control applications such as; passivant insulating coats and interlevel dielectrics in microelectronic circuits, or as protective transparent coats on solar cells or mirrors. Solubility and transparency of 12F-PEK along with its lower dielectric constant and other properties make it more useful as dielectric film and coating material in many applications.

  16. Synthesis and characterization of poly(silyl ether)s and modified poly(siloxane)s

    NASA Astrophysics Data System (ADS)

    Mabry, Joseph Mark

    Activated dihydridocarbonyltris(triphenylphosphine)ruthenium ( Ru) catalyzes the dehydrogenative silylation condensation copolymerization of ortho-quinones with alpha,o-dihydrido-oligodimethylsiloxanes to give high molecular weight copoly(arylene-1,2-dioxy/oligodimethylsiloxanylene)s in good chemical yield. The hydrosilylation polymerization of aliphatic o-dimethylsilyloxy ketones is also catalyzed by activated Ru to yield unsymmetrical poly(silyl ether)s. Likewise, Ru catalyzes the copolymerization of alpha,o-diketones with alpha,o-dihydrido-oligodimethylsiloxanes to yield symmetrical poly(silyl ether)s. A mechanism of the copolymerizations is proposed, in which beta-hydride elimination is favored over reductive elimination in the reaction of the ortho-quinones. Chiral centers affect the NMR spectra of the poly(silyl ether)s produced by hydrosilylation. The photoluminescence properties of the polymers were studied along with those of model compounds. The decrease in Tgs with increase in siloxane chain length as well as fluorescence spectra is discussed. RuH2(CO)(PPh3)3 (Ru), activated with a stoichiometric amount of styrene, catalyzes the anti-Markovnikov addition of an ortho C-H bond of benzophenone across the C-C double bonds of alpha,o-bis(trimethylsilyloxy)copoly(dimethylsiloxane/vinylmethylsiloxane), alpha,o-bis(vinyldimethsilyloxy)poly(dimethylsiloxane)s, and 1,3-divinyltetramethyldisiloxane to yield alpha,o-bis(trimethylsilyloxy)copoly[dimethylsiloxane/2-(2 '-benzophenonyl)ethylmethylsiloxane]s, alpha,o-bis[2-(2 '-benzophenonyl)ethyldimethylsilyloxy]poly(dimethylsiloxane)s, and 1,3-bis[2-(2'-benzophenonyl)ethyl]tetramethyldisiloxane, respectively. While the Mw/Mn and Tgs of the modified polysiloxanes are similar to those of the precursor polymers, an increase in molecular weight is observed upon heating. 1,3-bis[2-(2 '-Benzophenonyl)ethyl]tetramethyldisiloxane, a model compound, was utilized to test a mechanism for the increase in molecular weight. A

  17. Synthesis and characterizations of electrospun sulfonated poly (ether ether ketone) SPEEK nanofiber membrane

    NASA Astrophysics Data System (ADS)

    Hasbullah, N.; Sekak, K. A.; Ibrahim, I.

    2016-07-01

    A novel electrospun polymer electrolyte membrane (PEM) based on Sulfonated Poly (ether ether ketone) were prepared and characterized. The poly (ether ether ketone) PEEK was sulfonated using concentrated sulfuric acid at room temperature for 60 hours reaction time. The degree sulfonation (DS) of the SPEEK are 58% was determined by H1 NMR using area under the peak of the hydrogen shielding at aromatic ring of the SPEEK. Then, the functional group of the SPEEK was determined using Fourier transfer infrared (FTIR) showed O-H vibration at 3433 cm-1 of the sulfonated group (SO2-OH). The effect of the solvent and polymer concentration toward the electrospinning process was investigated which, the DMAc has electrospun ability compared to the DMSO. While, at 20 wt.% of the polymer concentration able to form a fine and uniform nanofiber, this was confirmed by FESEM that shown electrospun fiber mat SPEEK surface at nano scale diameter.

  18. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketone)s and Linear Poly(ether ketone)s.

    PubMed

    Morikawa, Atsushi

    2016-02-16

    Poly(ether ether ketone) dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4'-(4-fluorobenzoyl)diphenyl ether and 3,5-dihydroxy-4'-(4-fluorobenzoyl)diphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy)-3,5-bis(4-fluorobenzoyl)benzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketone)s having the same hydroxyl groups in the side chains as the chain ends of the dendrimer and hyperbranched polymers. Their properties, such as solubilities, reduced viscosities, and thermal properties, were compared with one another. Similar comparisons were also carried out among the corresponding methoxy group polymers, and the size of the molecules was shown to affect the properties.

  19. Poly(aryl-ether-ether-ketone) as a Possible Metalized Film Capacitor Dielectric: Accurate Description of the Band Gap Through Ab Initio Calculation

    DTIC Science & Technology

    2014-12-01

    Poly(aryl-ether-ether- ketone ) as a Possible Metalized Film Capacitor Dielectric: Accurate Description of the Band Gap Through Ab Initio...the originator. Army Research Laboratory Adelphi, MD 20783-1138 ARL-TR-7160 December 2014 Poly(aryl-ether-ether- ketone ) as a...REPORT DATE (DD-MM-YYYY) December 2014 2. REPORT TYPE Final 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Poly(aryl-ether-ether- ketone ) as

  20. Chemistry and adhesive properties of poly(arylene ether)s containing heterocyclic units

    NASA Technical Reports Server (NTRS)

    Connell, John W.

    1991-01-01

    Novel poly(arylene ether)s containing heterocyclic units were prepared, characterized, and evaluated as adhesives and composite matrices. The polymers were prepared by reacting a heterocyclic bisphenol with an activated aromatic dihalide in a polar aprotic solvent, using potassium carbonate. The polymerizations were generally carried out in N,N-dimethylacetamide at 155 C. In some cases, where the polymers were semicrystalline, higher temperatures and thus higher boiling solvents were necessary to keep the polymers in solution. Heterocyclic rings incorporated into the poly(arylene ether) backbone include phenylquinoxaline, phenylimidazole, benzimidazole, benzoxazole, 1,3,4-oxadiazole, and 1,2,4-triazole. The polymers were characterized by differential scanning calorimetry, solution viscosity, X-ray diffraction, thin film, and adhesive and (in some cases) composite properties. The glass transition temperatures, crystalline melt temperature, solubility, and mechanical properties varied depending upon the heterocyclic ring. The chemistry and properties of these materials are discussed.

  1. Amorphous phase separation in crystallizable polymer blends based on poly (aryl ether ketones) and poly (ether imide)

    SciTech Connect

    Kalika, D.S.; Bristow, J.F.

    1996-12-31

    The morphology of a series of miscible crystallizable blends based on poly (aryl ether ketones) [PAEK] and poly (ether imide) [PEI] has been investigated as a function of blend composition and crystallization condition by dielectric relaxation spectroscopy. For blends of poly (ether ether ketone) [PEEK] and PEI, dielectric scans of the crystallized samples reveal two glass-rubber relaxations corresponding to the coexistence of a mixed interlamellar amorphous phase, and a pure PEI phase located in interfibrillar/interspherulitic regions. The exclusion of a significant fraction of PEI outside of the crystal lamellae reflects a fundamental change in the nature of interaction between the interlamellar PEEK segments and the PEI chains owing to the constraints imposed on the PEEK segments by the crystal surfaces. The degree of PEI exclusion is dependent upon kinetic factors, i.e. the rate of PEEK crystallization relative to the rate of PEI diffusion away from the advancing crystal front. As a result, lower crystallization temperatures lead to an increase in the amount of PEI trapped in the interlamellar regions. In this work, the morphological characteristics of the PEEK/PEI blends are compared with those of blends comprised of poly (ether ketone ketone) [PEKK] and PEI. The introduction of the {open_quotes}kinked{close_quote} isophthalate moiety in the PEKK backbone has been shown to disrupt the persistence of order at the crystal-amorphous interface, and thereby leads to a reduction in the degree of constraint imposed by the crystal lamellae on the amorphous (interlamellar) PEKK segments. The impact of this reduction in crystalline constraint on the nature of the PEKK/PEI intersegmental interactions and the corresponding PEI segregation is discussed.

  2. Novel high T[sub g] high-strength poly(aryl ether)s

    SciTech Connect

    Banerjee, S.; Maier, G. . Lehrstuhl fuer Makromolekulare Stoffe)

    1999-08-01

    A novel 2-perfluoroalkyl-activated bisfluoro monomer has been synthesized successfully using a Pd(0)-catalyzed cross-coupling reaction of 4-fluoro-3-trifluoromethyl phenyl boronic acid with 4,4[prime]-dibromodiphenylbenzene. This monomer was converted to novel poly(aryl ether)s by nucleophilic displacement of the fluorine atoms on the benzene ring with several bisphenols. The products obtained by displacement of the fluorine atoms exhibit weight average molar masses up to 1.06 [times] 10[sup 5] g/mol in GPC. These poly(aryl ether)s showed outstanding thermooxidative stability up to 534 C for 5% weight loss in TGA under synthetic air and high glass transition temperatures (T[sub g]) even up to 300 C in DSC and DMTA. These polymers are soluble in a wide range of organic solvents, e.g., CHCl[sub 3], THF, NMP, DMF, toluene, etc., and are insoluble in DMSO and acetone. Transparent thin films of these polymers cast from DMF exhibited tensile strengths up to 115 MPa, moduli up to 2.59 GPa, and elongations up to 120% depending on their exact repeating unit structures. These values are comparable to those of high performance thermoplastic materials such as PEEK or Ultem PEI.

  3. Novel high T{sub g} high-strength poly(aryl ether)s

    SciTech Connect

    Banerjee, S.; Maier, G.

    1999-08-01

    A novel 2-perfluoroalkyl-activated bisfluoro monomer has been synthesized successfully using a Pd(0)-catalyzed cross-coupling reaction of 4-fluoro-3-trifluoromethyl phenyl boronic acid with 4,4{prime}-dibromodiphenylbenzene. This monomer was converted to novel poly(aryl ether)s by nucleophilic displacement of the fluorine atoms on the benzene ring with several bisphenols. The products obtained by displacement of the fluorine atoms exhibit weight average molar masses up to 1.06 {times} 10{sup 5} g/mol in GPC. These poly(aryl ether)s showed outstanding thermooxidative stability up to 534 C for 5% weight loss in TGA under synthetic air and high glass transition temperatures (T{sub g}) even up to 300 C in DSC and DMTA. These polymers are soluble in a wide range of organic solvents, e.g., CHCl{sub 3}, THF, NMP, DMF, toluene, etc., and are insoluble in DMSO and acetone. Transparent thin films of these polymers cast from DMF exhibited tensile strengths up to 115 MPa, moduli up to 2.59 GPa, and elongations up to 120% depending on their exact repeating unit structures. These values are comparable to those of high performance thermoplastic materials such as PEEK or Ultem PEI.

  4. Synthesis and characterization of poly(D,L-lactide)-poly(ethylene glycol) multiblock poly(ether-ester-urethane)s

    NASA Astrophysics Data System (ADS)

    Haw, Tan Ching; Ahmad, Azizan; Anuar, Farah Hannan

    2015-09-01

    In this study, poly(D,L-lactide)-poly(ethylene glycol) multiblock poly(ether-ester-urethane)s was synthesized in the framework of environmental friendly products to meet the need for highly flexible polymers. Triblock copolymer with poly(ethylene glycol) as center block and poly(D,L-lactide) as side block were first synthesized by ring-opening polymerization of D,L-lactide, followed by chain extension reaction of triblocks using hexamethylene diisocyanate (HMDI). NMR and infra-red spectroscopies were used to determine the molecular composition whereas XRD analysis revealed crystallinity behavior of synthesized multiblock copolymers.

  5. High temperature fuel cell membranes based on poly(arylene ether)s containing benzimidazole groups

    SciTech Connect

    Kim, Dae Sik; Kim, Yu Seung; Lee, Kwan - Soo; Boncella, James M; Kuiper, David; Guiver, Michael D

    2009-01-01

    Development of new high-performance polymer membranes that retain their proton conductivity under low humidity conditions is one of the most critical requirements to commercialize PEMFC systems. Current sulfonated proton exchange membranes acquire proton conductivity by water that solvates ion and carries proton. Consequently, a loss of water under low RH conditions immediately results in a loss of proton conductivity. One approach to maintain proton conductivity under low RH conditions is to replace water with a less volatile proton solvent. Kreuer has pointed out the possibility to develop fully polymeric proton-conducting membranes based on nitrogen-containing heterocycles such as imidazole, benzimidazole, and pyrazole. We have attempted to blend those less volatile proton solvent with sulfonated copolymers such as polystyrene sulfonic acid, Nafion, poly(arylene ether sulfone, BPSH-xx). [Ref. DOE review meeting 2007 and 2008] However, we observed that imidazole was slowly sublimated out as temperature and humidity increases which could cause poisoning of electro-catalyst, corrosion and losing conductivity. In this presentation, we report the synthesis of novel poly(arylene ether sulfone)s containing benzimidazole groups These benzimidazole containing polymer was blended with sulfonated poly(arylene ether sulfone). In the blend system, benzimidazole group attached to the polysulfone acts as a medium through the basic nitrogen for transfer of protons between the sulfonic acid groups. Proton conductivity of the blend membranes was investigated as a function of water content at 80 C and compared the performance with water based proton conduction system.

  6. Thermotropic behavior of poly(oxyethylene) cholesterol ethers.

    PubMed

    López-Quintela, M Arturo; Akahane, Akira; Rodríguez, Carlos; Kunieda, Hironobu

    2002-03-01

    The thermotropic behavior of poly(oxyethylene) cholesterol ether surfactants was studied by differential scanning calorimetry and small-angle X-ray scattering. Contrary to what is usually observed in conventional poly(oxyethylene)-type surfactant systems, poly(oxyethylene) cholesterol ether surfactants show a change of the fusion mechanism as the chain length is varied. For long chain lengths (n > or = 15) the usual solid-liquid transition is found, but for short chain lengths (n < or = 10) the transition goes through a birefringent lamellar phase. The appearance of this liquid crystal (LC) phase seems to be related with the predominance of the cholesterol part in the short chain polyoxyethylene surfactants. On the contrary, for long polyexyethylene chains the polymer gains in importance and only a solid crystalline structure is observed at low temperatures. An antiparallel packing structure with totally overlapped chains is found for both, the solid and the LC phase. The chains seem to be in a zigzag configuration, and only for the longest surfactant here studied (n = 30) a change of the chain configuration to a much shorter meander configuration is observed.

  7. Chemistry and properties of new poly(arylene ether imidazoles)

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Hergenrother, P. M.

    1990-01-01

    As part of a program to develop high-temperature high-performance structural resins for aerospace applications, the chemistry and properties of new poly(arylene ether imidazoles) were investigated. The polymers were prepared by the nucleophilic displacement reaction of aromatic bis(imidazolephenols) with activated aromatic difluoro compounds. The amorphous thermoplastic polymers exhibited glass transition temperatures from 230 to 301 C, inherent viscosities from 0.46 to 1.46 dL/g, and number-average molecular weights as high as 59,300 g/mole. The polymers exhibit good toughness, adhesive, composite, and film properties. The chemical, physical, and mechanical properties of these materials are discussed.

  8. Chemistry and properties of new poly(arylene ether imidazoles)

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Hergenrother, P. M.

    1990-01-01

    As part of a program to develop high-temperature high-performance structural resins for aerospace applications, the chemistry and properties of new poly(arylene ether imidazoles) were investigated. The polymers were prepared by the nucleophilic displacement reaction of aromatic bis(imidazolephenols) with activated aromatic difluoro compounds. The amorphous thermoplastic polymers exhibited glass transition temperatures from 230 to 301 C, inherent viscosities from 0.46 to 1.46 dL/g, and number-average molecular weights as high as 59,300 g/mole. The polymers exhibit good toughness, adhesive, composite, and film properties. The chemical, physical, and mechanical properties of these materials are discussed.

  9. Sulfonated poly(tetramethydiphenyl ether ether ketone) membranes for vanadium redox flow battery application

    NASA Astrophysics Data System (ADS)

    Mai, Zhensheng; Zhang, Huamin; Li, Xianfeng; Bi, Cheng; Dai, Hua

    Sulfonated poly(tetramethydiphenyl ether ether ketone) (SPEEK) with various degree of sulfonation is prepared and first used as ion exchange membrane for vanadium redox flow battery (VRB) application. The vanadium ion permeability of SPEEK40 membrane is one order of magnitude lower than that of Nafion 115 membrane. The low cost SPEEK membranes exhibit a better performance than Nafion at the same operating condition. VRB single cells with SPEEK membranes show very high energy efficiency (>84%), comparable to that of the Nafion, but at much higher columbic efficiency (>97%). In the self-discharge test, the duration of the cell with the SPEEK membrane is two times longer than that with Nafion 115. The membrane keeps a stable performance after 80-cycles charge-discharge test.

  10. Wear of ceramic-on-carbon fiber-reinforced poly-ether ether ketone hip replacements.

    PubMed

    Brockett, Claire L; John, Gemma; Williams, Sophie; Jin, Zhongmin; Isaac, Graham H; Fisher, John

    2012-08-01

    Total hip replacement has been a successful surgical intervention for over 50 years, with the majority of bearings using a polyethylene cup. Long-term failure due to osteolysis and loosening has been widely documented and alternative bearings have been sought. A novel carbon fiber-reinforced poly-ether ether ketone (CFR-PEEK) cup was investigated through experimental friction and wear studies. Friction studies demonstrated the bearings operated in a boundary lubrication condition, with friction factors higher than those for other hip replacement bearings. The wear study was conducted with 36 mm diameter bearings tested against Biolox Delta heads for a period of 10 million cycles. The mean volumetric wear rate was 0.3 mm(3)/Mc, indicating the ceramic-on-CFR-PEEK bearing to be a very low wearing option for total hip replacement.

  11. A sulfonated poly (aryl ether ether ketone ketone) isomer: synthesis and DMFC performance

    SciTech Connect

    Kim, Yu Seung; Liu, Baijun; Hu, Wei; Jiang, Zhenhua; Robertson, Gilles; Guiver, Michael

    2009-01-01

    A sulfonated poly(aryl ether ether ketone ketone) (PEEKK) having a well-defined rigid homopolymer-like chemical structure was synthesized from a readily-prepared PEEKK post-sulfonation with concentrated sulfuric acid at room temperature within several hours. The polymer electrolyte membrane (PEM) cast from the resulting polymer exhibited an excellent combination of thermal resistance, oxidative and dimensional stability, low methanol fuel permeability and high proton conductivity. Furthermore, membrane electrode assemblies (MEAs) were successfully fabricated and good direct methanol fuel cell (DMFC) performance was observed. At 2 M MeOH feed, the current density at 0.5 V reached 165 mA/cm, which outperformed our reported analogues and eveluated Nafion membranes.

  12. Enhanced osteogenic activity of poly ether ether ketone using calcium plasma immersion ion implantation.

    PubMed

    Lu, Tao; Qian, Shi; Meng, Fanhao; Ning, Congqin; Liu, Xuanyong

    2016-06-01

    As a promising implantable material, poly ether ether ketone (PEEK) possesses similar elastic modulus to that of cortical bones yet suffers from bio-inertness and poor osteogenic properties, which limits its application as orthopedic implants. In this work, calcium is introduced onto PEEK surface using calcium plasma immersion ion implantation (Ca-PIII). The results obtained from scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) confirm the modified layer with varying contents of calcium are formed on PEEK surfaces. Water contact angle measurements reveal the increasing hydrophobicity of both Ca-PIII treated surfaces. In vitro cell adhesion, viability assay, alkaline phosphatase activity and collagen secretion analyses disclose improved the adhesion, proliferation, and osteo-differentiation of rat bone mesenchymal stem cells (bMSCs) on Ca-PIII treated surfaces. The obtained results indicate that PEEK surface with enhanced osteogenic activity can be produced by calcium incorporation. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    SciTech Connect

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  14. [Recent development of research on the biotribology of carbon fiber reinforced poly ether ether ketone composites].

    PubMed

    Chen, Yan; Pan, Yusong

    2014-12-01

    Carbon fiber reinforced poly ether ether ketone (CF/PEEK) composite possesses excellent biocompatible, biomechanical and bioribological properties. It is one of the most promising implant materials for artificial joint. Many factors influence the bioribological properties of CF/PEEK composites. In this paper, the authors reviewed on the biotribology research progress of CF/PEEK composites. The influences of various factors such as lubricant, reinforcement surface modification, functional particles, friction counterpart and friction motion modes on the bio-tribological properties of CF/PEEK composites are discussed. Based on the recent research, the authors suggest that the further research should be focused on the synergistic effect of multiple factors on the wear and lubrication mechanism of CF/PEEK.

  15. Cationic Poly(benzyl ether)s as Self-Immolative Antimicrobial Polymers.

    PubMed

    Ergene, Cansu; Palermo, Edmund F

    2017-10-09

    Self-immolative polymers (SIMPs) are macromolecules that spontaneously undergo depolymerization into small molecules when triggered by specific external stimuli. We report here the first examples of antimicrobial SIMPs with potent, rapid, and broad-spectrum bactericidal activity. Their antibacterial and hemolytic activities were examined as a function of cationic functionality. Polymers bearing primary ammonium cationic groups showed more potent bactericidal activity against Escherichia coli, relative to tertiary and quaternary ammonium counterparts, whereas the quaternary ammonium polymers showed the lowest hemolytic toxicity. These antibacterial polycations undergo end-to-end depolymerization when triggered by an externally applied stimulus. Specifically, poly(benzyl ether)s end-capped with a silyl ether group and bearing pendant allyl side chains were converted to polycations by photoinitiated thiol-ene radical addition using cysteamine HCl. The intact polycations are stable in solution, but they spontaneously unzip into their component monomers upon exposure to fluoride ions, with excellent sensitivity and selectivity. Upon triggered depolymerization, the antibacterial potency was largely retained but the hemolytic toxicity was substantially reduced. Thus, we reveal the first example of a self-immolative antibacterial polymer platform that will enable antibacterial materials to spontaneously unzip into biologically active small molecules upon the introduction of a specifically designed stimulus.

  16. Poly(ether-ether-ketone) orthopedic bearing surface modified by self-initiated surface grafting of poly(2-methacryloyloxyethyl phosphorylcholine).

    PubMed

    Kyomoto, Masayuki; Moro, Toru; Yamane, Shihori; Hashimoto, Masami; Takatori, Yoshio; Ishihara, Kazuhiko

    2013-10-01

    We investigated the production of free radicals on a poly(ether-ether-ketone) (PEEK) substrate under ultraviolet (UV) irradiation. The amount of the ketyl radicals produced from the benzophenone (BP) units in the PEEK molecular structure initially increased rapidly and then became almost constant. Our observations revealed that the BP units in PEEK acted as photoinitiators, and that it was possible to use them to control the graft polymerization of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC). This "self-initiated surface graft polymerization" method is very convenient in the absence of external photoinitiator. We also investigated the effects of the monomer concentration and UV irradiation time on the extent of the grafted PMPC layer. Furthermore, as an application to improving the durability of artificial hips, we demonstrated the nanometer-scale photoinduced grafting of PMPC onto PEEK and carbon fiber-reinforced PEEK (CFR-PEEK) orthopedic bearing surfaces and interfaces. A variety of test revealed significant improvements in the water wettability, frictional properties, and wear resistance of the surfaces and interfaces.

  17. Comparison of surface modification of poly(ether urethanes) on physical properties and blood compatibility

    SciTech Connect

    Wrobleski, D.A.; Cash, D.L.; Hermes, R.E.

    1988-01-01

    Because of their good elastomeric properties including the ability to undergo repeated flexing without failure, polyurethanes are used in a number of biomedical applications including flexing diaphragms or coatings on surfaces in artificial hearts and heart assist devices. In particular, the poly(ether urethanes), are preferred for use in biomedical applications because of their greater hydrolytic stability as compared to poly(ester urethanes). However, poly(ether urethanes), as other polymeric materials in contact with blood, cause formation of thrombus and bacterial infections. These problems might be overcome by incorporation of antithrombogenic substances and/or antibacterial agents in the surface of the polymer. We have explored both of these methods by examining the infusion of polyvinylpyrrolidone (PVP) and poly(ethylene glycol) (PEG) into commercially available poly(ether urethanes) and the graft polymerization of N-vinyl pyrrolidone onto poly(ether urethanes). Preliminary results are presented here. 7 refs., 1 fig.

  18. Chain-extended poly(aryl ether ketones)

    SciTech Connect

    Robeson, L.M.; Winslow, P.A.; Matzner, M.; Harris, J.E.; Maresca, L.M.

    1992-06-09

    This patent describes a process for preparing a poly(aryl ether ketone) polymer. It comprises reacting (n) moles of HAr H with (n + 1) moles of YCOAr{sub 1}COY under Friedel-Crafts polymerization conditions; reacting the product obtained with 2XAR{sub 2}H under Friedel-Crafts polymerization conditions; reacting the product obtained with HOAr{sub 3}OH in the presence of a base and an aprotic solvent; wherein Ar and Ar{sub 1} are divalent aromatic groups, Ar{sub 2} is a divalent aromatic group wherein the substituents X and CO are in para or ortho position relative to each other, Ar{sub 3} is a residue of a dihydric phenol, X and Y are halogen, n is an integer of 1 to 50 and X is one or greater.

  19. Poly(hydroxy amide ethers): New high-barrier thermoplastics

    SciTech Connect

    Brennan, D.J.; White, J.E.; Haag, A.P.; Kram, S.L.; Brown, C.N.; Pikulin, S.

    1993-12-31

    Over the last several years the authors have been involved in a program to prepare thermoplastic resins having high-barrier to oxygen, good processing characteristics, and excellent mechanical properties. One result of these efforts has been the synthesis of poly(hydroxy amide ethers), a new class of high-barrier thermoplastics. These high-molecular-weight polymers are formed by reactions of aromatic diglycidyl ethers with amide-containing bisphenols in high-boiling alcohol solvent. The polymers have good to outstanding barrier to oxygen, with oxygen transmission rates (O{sub 2}TR) of 0.1 - 5.0 cc-mil/100 in{sup 2}-atm-day (barrier units or BU) at high relative humidity (60-80%). Glass transition temperatures (Tg) of the polymers range from 80 to 200{degrees}C. The example shown combines the Tg of an engineering thermoplastic (152{degrees}C) with good barrier (1.5 BU) and mechanical performance. The effect that structure has on O{sub 2}TR and Tg of the polymers will be discussed. Physical properties of selected examples will also be presented.

  20. Vibrational spectroscopic study of pure and silica-doped sulfonated poly(ether ether ketone) membranes

    NASA Astrophysics Data System (ADS)

    Rangasamy, Vijay Shankar; Thayumanasundaram, Savitha; Seo, Jin Won; Locquet, Jean-Pierre

    2015-03-01

    We report the vibrational properties of sulfonated poly(ether ether ketone) (SPEEK) membranes, used as electrolytes in proton exchange membrane (PEM) fuel cells, studied by Fourier transform infrared (FTIR) spectroscopy. We discuss the changes in the vibrational modes of the functional groups present in the polymer arising due to the sulfonation process and the subsequent incorporation of silica particles functionalized with sulfonic acid group. From the infrared spectra, we confirm the incorporation of sulfonic acid group in the polymer chain as well as in the functionalized silica particles. We have also measured the variations in the peak area ratio of the characteristic out-of-plane vibrations of the aromatic rings in the PEEK polymer at 1280 cm-1 with respect to a reference peak at 1305 cm-1. These values were correlated to the crystallinity (XC) values experimentally determined by DSC technique, providing a non-destructive means to calculate the crystallinity of polymer membranes. The calculated XC values were in good agreement with the experimental values. The crystallinity was observed to decrease with increasing degree of sulfonation (DS), indicating the crystalline-to-amorphous phase modification of the polymer by sulfonation, which along with the enhanced ion-exchange capacity and water uptake, is responsible for the improved ionic conductivity at higher DS values.

  1. Interface and properties of inorganic fullerene tungsten sulphide nanoparticle reinforced poly (ether ether ketone) nanocomposites

    NASA Astrophysics Data System (ADS)

    Wang, Nannan; Yang, Zhuxian; Wang, Yuan; Thummavichai, Kunyapat; Xia, Yongde; Ghita, Oana; Zhu, Yanqiu

    We report a simple and effective method to fabricate PEEK (poly ether ether ketone)/IF-WS2 (Inorganic Fullerene Tungsten Sulphide) nanocomposites with IF-WS2 content up to 8 wt%. We have used electron microscopies to characterise the morphology and structural features of the nancomposites, and FTIR and XPS to show that some chemical interface bondings were formed between the PEEK and IF-WS2. We demonstrate that the resulting PEEK/IF-WS2 nanocomposites showed an extraordinary 190% increase in thermal conductivity, 50 °C higher in degradation temperature, and mild improvements in strength and hardness. The increased degradation activation energy from 64 to 76 kJ/mol for neat PEEK and PEEK/IF-WS2 nanocomposites, respectively, is attributed to the synergistic interface between the PEEK matrix and IF-WS2 nanoparticles. The enhancements in both the mechanical and thermal properties will significantly expand the capacities of PEEK-based nanocomposites towards applications where thermal conductivity and stability are important.

  2. Crosslinked sulfonated poly(ether ether ketone) proton exchange membranes for direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Zhong, Shuangling; Cui, Xuejun; Cai, Hongli; Fu, Tiezhu; Zhao, Chengji; Na, Hui

    In the present study, a series of the crosslinked sulfonated poly(ether ether ketone) (SPEEK) proton exchange membranes were prepared. The photochemical crosslinking of the SPEEK membranes was carried out by dissolving benzophenone and triethylamine photo-initiator system in the membrane casting solution and then exposing the resulting membranes after solvent evaporation to UV light. The physical and transport properties of crosslinked membranes were investigated. The membrane performance can be controlled by adjusting the photoirradiation time. The experimental results showed that the crosslinked SPEEK membranes with photoirradiation 10 min had the optimum performance for proton exchange membranes (PEMs). Compared with the non-crosslinked SPEEK membranes, the crosslinked SPEEK membranes with photoirradiation 10 min markedly improved thermal stabilities and mechanical properties as well as hydrolytic and oxidative stabilities, greatly reduced water uptake and methanol diffusion coefficients with only slight sacrifice in proton conductivities. Therefore, the crosslinked SPEEK membranes with photoirradiation 10 min were particularly promising as proton exchange membranes for direct methanol fuel cell (DMFC) applications.

  3. Enhanced osteoblast responses to poly ether ether ketone surface modified by water plasma immersion ion implantation.

    PubMed

    Wang, Heying; Lu, Tao; Meng, Fanhao; Zhu, Hongqin; Liu, Xuanyong

    2014-05-01

    Poly ether ether ketone (PEEK) offers a set of characteristics superior for human implants; however, its application is limited by the bio-inert surface property. In this work, PEEK surface was modified using single step plasma immersion ion implantation (PIII) treatment with a gas mixture of water vapor as a plasma resource and argon as an ionization assistant. Field emission scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy were used to investigate the microstructure and composition of the modified PEEK surface. The water contact angle and zeta-potential of the surfaces were also measured. Osteoblast precursor cells MC3T3-E1 and rat bone mesenchymal stem cells were cultured on the PEEK samples to evaluate their cytocompatibility. The obtained results show that the hydroxyl groups as well as a "ravined structure" are constructed on water PIII modified PEEK. Compared with pristine PEEK, the water PIII treated PEEK is more favorable for osteoblast adhesion, spreading and proliferation, besides, early osteogenic differentiation indicated by the alkaline phosphatase activity is also up-regulated. Our study illustrates enhanced osteoblast responses to the PEEK surface modified by water PIII, which gives positive information in terms of future biomedical applications.

  4. Electrical conductivity of sulfonated poly(ether ether ketone) based composite membranes containing sulfonated polyhedral oligosilsesquioxane

    NASA Astrophysics Data System (ADS)

    Celso, Fabricio; Mikhailenko, Serguei D.; Rodrigues, Marco A. S.; Mauler, Raquel S.; Kaliaguine, Serge

    2016-02-01

    Composite proton exchange membranes (PEMs) intended for fuel cell applications were prepared by embedding of various amounts of dispersed tri-sulfonic acid ethyl POSS (S-Et-POSS) and tri-sulfonic acid butyl POSS (S-Bu-POSS) in thin films of sulfonated poly ether-ether ketone. The electrical properties of the PEMs were studied by Impedance spectroscopy and it was found that their conductivity σ changes with the filler content following a curve with a maximum. The water uptake of these PEMs showed the same dependence. The investigation of initial isolated S-POSS substances revealed the properties of typical electrolytes, which however in both cases possessed low conductivities of 1. 17 × 10-5 S cm-1 (S-Et-POSS) and 3.52 × 10-5 S cm-1 (S-Bu-POSS). At the same time, the insoluble in water S-POSS was found forming highly conductive interface layer when wetted with liquid water and hence producing a strong positive impact on the conductivity of the composite PEM. Electrical properties of the composites were analysed within the frameworks of effective medium theory and bounding models, allowing to evaluate analytically the range of possible conductivity values. It was found that these approaches produced quite good approximation of the experimental data and constituted a fair basis for interpretation of the observed relationship.

  5. Molecular sieve/sulfonated poly(ether ketone ether sulfone) composite membrane as proton exchange membrane

    NASA Astrophysics Data System (ADS)

    Changkhamchom, Sairung; Sirivat, Anuvat

    2012-02-01

    A proton exchange membrane (PEM) is an electrolyte membrane used in both polymer electrolyte membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFCs). Currently, PEMs typically used for PEMFCs are mainly the commercially available Nafion^ membranes, which is high cost and loss of proton conductivity at elevated temperature. In this work, the Sulfonated poly(ether ketone ether sulfone), (S-PEKES), was synthesized by the nucleophilic aromatic substitution polycondensation between bisphenol S and 4,4'-dichlorobenzophenone, and followed by the sulfonation reaction with concentrated sulfuric acid. The molecular sieve was added in the S-PEKES matrix at various ratios to form composite membranes to be the candidate for PEM. Properties of both pure sulfonated polymer and composite membranes were compared with the commercial Nafion^ 117 membrane from Dupont. S-PEKES membranes cast from these materials were evaluated as a polymer electrolyte membrane for direct methanol fuel cells. The main properties investigated were the proton conductivity, methanol permeability, thermal, chemical, oxidative, and mechanical stabilities by using a LCR meter, Gas Chromatography, Thermogravimetric Analysis, Fourier Transform Infrared Spectroscopy, Fenton's reagent, and Universal Testing Machine. The addition of the molecular sieve helped to increase both the proton conductivity and the methanol stability. These composite membranes are shown as to be potential candidates for use as a Proton Exchange Membrane (PEM).

  6. Self-initiated surface graft polymerization of 2-methacryloyloxyethyl phosphorylcholine on poly(ether ether ketone) by photoirradiation.

    PubMed

    Kyomoto, Masayuki; Ishihara, Kazuhiko

    2009-03-01

    In the present paper, we reported the fabrication of a highly hydrophilic nanometer-scale modified surface on a poly(ether ether ketone) (PEEK) substrate by photoinduced graft polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) in the absence of photoinitiators. Photoirradiation results in the generation of semibenzopinacol-containing radicals of benzophenone units in the PEEK molecular structure, which acts as a photoinitiator during graft polymerization. The poly(MPC)-grafted PEEK surface fabricated by a novel and simple polymerization system exhibited unique characteristics such as high wettability and high antiprotein adsorption, which makes it highly suitable for medical applications.

  7. New aromatic activated dihalides and bisphenol monomers for the preparation of novel poly(arylene ethers)

    NASA Technical Reports Server (NTRS)

    Wolfe, James F.

    1993-01-01

    The goal of this research program was to synthesize a series of unique monomers of type I to be utilized at NASA-Langley in the preparation of new poly(arylene ether ketones), poly(arylene ether ketosulfones), and poly(arylene ether ketophosphine oxides). These A-A and A-B monomer systems, which possess activated aryl halide and/or phenolic end groups, are accessible via condensation reactions of appropriately substituted aryl acetonitrile carbanions with activated aryl dihalides followed by oxidative decyanation.

  8. Crystal morphology and phase identifications in poly(aryl ether ketones)s and their copolymers

    SciTech Connect

    Ho, R.M.; Cheng, S.Z.D.; Hsiao, B.S.

    1995-12-01

    A series of poly(aryl ether ketone ketone)s prepared from diphenyl ether (DPE) and terephthalic acid M or isophthalic acid (T) have been investigated. PEKK(T) has been reported to exhibit two polymorphism (form I and form II) based on wide angle X-ray diffraction (WAXD) and electron diffraction (ED) experiments.

  9. Liquid-crystal photoalignment by photosensitive fluorinated poly(arylene ether)

    SciTech Connect

    Li Xiangdan; Zhong Zhenxin; Lee, Seung Hee; Ghang, Gilson; Lee, Myong-Hoon

    2005-03-28

    We report a liquid-crystal (LC) photoalignment material with a high photosensitivity based on the fluorinated poly(arylene ether) containing a chalcone unit in the main chain. The fluorinated poly(arylene ether) exhibited defect-free homogeneous alignment of LCs upon irradiation of linearly polarized UV light for 10 s. Spectroscopic analyses revealed that [2+2] cycloaddition between the chalcone moieties generated the surface anisotropy to induce an efficient alignment of LCs.

  10. Stress shielding and fatigue limits of poly-ether-ether-ketone dental implants.

    PubMed

    Lee, Woo-Taek; Koak, Jai-Young; Lim, Young-Jun; Kim, Seong-Kyun; Kwon, Ho-Beom; Kim, Myung-Joo

    2012-05-01

    The poly-ether-ether-ketone (PEEK) polymer is of great interest as an alternative to titanium in orthopedics because of its biocompatibility and low elastic modulus. This study evaluated the fatigue limits of PEEK and the effects of the low elastic modulus PEEK in relation to existing dental implants. Compressive loading tests were performed with glass fiber-reinforced PEEK (GFR-PEEK), carbon fiber-reinforced PEEK (CFR-PEEK), and titanium rods. Among these tests, GFR-PEEK fatigue tests were performed according to ISO 14801. For the finite element analysis, three-dimensional models of dental implants and bone were constructed. The implants in the test groups were coated with a 0.5-mm thick and 5-mm long PEEK layer on the upper intrabony area. The strain energy densities (SED) were calculated, and the bone resorption was predicted. The fatigue limits of GFR-PEEK were 310 N and were higher than the static compressive strength of GFR-PEEK. The bone around PEEK-coated implants showed higher levels of SED than the bone in direct contact with the implants, and the wider diameter and stiffer implants showed lower levels of SED. The compressive strength of the GFR-PEEK and CFR-PEEK implants ranged within the bite force of the anterior and posterior dentitions, respectively, and the PEEK implants showed adequate fatigue limits for replacing the anterior teeth. Dental implants with PEEK coatings and PEEK implants may reduce stress shielding effects. Dental implant application of PEEK polymer-fatigue limit and stress shielding. Copyright © 2012 Wiley Periodicals, Inc.

  11. Polydopamine-functionalized poly(ether ether ketone) tube for capillary electrophoresis-mass spectrometry.

    PubMed

    Zhou, Wei; Zhang, Wenpeng; Liu, Yikun; Yu, Xinhong; Chen, Zilin

    2017-09-22

    Capillary electrophoresis-mass spectrometry (CE-MS) is a hyphenated technique that combines the advantages like low sample consumption, high separation efficiency, short analytical time in CE and high sensitivity, powerful molecular structure elucidation in MS. Polyimide-coated fused silica capillary has become the most dominant capillary for CE, but it suffers from swelling and aminolysis of polyimide coating when treated with organic solvents and alkaline buffer in the CE-MS interface in which the polyimide coating at the end of the capillary is exposed to the solution, and this phenomenon can result in current instability, irregular electrospray and clogging at outlet after prolonged use. In this work, poly(ether ether ketone) (PEEK) capillary was explored as separation capillary for CE-MS. The problems like swelling and aminolysis of polyimide coating were solved due to the high thermal and chemical stability of PEEK material. After modification with polydopamine, PEEK capillary (PD-PEEK) can generate adjustable electroosmotic flow and provide good separation selectivity. The zwitterion polymer of polydopamine can provide cathodic electroosmotic flow (EOF) at high pH value (pH ≥ 5) and anodic EOF at low pH value (pH ≤ 4), and the EOF mobility can also be adjusted by controlling the modification time of polydopamine. Good separation performance was obtained in the analysis for several classes of compounds including amino acids, phenols and plant hormones at rational EOF direction. Repeatability of the PD-PEEK capillary was studied, with relative standard deviations for intra-day, inter-day runs and between tubes less than 4.94%. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Synthesis and Characterization of Poly (Arylene Ether Benzimidazole) Oligomers

    NASA Technical Reports Server (NTRS)

    Leonard, Michael J.

    1995-01-01

    Several poly(arylene ether benzimidazole) oligomers were prepared by the nucleophilic aromatic substitution reaction of a bisphenol benzimidazole and various alkyl-substituted aromatic bisphenols with an activated aromatic dihalide in N, N-dimethylacetarnide. Moderate to high molecular weight terpolymers were obtained in all cases, as shown by their inherent viscosities, which ranged from 0.50 to 0.87 dL g(sup -1). Glass transition temperatures (T(sub g)s) of polymer powders ranged from 267-280 C. Air-dried unoriented thin film T(sub g)s were markedly lower than those of the powders, whereas T(sub g)s of films dried in a nitrogen atmosphere were identical to those of the corresponding powders. In addition, air-dried films were dark amber and brittle, whereas nitrogen-dried films were yellow and creasable. Nitrogen-dried films showed slightly higher thin-film tensile properties than the air-dried films, as well.

  13. Material with high dielectric constant, low dielectric loss, and good mechanical and thermal properties produced using multi-wall carbon nanotubes wrapped with poly(ether sulphone) in a poly(ether ether ketone) matrix

    NASA Astrophysics Data System (ADS)

    Zhang, Shuling; Wang, Hongsong; Wang, Guibin; Jiang, Zhenhua

    2012-07-01

    A material with high dielectric constant, low dielectric loss, and good mechanical and thermal properties was produced using multi-wall carbon nanotubes (MWCNTs) wrapped with poly(ether sulphone) (PES) dispersed in a poly(ether ether ketone) (PEEK) matrix. The material was fabricated using melt-blending, and MWCNT/PEEK composites show different degrees of improvement in the measured dielectric, mechanical, and thermal properties as compared to pure PEEK. This is attributed to the high conductivity of MWCNTs, the effect of wrapping MWCNTs with PES, the good dispersion of the wrapped MWCNTs in PEEK, and the strong interfacial adhesion between the wrapped MWCNTs and the PEEK.

  14. Synthesis and fluorescence properties of divalent europium-poly(methacrylate containing crown ether structure) complexes

    SciTech Connect

    Higashiyama, N.; Nakamura, H.; Mishima, T.; Shiokawa, J.; Adachi, G. )

    1991-02-01

    This paper reports on divalent europium complexes with poly(methacrylate containing crown ether structure)s, poly(crown ether)s, prepared and their fluorescence properties studied. The polymers used were poly(15-crown-5-methyl methacrylate) (PMA15C5), copoly(15- crown-5-methyl methacrylate-X) (copoly(MA15C5-X)); (X = MMA, EMA, BMA, 2-methoxyethyl methacrylate (MAGI) 3,6,9,12,15- pentaoxahexadecyl methacrylate (MAG5)), poly(18-crown-6- methyl methacrylate) (PMA18C6), and copoly(18-crown-6-methyl methacrylate-MMA) (copoly(MA18C6-MMA)), which were obtained by bulk polymerization. The fluorescence properties of Eu{sup 2+} polymers activated by complexing Eu{sup 2+} ions with crown ether groups were measured in powder form. The Eu{sup 2+}-poly (crown ether)s irradiated by UV light generally gave blue bright emission in the region of 420-465 nm. It was Eu{sup 2+}-copoly(Ma15C5-X); (X = MMA, EMA, and MAG1) that showed the largest emission intensity among the Eu{sup 2+} polymers, and its emission intensity was ca. 20% of that for CaWO{sub 4}:Pb (NBS1026) whose quantum efficiency is about 76%. The intensities of emission for the Eu{sup 2+} polymers containing 15-crown-5 were much larger than that for the ones containing 18-crown-6.

  15. Chemistry and properties of poly(arylene ether 1,3,4-oxadiazole)s and poly(arylene ether 1,2,4-triazole)s

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Hergenrother, P. M.; Wolf, P.

    1992-01-01

    Poly(arylene ether)s containing l,3,4-oxadiazole and 1,2,4-triazole units were prepared by the aromatic nucleophilic displacement reaction of bisphenol oxadiazole and bisphenol triazole compounds with activated aromatic dihalides. The polymers exhibited glass transition temperatures (Tg) ranging from 182 to 242 C, and several polymers exhibited melting transitions (Tm) ranging from 265 to 390 C. Inherent viscosities ranged from 1.02 to 3.40 dl/g, indicating relatively high molecular weights. Thin films exhibited tensile strengths, moduli, and elongations at 23 C of 90-110 MPa, 2.7-3.6 GPa, and 4-7 percent, respectively. Titanium-to-titanium tensile shear specimens of a poly(arylene ether 1,3,4-oxadiazole) exhibited tensile shear strengths at 23 and 150 C of 22.1 and 17.9 MPa, respectively.

  16. Poly(ether ester) Ionomers as Water-Soluble Polymers for Material Extrusion Additive Manufacturing Processes.

    PubMed

    Pekkanen, Allison M; Zawaski, Callie; Stevenson, André T; Dickerman, Ross; Whittington, Abby R; Williams, Christopher B; Long, Timothy E

    2017-04-12

    Water-soluble polymers as sacrificial supports for additive manufacturing (AM) facilitate complex features in printed objects. Few water-soluble polymers beyond poly(vinyl alcohol) enable material extrusion AM. In this work, charged poly(ether ester)s with tailored rheological and mechanical properties serve as novel materials for extrusion-based AM at low temperatures. Melt transesterification of poly(ethylene glycol) (PEG, 8k) and dimethyl 5-sulfoisophthalate afforded poly(ether ester)s of sufficient molecular weight to impart mechanical integrity. Quantitative ion exchange provided a library of poly(ether ester)s with varying counterions, including both monovalent and divalent cations. Dynamic mechanical and tensile analysis revealed an insignificant difference in mechanical properties for these polymers below the melting temperature, suggesting an insignificant change in final part properties. Rheological analysis, however, revealed the advantageous effect of divalent countercations (Ca(2+), Mg(2+), and Zn(2+)) in the melt state and exhibited an increase in viscosity of two orders of magnitude. Furthermore, time-temperature superposition identified an elevation in modulus, melt viscosity, and flow activation energy, suggesting intramolecular interactions between polymer chains and a higher apparent molecular weight. In particular, extrusion of poly(PEG8k-co-CaSIP) revealed vast opportunities for extrusion AM of well-defined parts. The unique melt rheological properties highlighted these poly(ether ester) ionomers as ideal candidates for low-temperature material extrusion additive manufacturing of water-soluble parts.

  17. Low dielectric fluorinated poly(phenylene ether ketone) film and coating

    NASA Technical Reports Server (NTRS)

    Cassidy, Patrick E. (Inventor); Tullos, Gordon L. (Inventor); St.clair, Anne K. (Inventor)

    1990-01-01

    The present invention relates to film and coating materials prepared from novel fluorinated poly(phenylene ether ketones). A fluorinated poly(phenylene ether ketone) is prepared by reacting a bisphenol with 1,1,1,3,3,3 hexafluoro-2,2-bis 4-(4-halobenzoyl) phenyl propane (wherein halo is fluoro or chloro), which is a novel monomer formed as the reaction product of halobenzene (wherein halo is fluoro or chloro) and 1,1,1,3,3,3 hexafluoro-2,2-bis (p-chloro formyl phenyl) propane. Especially beneficial results of this invention are that films and coating materials prepared from the novel fluorinated poly(phenylene ether ketone) are essentially optically transparent/colorless and have a lower dielectric constant than otherwise comparable, commercially available poly(phenylene ether ketones). Moreover, unlike the otherwise comparable commercially available materials, the novel fluorinated poly(phenylene ether ketones) of the present invention can be solution cast or sprayed to produce the films and coatings. Furthermore, the long term thermal stability of the polymers of the present invention is superior to that of the commercially available materials.

  18. A gemini quaternary ammonium poly (ether ether ketone) anion-exchange membrane for alkaline fuel cell: design, synthesis, and properties.

    PubMed

    Si, Jiangju; Lu, Shanfu; Xu, Xin; Peng, Sikan; Xiu, Ruijie; Xiang, Yan

    2014-12-01

    To reconcile the tradeoff between conductivity and dimensional stability in AEMs, a novel Gemini quaternary ammonium poly (ether ether ketone) (GQ-PEEK) membrane was designed and successfully synthesized by a green three-step procedure that included polycondensation, bromination, and quaternization. Gemini quaternary ammonium cation groups attached to the anti-swelling PEEK backbone improved the ionic conductivity of the membranes while undergoing only moderate swelling. The grafting degree (GD) of the GQ-PEEK significantly affected the properties of the membranes, including their ion-exchange capacity, water uptake, swelling, and ionic conductivity. Our GQ-PEEK membranes exhibited less swelling (≤ 40 % at 25-70 °C, GD 67 %) and greater ionic conductivity (44.8 mS cm(-1) at 75 °C, GD 67 %) compared with single quaternary ammonium poly (ether ether ketone). Enhanced fuel cell performance was achieved when the GQ-PEEK membranes were incorporated into H2 /O2 single cells.

  19. Modified nanocrystal cellulose/fluorene-containing sulfonated poly(ether ether ketone ketone) composites for proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Wei, Yingcong; Shang, Yabei; Ni, Chuangjiang; Zhang, Hanyu; Li, Xiaobai; Liu, Baijun; Men, Yongfeng; Zhang, Mingyao; Hu, Wei

    2017-09-01

    Highly sulfonated poly(ether ether ketone ketone)s (SFPEEKKs) with sulfonation degrees of 2.34 (SFPEEKK5) and 2.48 (SFPEEKK10) were synthesized through the direct sulfonation of a fluorene-containing poly(ether ether ketone ketone) under a relatively mild reaction condition. Using the solution blending method, sulfonated nanocrystal cellulose (sNCC)-enhanced SFPEEKK composites (SFPEEKK/sNCC) were successfully prepared for investigation as proton exchange membranes. Transmission electron microscopy showed that sNCC was uniformly distributed in the composite membranes. The properties of the composite membranes, including thermal stability, mechanical properties, water uptake, swelling ratio, oxidative stability and proton conductivity were thoroughly evaluated. Results indicated that the insertion of sNCC could contribute to water management and improve the mechanical performance of the membranes. Notably, the proton conductivity of SFPEEKK5/sNCC-5 was as high as 0.242 S cm-1 at 80 °C. All data proved the potential of SFPEEKK/sNCC composites for proton exchange membranes in medium-temperature fuel cells.

  20. Simulated space environment effects on the optical properties of poly(arylene ethers)

    NASA Technical Reports Server (NTRS)

    Sykes, George F.; Hoogstraten, Craig A.; Slemp, Wayne S.; Hergenrother, Paul M.

    1987-01-01

    Results are reported from a study of the stability of poly(arylene ethers) formed in a reaction of 1,3 -bis(4-chlorobenzoyl)benzene and various bisphenols after experiencing long-term exposure to space conditions. Transparent poly(arylene ethers) films were subjected to separate electron and UV bombardments, as were polysulfone and Kapton films for comparisons. The order of exposure to the two types of radiation was reversed for two sample populations. The optical properties and glass transition temperatures of the samples were determined after irradiation. The poly(arylene ethers) films exhibited good resistance to the electron radiation but suffered severe degradation in the UV environment. The loss of optical transmissivity was proportional to the UV radiation dose.

  1. Synthesis and characterization of high temperature curable poly(arylene ether) structural adhesive and composite matrices

    SciTech Connect

    Mecham, S.J.; Jayaraman, S.; Bobbitt, M.M.

    1996-12-31

    Crosslinked poly(arylene ether) systems are projected to display many desirable properties suitable for aerospace structural adhesive and composite matrix applications. The synthesis and characterization of a series of processable high temperature curing poly(arylene ether) oligomers incorporating terminally reactive phenylethynyl endgroups will be discussed. Characterization of the oligomers includes NMR, intrinsic viscosity, parallel plate rheological behavior, TGA, and DSC. Curing of these oligomers was conducted at or above 380{degrees}C, providing a large processing window. Thermal stability is very good and the melt viscosity of the oligomers in the processing temperature range is exceptionally low.

  2. A facile synthesis of highly stable multiblock poly(arylene ether)s based alkaline membranes for fuel cells

    NASA Astrophysics Data System (ADS)

    Jasti, Amaranadh; Shahi, Vinod K.

    2014-12-01

    Herein, we are disclosing simple route for the preparation of alkaline membranes (AMs) based on aminated multiblock poly(arylene ether)s (AMPEs) synthesized by nucleophilic substitution-poly condensation followed by quaternization and alkalization reactions. In this procedure, four quaternary ammonium groups are successfully introduced without use of carcinogenic reagents such as chloromethylmethyl ether (CMME). Hydrophilic/hydrophobic phase separation is responsible for their high hydroxide conductivity (∼150 mS cm-1 at 80 °C) due to development of interconnected ion transport pathway. AMs are exhibiting good alkaline stability due to the presence of two vicinal quaternary ammonium groups and avoid degradation such as Sommelet-Hauser rearrangement and Hofmann elimination. Vicinal quaternary ammonium groups also resist nucleophilic (OH-) attack and suppress the Stevens rearrangement as well as SN2 substitution reaction due to stearic hindrance. Optimized AM (AMPE-M20N15 (55% DCM)) exhibits about 0.95 V open circuit voltage (OCV) and 48.8 mW cm-2 power density at 65 °C in alkaline direct methanol fuel cell (ADMFC) operation. These results suggest promising begin for the preparation of stable and conductive AMs for ADMFC applications and useful for developing hydroxide conductive materials.

  3. Cross-linked sulfonated poly(ether ether ketone) by using diamino-organosilicon for proton exchange fuel cells.

    PubMed

    Kayser, Marie J; Reinholdt, Marc X; Kaliaguine, Serge

    2011-03-31

    Fuel cells are at the battlefront to find alternate sources of energy to the highly polluting, economically and environmentally constraining fossil fuels. This work uses an organosilicon molecule presenting two amine functions, bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS) with the aim of preparing cross-linked sulfonated poly(ether ether ketone) (SPEEK) based membranes. The hybrid membranes obtained at varying APTMDS loadings are characterized for their acid, proton conductivity, water uptake, and swelling properties. APTMDS may be considered as an extreme case of silica nanoparticle and is therefore most advantageously distributed within the polymeric matrix. The two amine groups can interact, via electrostatic interactions, with the sulfonic acid groups of SPEEK, resulting in a double anchoring of the molecule. The addition of a small amount of APTMDS is enhancing the mechanical and hydrolytic properties of the membranes and allows some unfolding of the polymer chains, rendering some acid sites accessible to water molecules and thus available for proton transport.

  4. Electro-osmotic drag effect on the methanol permeation for sulfonated poly(ether ether ketone) and nafion 117 membranes.

    PubMed

    Chi, Nguyen Thi Que; Bae, Byungchan; Kim, Dukjoon

    2013-11-01

    Electro-osmotic drag effect on the methanol permeation was investigated for sulfonated poly(ether ether ketone) (sPEEK) membrane, and its result was compared with that of Nafion 117 membrane. The electro-osmotic drag coefficient was determined from the limiting current density measured at different temperature. The methanol permeability of sPEEK membrane increased with temperature but its temperature dependence was not as strong as that of Nafion 117 membrane. The methanol permeability or the total methanol flux of Nafion 117 membrane was at least twice higher than that of sPEEK70 membrane (sPEEK membrane with 70% sulfonation degree), as the methanol permeation was highly contributed by the electro-osmotic drag effect. This higher electro-osmotic drag of Nafion 117 membrane is attributed to the bigger ion cluster and waster channel in nanophase and thus more free water absorption than sPEEK membrane.

  5. Rheological and electrical percolation in melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

    NASA Astrophysics Data System (ADS)

    Bangarusampath, D. S.; Ruckdäschel, Holger; Altstädt, Volker; Sandler, Jan K. W.; Garray, Didier; Shaffer, Milo S. P.

    2009-11-01

    Multi-wall carbon nanotubes were dispersed homogeneously throughout a poly(ether ether ketone) matrix by melt processing. The influence of nanotube content on both rheological and electrical properties was analysed. The dynamic storage modulus, G', shows a characteristic solid-like behavior above 1 wt% nanotubes. A sharp transition from an electrically insulating to a conductive composite was observed between 1 and 1.5 wt%. By applying a power-law relation, the rheological and electrical percolation thresholds were found to be 0.9 wt%, and 1.3 wt%, respectively. Considering this data, Guth's filler reinforcement theory provides a valuable estimation of the aspect ratio of the nanotubes after processing and indicates substantial length degradation during the dispersion process.

  6. An estimation of fatigue life for a carbon fibre/poly ether ether ketone hip joint prosthesis.

    PubMed

    Akay, M; Aslan, N

    1995-01-01

    A fracture mechanics approach was applied to estimate the life of a prosthesis injection moulded from short carbon fibre reinforced poly ether ether ketone. Flexural modulus and strength, fracture toughness, fatigue endurance limit, fatigue crack growth rate and threshold stress intensity factor were determined. The dimensions of the test pieces were selected to yield fibre orientation and fibre length distributions similar to those obtained in the prosthesis. Stress levels generated in the prosthesis under different activities were estimated by conducting three-dimensional finite element analysis. It was shown by a fracture mechanics approach that a fatigue failure due to the propagation of an embedded elliptical slit, under these stresses, would be unlikely for a crack length smaller than 1.85 mm. However, the cement would fail under the same conditions, irrespective of the type of the prosthesis employed.

  7. Enhanced response of microbial fuel cell using sulfonated poly ether ether ketone membrane as a biochemical oxygen demand sensor.

    PubMed

    Ayyaru, Sivasankaran; Dharmalingam, Sangeetha

    2014-03-25

    The present study is focused on the development of single chamber microbial fuel cell (SCMFC) using sulfonated poly ether ether ketone (SPEEK) membrane to determine the biochemical oxygen demand (BOD) matter present in artificial wastewater (AW). The biosensor produces a good linear relationship with the BOD concentration up to 650 ppm when using artificial wastewater. This sensing range was 62.5% higher than that of Nafion(®). The most serious problem in using MFC as a BOD sensor is the oxygen diffusion into the anode compartment, which consumes electrons in the anode compartment, thereby reducing the coulomb yield and reducing the electrical signal from the MFC. SPEEK exhibited one order lesser oxygen permeability than Nafion(®), resulting in low internal resistance and substrate loss, thus improving the sensing range of BOD. The system was further improved by making a double membrane electrode assembly (MEA) with an increased electrode surface area which provide high surface area for electrically active bacteria.

  8. Effect of cationic groups in poly(arylene ether sulfone) membranes on reverse electrodialysis performance.

    PubMed

    Cho, Doo Hee; Lee, Kang Hyuck; Kim, Young Mi; Park, Sang Hyun; Lee, Won Hyo; Lee, Sang Min; Lee, Young Moo

    2017-02-16

    In this work, three functional groups were introduced in poly(arylene ether sulfone) membranes to investigate the effects of cationic functional groups in the membranes on reverse electrodialysis performance. Our results showed that controlling the swelling behaviour of the membranes was an important factor for increasing the permselectivity while maintaining their high conductivity.

  9. Electrochemical preparation of ether ketones from (poly)propylene glycol monoethers

    SciTech Connect

    Snoble, K.A.J.

    1984-02-14

    This invention is a method for preparing an ether ketone comprising electrolyzing a solution containing a (poly)propylene glycol monoether, hydroxyl ions and optionally water in an electrolytic cell having an anode at least partially coated with nickel peroxide, silver peroxide, cobalt peroxide or copper peroxide.

  10. Separation of Dimethyl Ether from Syn-Gas Components by Poly(dimethylsiloxane) and Poly(4-methyl-1-pentene) Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2011-05-01

    Permeability and selectivity in gas transport through poly(4-methyl-1-pentene) (TPX) and poly(dimethylsiloxane) (PDMS) using variable temperature mixed gas experiments is reported. Selected gases include H2, CO, CH4, CO2, and dimethyl ether (DME). The DME data is the first to be reported through these membranes. In this paper, the chosen polymers reflect both rubbery and crystalline materials. Rubbery polymers tend to be weakly size sieving, which, in this work, has resulted in larger permeabilities, lower separation factors, and lower activation energies of permeation (Ep). Conversely, the crystalline TPX membranes showed much greater sensitivity to penetrant size; although the gas condensability also played a role in transport.

  11. Preparation of well-defined poly(ether-ester) macromers: photogelation and biodegradability.

    PubMed

    Nakayama, Yasuhide; Okuda, Kanna; Takamizawa, Keiichi; Nakayama, Atsuyoshi

    2011-04-01

    Two series of poly(ether-ester)-based bis-functional macromers terminated with acrylate groups and a well-defined number of ester bonds were synthesized. One series had a chain of 1, 3 or 5 ester bonds at both ends of the central poly(ethylene glycol) block (molecular weight, about 1000), while the other had an alternating structure of oligo(ethylene glycol) each of them linked to two ester bonds, in which 6 or 10 ester bonds were incorporated equally in the macromer molecules and the total molecular weight was adjusted by about 1000. Irradiation of all poly(ether-ester) macromers mixed with camphorquinone resulted in the formation of gels. Gel yield increased and hydrophilic properties of the gels produced decreased with irradiation time. The elastic modulus of the gels decreased with the number of ester bonds. Upon incubation in a PBS solution (pH 8.04), all gels were gradually degraded with time. At 3 weeks of incubation, the degradation ratio increased linearly with the number of ester bonds per unit of molecular weight of the macromers. The order of in vivo degradation rates determined from weight loss was similar to that of the in vitro study. Thus, these poly(ether-ester) macromers may be useful for biodegradable biomaterials or tissue engineering scaffolds.

  12. Reactive Poly(Amic Acid)/ Poly(Glycidyl Methacrylate-r-Poly(ethylene Glycol) Methyl Ether Methacrylate) Blends as Gas Permeation Membranes

    NASA Astrophysics Data System (ADS)

    Beaulieu, Michael; Watkins, James

    2012-02-01

    Polymers containing polar moieties, such as ether groups show an affinity for acidic gases, such as CO2 due to dipole-quadrapole interactions. Polymer blends in which one of the components is poly(ethylene glycol) (PEG) have been studied extensively in literature as a CO2/light gas permeation membrane, but due to the crystallization and poor mechanical properties have been difficult to incorporate PEG above 60wt%. In this study, a series of random copolymers containing both glycidyl methacrylate and poly(ethylene glycol) methyl ether methacrylate in different ratios are blended with a poly(amic acid) prepolymer made from 4, 4'-oxydianiline and pyromellitic dianhydride to create gas permeation membranes. By using a reactive blend PEG loadings above 70% have been realized with sufficient mechanical properties, and since the side chain on the PEGMA is short these blends do not suffer from crystallization.

  13. Ketimine modifications as a route to novel amorphous and derived semicrystalline poly(arylene ether ketone) homo- and copolymers

    NASA Technical Reports Server (NTRS)

    Mohanty, D. K.; Lowery, R. C.; Lyle, G. D.; Mcgrath, J. E.

    1987-01-01

    A series of amine terminal amorphous poly(arylene ether ketone) oligomers of controlled molecular weights (2-15 K) were synthesized. These oligomers have been found to undergo 'self-crosslinking' reactions upon heating above 220 C, via the reaction of the terminal amine groups with the in-chain keto carbonyl functionalities. The resulting networks are ductile, chemically resistant, and nonporous. The networks obtained via generated ketimine functionality were characterized by solid state NMR. They have also been found to be remarkably stable toward hydrolysis. Ketimine functional bishalide monomers have also been synthesized. Such monomers have been utilized to synthesize a wide variety of amorphous poly(arylene ether) ketimine polymers. A high molecular weight hydroquinone functional poly(arylene ether) ketimine has been acid treated to regenerate a poly(arylene ether ketone) backbone in solution. This novel procedure thus allows for the synthesis of important matrix resins under relatively mild conditions.

  14. 40 CFR 721.7700 - Poly(oxy-1,2-ethanediyl), α-hydro-ω-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1). 721.7700 Section 721.7700... Poly(oxy-1,2-ethanediyl), α-hydro-ω-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3... substance identified as poly(oxy-1,2-ethanediyl),α-hydro-ω-(oxiranylmethoxy)-, ether with...

  15. Conductivity enhancement of sulfonated poly(ether ketone ketone) blends using electric field structuring techniques

    NASA Astrophysics Data System (ADS)

    Gasa, Jeffrey V.; Shaw, Montgomery T.

    2004-03-01

    Binary blends composed of an ion-containing polymer and a secondary component were cast under an applied elec. field to produce membranes with anisotropic morphologies. The ion-containing polymer was sulfonated poly(ether ketone ketone) (SPEKK) and the secondary component was either poly(ether imide) (PEI) or styrene-acrylonitrile (SAN) copolymer. A range of compositions and sulfonation levels were studied using this blend system. Optical and SEM micrographs of the resulting membranes showed columnar structures that were oriented along the direction of the field. It was found that electric field alignment only occurs when SPEKK is the dispersed phase but not when it is the matrix. The results show that the conductivities of the membranes that were cast under an electric field were significantly higher than those of the membranes cast without electric field. The conductivity measurements were interpreted in terms of a composite equation with structure-dependent parameters.

  16. Effect of surfactants and temperature on the hyperfiltration performance of poly(ether/urea) membranes

    NASA Technical Reports Server (NTRS)

    Leban, M. I.; Wydeven, T. J.

    1984-01-01

    The individual and combined effects of pasteurization temperature (347 K) and surfactants (anionic, cationic, and neutral) on a poly(ether/urea) thin-film hyperfiltration membrane were studied. Performance of this positively charged membrane was measured in terms of sodium chloride rejection and water flux. The observed effect was mostly on water flux and minimal on salt rejection. Pasteurization temperature caused an irreversible flux decline (flux decline slope of 0.09). The gradual flux reduction caused by neutral and cationic surfactants was reversible, whereas the flux reduction caused by anionic surfactant was irreversible and of similar magnitude to flux reduction caused by pasteurization temperature. The effects of anionic surfactant and pasteurization temperature were additive. Because of flux decline at elevated temperatures the poly(ether/urea) membrane is not very attractive for long-term spaceflight use.

  17. Effect of surfactants and temperature on the hyperfiltration performance of poly(ether/urea) membranes

    NASA Technical Reports Server (NTRS)

    Leban, M. I.; Wydeven, T. J.

    1984-01-01

    The individual and combined effects of pasteurization temperature (347 K) and surfactants (anionic, cationic, and neutral) on a poly(ether/urea) thin-film hyperfiltration membrane were studied. Performance of this positively charged membrane was measured in terms of sodium chloride rejection and water flux. The observed effect was mostly on water flux and minimal on salt rejection. Pasteurization temperature caused an irreversible flux decline (flux decline slope of 0.09). The gradual flux reduction caused by neutral and cationic surfactants was reversible, whereas the flux reduction caused by anionic surfactant was irreversible and of similar magnitude to flux reduction caused by pasteurization temperature. The effects of anionic surfactant and pasteurization temperature were additive. Because of flux decline at elevated temperatures the poly(ether/urea) membrane is not very attractive for long-term spaceflight use.

  18. Graft-crosslinked copolymers based on poly(arylene ether ketone)-gc-sulfonated poly(arylene ether sulfone) for PEMFC applications.

    PubMed

    Zhang, Xuan; Hu, Zhaoxia; Luo, Linqiang; Chen, Shanshan; Liu, Jianmei; Chen, Shouwen; Wang, Lianjun

    2011-07-15

    Novel poly(arylene ether ketone) polymers with fluorophenyl pendants and phenoxide-terminated wholly sulfonated poly(arylene ether sulfone) oligomers are prepared via Ni(0)-catalyzed and nucleophilic polymerization, respectively, and subsequently used as starting materials to obtain graft-crosslinked membranes as polymer electrolyte membranes. The phenoxide-terminated sulfonated moieties are introduced as hydrophilic parts as well as crosslinking units. The chemical structure and morphology of the obtained membranes are confirmed by (1) H NMR and tapping-mode AFM. The properties required for fuel cell applications, including water uptake and dimensional change, as well as proton conductivity, are investigated. AFM results show a clear nanoscale phase-separation microstructure of the obtained membranes. The membranes show good dimensional stability and reasonably high proton conductivities under 30-90% relative humidity. The anisotropic proton conductivity ratios (σ(formula see text) ) of the membranes in water are in the range 0.65-0.92, and increase with an increase in hydrophilic block length. The results indicate that the graft-crosslinked membranes are promising candidates for applications as polymer electrolyte membranes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Characterization of sulfonated poly(ether ether ketone)/poly(vinylidene fluoride-co-hexafluoropropylene) composite membrane for vanadium redox flow battery application

    NASA Astrophysics Data System (ADS)

    Li, Zhaohua; Liu, Le; Yu, Lihong; Wang, Lei; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

    2014-12-01

    Sulfonated poly(ether ether ketone) (SPEEK) and poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-co-HFP)) composite membranes are prepared and investigated in detail for vanadium redox flow battery (VRFB) application. With the high hydrophobicity and stability of P(VDF-co-HFP), the properties of composite membranes such as mechanical property and vanadium ion permeability are effectively improved, showing good trends with the increasing of P(VDF-co-HFP) mass ratio. The VRFB single cell assembled with the composite membrane of 15 wt.% P(VDF-co-HFP) (SPEEK-15% membrane) exhibits higher coulombic efficiency (CE, 95.4%) and energy efficiency (EE, 83.8%) than that assembled with Nafion 117 membrane (CE 91.1% and EE 78.4%) at the current density of 80 mA cm-2. Furthermore, the SPEEK-15% membrane maintains a stable performance during 100 cycles at the current density of 80 mA cm-2. Therefore the SPEEK/P(VDF-co-HFP) composite membrane could be used as low-cost and high-performance membrane for VRFB application.

  20. Space radiation effects on poly(aryl-ether-ketone) thin films and composites

    NASA Technical Reports Server (NTRS)

    Funk, Joan G.; Sykes, George F., Jr.

    1988-01-01

    The purpose of this study was to assess the space durability of poly(aryl-ether-ketone) (PEEK) in the forms of films and graphite fiber reinforced composites. The influence of the film's crystallinity on electron radiation stability was evaluated using X-ray diffraction, DSC, FTIR, and mechanical property tests. The mechanical properties of the composites material were evaluated after electron radiation and after electron radiation followed by thermal cycling simulating 30 years in geosynchronous orbit.

  1. Space radiation effects on poly(aryl-ether-ketone) thin films and composites

    NASA Technical Reports Server (NTRS)

    Funk, Joan G.; Sykes, George F., Jr.

    1988-01-01

    The purpose of this study was to assess the space durability of poly(aryl-ether-ketone) (PEEK) in the forms of films and graphite fiber reinforced composites. The influence of the film's crystallinity on electron radiation stability was evaluated using X-ray diffraction, DSC, FTIR, and mechanical property tests. The mechanical properties of the composites material were evaluated after electron radiation and after electron radiation followed by thermal cycling simulating 30 years in geosynchronous orbit.

  2. Poly(arylene ether ketone) carrying hyperquaternized pendants: Preparation, stability and conductivity

    NASA Astrophysics Data System (ADS)

    Shen, Kunzhi; Zhang, Zhenpeng; Zhang, Haibo; Pang, Jinhui; Jiang, Zhenhua

    2015-08-01

    A new strategy to synthesize comb-shaped poly(arylene ether ketone) ionomers with hyperquaternized pendants was detailed in this work. Poly(arylene ether ketone) with electron-rich phenyl rings on the side chain was copolymerized. These electron-rich phenyl rings which could be chloromethylated and serve as precursors to cationic sites, are introduced during monomer synthesis. After chloromethylation and quaternization on the side chain, these resulting anion exchange membranes exhibit high conductivities and good dimensional stability, which benefit from the side chain type structure. The highest chloride conductivity of 0.047 S cm-1 was observed in PAEK-QTPM-30 (IEC = 1.58 mmol g-1) and swelling ratio is 31.7% at 80 °C. The structural properties of the synthesized poly(arylene ether ketone)s were investigated by 1H NMR spectroscopy. The anion exchange membranes showed excellent thermal stability up to 200 °C under nitrogen and good chemical stability for high conductivity after treating in alkaline condition up to 30 days. These membranes were studied by IEC, water uptake, dimensional stability. The nano-phase separation from ionic aggregation was confirmed by SAXS. This work implies a viable strategy to improve the performance of anion exchange membranes.

  3. Thin film composite nanofiltration membranes fabricated from quaternized poly(ether ether ketone) with crosslinkable moiety using a benign solvent.

    PubMed

    Dong, Xue; Zhang, Qifeng; Zhang, Suobo; Li, Shenghai

    2016-02-01

    Thin film composite nanofiltration membranes were fabricated through dip-coating and in situ cross-linking of quaternized poly(ether ether ketone) containing a certain amount of tertiary amine groups (QAPEEKs) on polyacrylonitrile (PAN) support. The effects of the variables in membrane formation such as the coating polymer concentration, the curing temperature, and the cross-linking agent types on resultant membrane were studied and the membrane properties such as the barrier layer chemical structure, the surface element composition and morphology were investigated. The obtained performance of uncross-linked and cross-linked QAPEEK-70 thin film composites in nanofiltration test was compared. The results indicated that the cross-linking improved the composite membranes' performance. For instance, the membrane cross-linked by bisphenol A diglycidyl ether (BPADGE) named M-C-BPADGE exhibited a MgCl2 rejection of 97.8%, a water flux of 11.8Lm(-2)h(-1), a MWCO of 800Da and corresponding pore size of 0.69nm, while for its uncross-linked membrane named M-U, a MgCl2 rejection of 91.2%, a water flux of 13.5Lm(-2)h(-1), a MWCO with 960Da and a pore size of 0.77nm were found. Furthermore, the M-C-BPADGE membrane exhibited selectivities of 16.0 for separation of mixed Mg(2+) and Na(+) cations, much larger than selectivity of 5.2 obtained for M-U, suggesting that the cross-linked membranes are promising in cation separation.

  4. A new interpretation of SAXS peaks in sulfonated poly(ether ether ketone) (sPEEK) membranes for fuel cells.

    PubMed

    Mendil-Jakani, H; Zamanillo Lopez, I; Legrand, P M; Mareau, V H; Gonon, L

    2014-06-21

    The structure of a commercial sulfonated poly(ether ether ketone) (sPEEK) membrane was analyzed by Small-Angle X-Ray Scattering (SAXS) for different water uptakes obtained after immersion in liquid water at various temperatures. For low membrane swelling, the SAXS profile displays only a wide-angle peak in the 0.2-0.3 Å(-1) region. As the membrane swells, two supplementary correlation peaks arise and shift towards small angles, which are the signature of a structural evolution of the membrane, whereas the wide angle peak remains stable. The SAXS spectra of sPEEK membranes can thus display three correlation peaks simultaneously. Therefore we propose a new interpretation of these SAXS spectra which conclude that the two small angle peaks are attributed to the so-called matrix and ionomer peaks and the wide-angle peak is ascribed to the mean separation distance between sulfonic acid groups grafted onto the polymer backbone. This peak attribution implies that the sPEEK nano-phase separation is triggered by an immersion in hot water (ionomer peak apparition). Our new peak attribution was confirmed by studying the impact of temperature, electron density contrast and ionic exchange capacity.

  5. Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

    NASA Astrophysics Data System (ADS)

    Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

    2017-05-01

    A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

  6. Hydrogen bond cross-linked sulfonated poly(imino ether ether ketone) (PIEEK) for fuel cell membranes

    NASA Astrophysics Data System (ADS)

    Chang, Guanjun; Shang, Zhenfang; Yang, Li

    2015-05-01

    A new diamine monomer, 3,3‧-dihydroxydiphenylamine, is prepared by the palladium catalyzed C-N coupling reaction and the following reduction reaction of 3-bromoanisole and m-anisidine. A series of novel hydrogen bond cross-linked sulfonated poly(imino ether ether ketone) (SPIEEK) are obtained by the copolymerization of sodium 5,5‧-carbonylbis(2-fluorobenzene sulfonate), 4,4‧-difluorobenzophenone with 3,3‧-dihydroxydiphenylamine. The structures of resulting polymers are characterized by means of FT-IR, 1H NMR spectroscopy, and elemental analysis; the results show an agreement with the proposed structure. The resulting SPIEEK membranes display much better resistance to swelling than these without imino groups due to the strong interchain interaction through imino and sulfonic acid groups. The SPIEEK-60 and SPIEEK-80 membrane show the proton conductivity of 0.118 and 0.154 S cm-1 at 80 °C which is higher than Nafion 117 (0.082 S cm-1 at 80 °C). Moreover, the SPIEEK membranes exhibit good mechanical properties and lower methanol permeability due to the hydrogen bondings between the polymer chains.

  7. Nanocomposite Based on Functionalized Gold Nanoparticles and Sulfonated Poly(ether ether ketone) Membranes: Synthesis and Characterization

    PubMed Central

    Venditti, Iole; Fontana, Laura; Scaramuzzo, Francesca A.; Russo, Maria Vittoria; Battocchio, Chiara; Carlini, Laura; Gonon, Laurent; Mareau, Vincent H.; Fratoddi, Ilaria

    2017-01-01

    Gold nanoparticles, capped by 3-mercapto propane sulfonate (Au-3MPS), were synthesized inside a swollen sulfonated poly(ether ether ketone) membrane (sPEEK). The formation of the Au-3MPS nanoparticles in the swollen sPEEK membrane was observed by spectroscopic and microscopic techniques. The nanocomposite containing the gold nanoparticles grown in the sPEEK membrane, showed the plasmon resonance λmax at about 520 nm, which remained stable over a testing period of three months. The size distribution of the nanoparticles was assessed, and the sPEEK membrane roughness, both before and after the synthesis of nanoparticles, was studied by AFM. The XPS measurements confirm Au-3MPS formation in the sPEEK membrane. Moreover, AFM experiments recorded in fluid allowed the production of images of the Au-3MPS@sPEEK composite in water at different pH levels, achieving a better understanding of the membrane behavior in a water environment; the dynamic hydration process of the Au-3MPS@sPEEK membrane was investigated. These preliminary results suggest that the newly developed nanocomposite membranes could be promising materials for fuel cell applications. PMID:28772619

  8. Reinforcement of poly ether sulphones (PES) with exfoliated graphene oxide for aerospace applications

    NASA Astrophysics Data System (ADS)

    Balasubramanian, K.

    2012-09-01

    Composite materials have been used for aerospace for some time now and have gained virtually 100% acceptance as the materials of choice. Speciality polymers like poly ether sulphones (PES), poly ether ether ketones(PEEK), poly ether imides (PEI) are highly preferred materials as plastic matrix due to their superior temperature performance, excellent wear & friction resistance, excellent dimensional accuracy, high tensile strength, high modulus, precise machinability and chemical resistance. In recent years nanoadditives like single and multiwall carbon nanotubes, graphenes and graphene oxides(GO) are finding huge market potential in aerospace and automobile industries. But manufacture related factors such as particle/ matrix interphases, surface activation, mixing process, particle agglomeration, particle size and shape may lead to different property effects. In this research GO/PES composites were prepared by high shear melt blending technique. GO monolayers were exfoliated from natural graphite flake and dispersed homogeneously in PES matrix for the GO content ranging between 0.5 to 2.0 volume percentage with a high shear twin screw batch mixer. These melt blended nanocomposites were injection moulded for mechanical property validation of tensile strength, flexural modulus and impact resistance. Addition of 0.5 volume percentage of GO enhanced the tensile strength and flexural modulus by 40% and 90% respectively. The results show that addition of GO to PES increase mechanical properties due to the formation of continuous network, good dispersion and strong interfacial interactions. The strong interfacial interactions were accounted for the increase in glass transition temperature. Also there was a significant improvement in the impact resistance of the PES/ GO nanocomposite. The injection moulded samples were tested for stealth performance by measuring the electromagnetic shielding property.

  9. 40 CFR 721.7260 - Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether. 721.7260 Section 721.7260 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.7260 Polymer of poly-ethylene-polyamine and...

  10. Surface decorated poly(ester-ether-urethane)s nanoparticles: a versatile approach towards clinical translation.

    PubMed

    Piras, Anna Maria; Sandreschi, Stefania; Malliappan, Sivakumar Ponnurengam; Dash, Mamoni; Bartoli, Cristina; Dinucci, Dinuccio; Guarna, Francesco; Ammannati, Enrico; Masa, Marc; Múčková, Marta; Schmidtová, Ludmila; Chiellini, Emo; Chiellini, Federica

    2014-11-20

    Poly(ester-ether-urethane)s copolymers are a resourceful class of biopolymers for the preparation of nanocarriers for drug delivery applications. However, a simple clinical translation for this synthetic material with biological and quality features is still needed. In this view, poly(ε-caprolactone)-co-poly(ethylene glycol) copolymers were synthesized as semi-bulk pilot (Kg) scale under mild conditions in absence of catalyst, bearing functional termini such as fluorescein tag and anticancer targeting moieties. The obtained materials were processed into surface decorated paclitaxel (PTX) loaded nanoparticles (NPs). The NPs were fully characterized in vitro and in vivo biodistribution in healthy mice evidenced no sign of toxicity and lower levels of PTX in lung and spleen, compared to clinically applied PTX dosage form.

  11. Effects of Poly(cyclohexanedimethylene terephthalate) on Microstructures, Crystallization Behavior and Properties of the Poly(ester ether) Elastomers

    PubMed Central

    Feng, Yi-Cheng; Zhao, Hui; Hao, Tong-Hui; Hu, Guo-Hua; Jiang, Tao; Zhang, Qun-Chao

    2017-01-01

    To understand the role of molecular structure on the crystallization behavior of copolyester in thermoplastic poly(ether ester) elastomers (TPEEs), series of poly(butylene-co-1,4-cyclohexanedimethylene terephthalate) (P(BT-co-CT))-b-poly(tetramethylene glycol) (PTMG) are synthesized through molten polycondensation process. The effects of poly(cyclohexanedimethylene terephthalate) (PCT) content on the copolymer are investigated by Fourier transform infrared spectroscopy (FT-IR), 1H and 13C nuclear magnetic resonance (NMR), gel permeation chromatographs (GPC), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), mechanical, and visible light transmittance tests. FT-IR and NMR results confirm the incorporation of PCT onto the copolymer. WAXD and DSC indicate that the crystalline structure of the copolymers changed from α-PBT lattice to trans-PCT lattice when the molar fraction of PCT (MPCT) is above 30%, while both crystallization and melting temperatures reach the minima. An increase in MPCT led to an increase in the number sequence length of PCT, the thermal stability and the visible light transmittance of the copolymer, but to a slight decrease in tensile strength and elastic modulus. PMID:28773054

  12. Preparation and solution behavior of a thermoresponsive diblock copolymer of poly(ethyl glycidyl ether) and poly(ethylene oxide).

    PubMed

    Ogura, Michihiro; Tokuda, Hiroyuki; Imabayashi, Shin-ichiro; Watanabe, Masayoshi

    2007-08-28

    A thermoresponsive diblock copolymer, poly(ethyl glycidyl ether)-block-poly(ethylene oxide) (PEGE-b-PEO), is synthesized by successive anionic ring-opening polymerization of ethyl glycidyl ether and ethylene oxide using 2-phenoxyethanol as a starting material, and its solution behavior is elucidated in water. In a dilute 1 wt % solution, the temperature-dependent alteration in the polymer hydrodynamic radius (RH) is measured in the temperature range between 5 and 45 degrees C by pulse-gradient spin-echo NMR and dynamic light scattering. The RH value increased with temperature in two steps, where the first step at 15 degrees C corresponds to the core-shell micelle formation and the second step at 40 degrees C corresponds to the aggregation of the core-shell micelles. The formation of the core-shell micelles is supported by the solubilization of a dye (1,6-diphenyl-1,3,5-hexatriene) in the hydrophobic core, which is recognized for a copolymer solution in the temperature range between 20 and 40 degrees C. In this temperature range, the core-shell micelles and the unimers coexist and the fraction of the former gradually increases with increasing temperature, suggesting equilibrium between the micelles and the unimers. In the concentrated regime (40 wt % solution), the solution forms a gel and the small-angle X-ray scattering measurements reveal the successive formation of hexagonal and lamellar liquid crystal phases with increasing temperature.

  13. Anti-infective and osteointegration properties of silicon nitride, poly(ether ether ketone), and titanium implants.

    PubMed

    Webster, T J; Patel, A A; Rahaman, M N; Sonny Bal, B

    2012-12-01

    Silicon nitride (Si(3)N(4)) is an industrial ceramic used in spinal fusion and maxillofacial reconstruction. Maximizing bone formation and minimizing bacterial infection are desirable attributes in orthopedic implants designed to adhere to living bone. This study has compared these attributes of Si(3)N(4) implants with implants made from two other orthopedic biomaterials, i.e. poly(ether ether ketone) (PEEK) and titanium (Ti). Dense implants made of Si(3)N(4), PEEK, or Ti were surgically implanted into matching rat calvarial defects. Bacterial infection was induced with an injection of 1×10(4)Staphylococcus epidermidis. Control animals received saline only. On 3, 7, and 14days, and 3months post-surgery four rats per time period and material were killed, and calvariae were examined to quantify new bone formation and the presence or absence of bacteria. Quantitative evaluation of osteointegration to adjacent bone was done by measuring the resistance to implant push-out (n=8 rats each for Ti and PEEK, and n=16 rats for Si(3)N(4)). Three months after surgery in the absence of bacterial injection new bone formation around Si(3)N(4) was ∼69%, compared with 24% and 36% for PEEK and Ti, respectively. In the presence of bacteria new bone formation for Si(3)N(4), Ti, and PEEK was 41%, 26%, and 21%, respectively. Live bacteria were identified around PEEK (88%) and Ti (21%) implants, whereas none were present adjacent to Si(3)N(4). Push-out strength testing demonstrated statistically superior bone growth onto Si(3)N(4) compared with Ti and PEEK. Si(3)N(4) bioceramic implants demonstrated superior new bone formation and resistance to bacterial infection compared with Ti and PEEK. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  14. Controlled release of protein from biodegradable multi-sensitive injectable poly(ether-urethane) hydrogel.

    PubMed

    Li, Xiaomeng; Wang, Yangyun; Chen, Jiaming; Wang, Yinong; Ma, Jianbiao; Wu, Guolin

    2014-03-12

    The synthesis and characterization of multi-sensitive polymers for use as injectable hydrogels for controlled protein/drug delivery is reported. A series of biodegradable multi-sensitive poly(ether-urethane)s were prepared through a simple one-pot condensation of poly(ethylene glycol), 2,2'-dithiodiethanol, N-methyldiethanolamine, and hexamethylene diisocyanate. The sol-gel phase transition behaviors of the obtained copolymers were investigated. Experimental results showed that the aqueous medium comprising the multi-segment copolymers underwent a sol-to-gel phase transition with increasing temperature and pH. At a certain concentration, the copolymer solution could immediately change to a gel under physiological conditions (37 °C and pH 7.4), indicating their suitability as in situ injectable hydrogels in vivo. Insulin was used as a model protein drug for evaluation of the injectable hydrogels as a site-specific drug delivery system. The controlled release of insulin from the hydrogel devices was demonstrated by degradation of the copolymer, which is modulated via the 2,2'-dithiodiethanol content in the poly(ether-urethane)s. These hydrogels having multi-responsive properties may prove to be promising candidates for injectable and controllable protein drug delivery devices.

  15. Parallel Synthesis of Poly(amino ether)-Templated Plasmonic Nanoparticles for Transgene Delivery

    PubMed Central

    2015-01-01

    Plasmonic nanoparticles have been increasingly investigated for numerous applications in medicine, sensing, and catalysis. In particular, gold nanoparticles have been investigated for separations, sensing, drug/nucleic acid delivery, and bioimaging. In addition, silver nanoparticles demonstrate antibacterial activity, resulting in potential application in treatments against microbial infections, burns, diabetic skin ulcers, and medical devices. Here, we describe the facile, parallel synthesis of both gold and silver nanoparticles using a small set of poly(amino ethers), or PAEs, derived from linear polyamines, under ambient conditions and in absence of additional reagents. The kinetics of nanoparticle formation were dependent on PAE concentration and chemical composition. In addition, yields were significantly greater in case of PAEs when compared to 25 kDa poly(ethylene imine), which was used as a standard catonic polymer. Ultraviolet radiation enhanced the kinetics and the yield of both gold and silver nanoparticles, likely by means of a coreduction effect. PAE-templated gold nanoparticles demonstrated the ability to deliver plasmid DNA, resulting in transgene expression, in 22Rv1 human prostate cancer and MB49 murine bladder cancer cell lines. Taken together, our results indicate that chemically diverse poly(amino ethers) can be employed for rapidly templating the formation of metal nanoparticles under ambient conditions. The simplicity of synthesis and chemical diversity make PAE-templated nanoparticles useful tools for several applications in biotechnology, including nucleic acid delivery. PMID:25084138

  16. A Novel, Poly(Ethyl Ethylene Ether) Inhibitor to Trypsin from Marine Cyanobacteria, Lyngbya confervoides.

    PubMed

    Devi, Ambika; Prasanth, Shankar; Murugesh, Easwaran; Haridas, Karickal R; Sabu, Abdulhameed; Haridas, Madhathilkovilakathu

    2016-03-01

    A novel, poly(ethyl ethylene ether) inhibitor to trypsin was purified from marine cyanobacteria, Lyngbya confervoides from the coastal areas of Thalassery, North Kerala. The kinetics and the thermodynamic parameters of its interactions with the enzyme were also studied. It was demonstrated that the substrate binding, catalytic triad of the enzyme could be blocked by the inhibitor, as expressed by molecular simulation studies. The study also showed that the cyanobacterial group could prove to be a potential source of novel enzyme inhibitors for various applications.

  17. Preparation of Sulfonated Poly(aryl ether sulfone) Electrospun Mat/Phosphosilicate Composite Proton Exchange Membrane

    NASA Astrophysics Data System (ADS)

    Wang, Limei; Dou, Liyan; Guan, Guoying

    2017-03-01

    Side-chain-type sulfonated poly(aryl ether sulfone) (SPES) was synthesized and then electrospun into mats. Phosphosilicate glass (PS) via in situ sol-gel synthesis was enclosed in the mats to form a new reinforced composite membrane. The SPES/PS composite membranes showed satisfactory dimensional change behavior with varying humidity. Especially, the composite membrane exhibits excellent proton conductivity at harsh measurement conditions of low humidity at 80°C. The composite membrane with outstanding combined properties has potential applications for high temperature polymer electrolyte membrane fuel cells.

  18. Poly(arylene ether-co-imidazole)s as toughness modifiers for epoxy resins

    NASA Technical Reports Server (NTRS)

    Mcdaniel, Patricia D. (Inventor); Connell, John W. (Inventor)

    1994-01-01

    A toughened epoxy was prepared by reacting an epoxy resin with a poly(arylene ether-co-imidazole)s (PAEI). The epoxy resin comprises N,N,N',N'tetraglycidyl-4,4'- methylenebisbenzenamine and 4-aminophenyl sulfone. The PAEI was prepared by reacting an aromatic bisphenol, a bisphenol imidazole, and an activated aromatic dihalide or dinitro compound in the presence of potassium carbonate in a polar aprotic solvent at an elevated temperature. The epoxies which were modified with these particular PAEI's showed a significant increase in toughness with only a 10 weight percent loading of the PAEI into the epoxy. These toughened epoxies were used to prepare composites and molded parts.

  19. Crystal structures of poly(aryl ether) dendrons with palladium scorpionate complexes at their focal point.

    PubMed

    Sánchez-Méndez, Alberto; de Jesús, Ernesto; Flores, Juan C; Gómez-Sal, Pilar

    2007-06-11

    Novel palladium(II) complexes with bis(pyrazol-1-yl)methane ligands at the focal point of G0-G3 poly(aryl ether) Fréchet-type dendrons are reported. The molecular structures of the metallodendrimer series G0, G1, and G2 [(dend)CH(3,5-Me2pz)2(PdCl2)] have been determined by X-ray diffraction methods. The three structures show a similar three-dimensional organization of the metal complex, which is progressively engulfed by the branches with increasing dendrimer generation.

  20. Preparation of Sulfonated Poly(aryl ether sulfone) Electrospun Mat/Phosphosilicate Composite Proton Exchange Membrane

    NASA Astrophysics Data System (ADS)

    Wang, Limei; Dou, Liyan; Guan, Guoying

    2017-01-01

    Side-chain-type sulfonated poly(aryl ether sulfone) (SPES) was synthesized and then electrospun into mats. Phosphosilicate glass (PS) via in situ sol-gel synthesis was enclosed in the mats to form a new reinforced composite membrane. The SPES/PS composite membranes showed satisfactory dimensional change behavior with varying humidity. Especially, the composite membrane exhibits excellent proton conductivity at harsh measurement conditions of low humidity at 80°C. The composite membrane with outstanding combined properties has potential applications for high temperature polymer electrolyte membrane fuel cells.

  1. Poly(aryl ethers) and related polysiloxane copolymer molecular coatings: Preparation and radiation degradation

    NASA Technical Reports Server (NTRS)

    Mcgrath, J. E.

    1982-01-01

    The radiation degradation of poly(arylene ether sulfones) and related materials is studied. These basic studies are important both as a means to developing stronger, more stable matrix resins for composite materials, as well as to improve the data base in regard to chemical structure-physical property relationships. Thirty homo and copolymers were synthesized, at least partially characterized and, in several cases suitable film casting techniques were developed. Four samples were chosen for initial radiation degradation. Poly(dimethyl siloxane) soft bocks/segments can preferentially migrate to the surface of copolymer films. Since siloxanes are utilized as thermal control coatings, this form of 'molecular' coating is of interest. The chemistry for preparing such copolymers with any of the polymers described was demonstrated.

  2. 40 CFR 721.10398 - Poly(oxy-1,2-ethanediyl),. alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic). 721.10398 Section 721.10398 Protection of...-ethanediyl),. alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic). (a) Chemical substance... poly(oxy-1,2-ethanediyl), .alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (PMN P-10-495)...

  3. 40 CFR 721.10398 - Poly(oxy-1,2-ethanediyl),. alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic). 721.10398 Section 721.10398 Protection of...-ethanediyl),. alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic). (a) Chemical substance... poly(oxy-1,2-ethanediyl), .alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (PMN P-10-495)...

  4. 40 CFR 721.10398 - Poly(oxy-1,2-ethanediyl),. alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic). 721.10398 Section 721.10398 Protection of...-ethanediyl),. alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (generic). (a) Chemical substance... poly(oxy-1,2-ethanediyl), .alpha., -monoalkyl ethers-.omega.-mono (hydrogen maleate)- (PMN P-10-495)...

  5. Fibers by bioresorbable poly(ester-ether-ester)s as potential suture threads: a preliminary investigation.

    PubMed

    Guerra, G D; Cerrai, P; Tricoli, M; Maltinti, S; Anguillesi, I; Barbani, N

    1999-01-01

    Fibers made by a bioresorbable poly(epsilon-caprolactone)-block-poly(oxyethylene)-block-poly(epsilon-caprolactone) copolymer, having a number average molecular mass of about 200,000 Da and an average molar composition of 66% oxycaproyl units and 34% oxyethylene units, were melt-spun, with the aim at using them as suture threads. Their properties were investigated by the stress-strain test and by differential scanning calorimetry (DSC). The results obtained show that the properties of this material depend very strongly on the alignment of its macromolecules. In particular, the only partial alignment, obtainable by a relatively moderate drawing just after the extrusion, leads to values of elongation at break too high for use of the fibers as suture threads. The DSC analysis reveals interesting properties of the material, but also confirms their strong dependence on the extrusion procedure and on the mechanical treatment. In conclusion, the results of this preliminary study show that the spinning technique must be improved, and that further investigations are necessary to ascertain the possibility of using these poly(ester-ether-ester)s for the fabrication of suture threads.

  6. Sulfonated poly(ether sulfone)s containing pyridine moiety for PEMFC.

    PubMed

    Jang, Hohyoun; Islam, Md Monirul; Lim, Youngdon; Hossain, Md Awlad; Cho, Younggil; Joo, Hyunho; Kim, Whangi; Jeon, Heung-Seok

    2014-10-01

    Sulfonated poly(ether sulfone)s with varied degree of sulfonation (DS) were prepared via post-sulfonation of synthesized pyridine based poly(ether sulfone) (PPES) using concentrated sulfuric acid as sulfonating agent. The DS was varied with different mole ratio of 4,4'-(2,2-diphenylethenylidene)diphenol, DHTPE in the polymer unit. PPES copolymers were synthesized by direct polycondensation of pyridine unit with bis-(4-fluorophenyl)-sulfone, 4, 4'-sulfonyldiphenol and DHTPE. The structure of the resulting PPES copolymer membranes with different sulfonated units were studied by 1H NMR spectroscopy and thermogravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymer with water. The ion exchange capacity (IEC) and proton conductivity were evaluated according to the increase of DS. The water uptake (WU) of the resulting membranes was in the range of 17-58%, compared to that of Nafion 211 28%. The membranes provided proton conductivities of 65-95 mS/cm in contrast to 103 mS/cm of Nafion 211.

  7. Modification of poly(ether urethane) with fluorinated phosphorylcholine polyurethane for improvement of the blood compatibility.

    PubMed

    Tan, Dongsheng; Zhang, Xiaoqing; Li, Jiehua; Tan, Hong; Fu, Qiang

    2012-02-01

    In order to improve the blood compatibility, poly(ether urethane) (PEU) and fluorinated phosphorylcholine polyurethane (P-HFPC) were used to prepare PU/P-HFPC blends by solution mixing. The hemocompatibility in vitro was evaluated with protein adsorption and platelet-rich plasma (PRP) contact tests. It was found that the amount of adsorbed protein on surface was decreased by 87%, and almost no platelet adhesion and activation was observed on the surface of blends when P-HFPC content was above 5 wt %. After adding P-HFPC, the blends basically kept favorable mechanical properties of PEU though the content of P-HFPC rises to 20 wt %. To better understand the relationship between structure and properties, the phase structure and surface property of the blend films were further investigated via differential scanning calorimetry, dynamic mechanical analysis, atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. The results indicated that the fluorinated phosphorylcholine units could be easily enriched on the surface of blend films due to the phase separation between the PEU and P-HFPC. Therefore, ordinary poly(ether urethane)s can obtain both satisfactory blood compatibility and good mechanical properties just by blending with small amount of P-HFPC.

  8. Transparent Films from CO2‐Based Polyunsaturated Poly(ether carbonate)s: A Novel Synthesis Strategy and Fast Curing

    PubMed Central

    Subhani, Muhammad Afzal; Köhler, Burkhard; Gürtler, Christoph; Leitner, Walter

    2016-01-01

    Abstract Transparent films were prepared by cross‐linking polyunsaturated poly(ether carbonate)s obtained by the multicomponent polymerization of CO2, propylene oxide, maleic anhydride, and allyl glycidyl ether. Poly(ether carbonate)s with ABXBA multiblock structures were obtained by sequential addition of mixtures of propylene oxide/maleic anhydride and propylene oxide/allyl glycidyl ether during the polymerization. The simultaneous addition of both monomer mixtures provided poly(ether carbonate)s with AXA triblock structures. Both types of polyunsaturated poly(ether carbonate)s are characterized by diverse functional groups, that is, terminal hydroxy groups, maleate moieties along the polymer backbone, and pendant allyl groups that allow for versatile polymer chemistry. The combination of double bonds substituted with electron‐acceptor and electron‐donor groups enables particularly facile UV‐ or redox‐initiated free‐radical curing. The resulting materials are transparent and highly interesting for coating applications. PMID:27028458

  9. Preparing alkaline anion exchange membrane with enhanced hydroxide conductivity via blending imidazolium-functionalized and sulfonated poly(ether ether ketone)

    NASA Astrophysics Data System (ADS)

    Li, Zhen; Jiang, Zhongyi; Tian, Huimin; Wang, Siwen; Zhang, Bei; Cao, Ying; He, Guangwei; Li, Zongyu; Wu, Hong

    2015-08-01

    The development of alkaline anion exchange membrane (AEM) with both high ion conductivity and stabilities is of great significance for fuel cell applications. In this study, a facile acid-base blending method is designed to improve AEM performances. Basic imidazolium-functionalized poly (ether ether ketone) with a high functionalization degree is employed as polymer matrix to pursue high ion-exchange capacity (IEC) as well as high hydroxide conductivity, meanwhile acidic sulfonated poly (ether ether ketone) (SPEEK) is employed as the cross-linking agent to enhance the stabilities of the blend membranes. Particularly, an in-situ Menshutkin/crosslinking method is exploited to prevent the flocculation in the preparation process of blend membranes. As a result, dense and defect-free blend membranes are obtained. The blend membranes exhibit high level of IEC up to 3.15 mmol g-1, and consequently possess elevated hydroxide conductivity up to 31.59 mS cm-1 at 30 °C. In addition, benefiting from the strong electrostatic interaction introduced by the acid-base blending, the stabilities and methanol resistance of blend membranes are enhanced.

  10. Separator Membrane from Crosslinked Poly(Vinyl Alcohol) and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride)

    PubMed Central

    Rohatgi, Charu Vashisth; Dutta, Naba K.; Choudhury, Namita Roy

    2015-01-01

    In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA) with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride) (PMVE-MA). Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity), thermal and electrochemical properties using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications. PMID:28347019

  11. Degradation of imidazolium- and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone) anion exchange membranes.

    PubMed

    Chen, Dongyang; Hickner, Michael A

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by ¹H NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 °C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 °C but much lower stability at 80 °C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  12. Degradation of Imidazolium- and Quaternary Ammonium-Functionalized Poly(fluorenyl ether ketone sulfone) Anion Exchange Membranes

    SciTech Connect

    Chen, DY; Hickner, MA

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by H-1 NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 degrees C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 degrees C but much lower stability at 80 degrees C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  13. Chemistry and properties of poly(arylene ether benzoxazole)s

    NASA Technical Reports Server (NTRS)

    Smith, J. G., Jr.; Connell, J. W.; Hergenrother, P. M.

    1992-01-01

    Several new poly(arylene ether benzoxazole)s (PAEBs) were prepared by the nucleophilic displacement reaction of activated aromatic difluorides with two novel bis(hydroxyphenyl benzoxazole), using potassium carbonate. The 6F-containing PAEBs exhibited better solubility and higher Tgs than did the 6,6'-bis-(2-(4-hydroxyphenyl)benzoxazole)-derived polymers. Several of the 6,6'bis(2-(4-hydroxyphenyl)benzoxazole)-derived polymers exhibited crystallinity by DSC and wide-angle X-ray diffraction. Unorientated thin film properties of the 6F-containing PAEBs were comparable to those of other 6F-containing PAEBS that were previously reported. The chemistry and the physical and mechanical properties of the above polymers are discussed.

  14. Chitin nanowhisker-supported sulfonated poly(ether sulfone) proton exchange for fuel cell applications.

    PubMed

    Zhang, Chan; Zhuang, Xupin; Li, Xiaojie; Wang, Wei; Cheng, Bowen; Kang, Weimin; Cai, Zhanjun; Li, Mengqin

    2016-04-20

    To balance the relationship among proton conductivity and mechanic strength of sulfonated poly(ether sulfone) (SPES) membrane, chitin nanowhisker-supported nanocomposite membranes were prepared by incorporating whiskers into SPES. The as-prepared chitin whiskers were prepared by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) mediated oxidation of α-chitin from crab shells. The structure and properties of the composite membranes were examined as proton exchange membrane (PEM). Results showed that chitin nanowhiskers were dispersed incompactly in the SPES matrix. Thermal stability, mechanical properties, water uptake and proton conductivity of the nanocomposite films were improved from those of the pure SPES film with increasing whisker content, which ascribed to strong interactions between whiskers and between SPES molecules and chitin whiskers via hydrogen bonding. These indicated that composition of filler and matrix got good properties and whisker-supported membranes are promising materials for PEM.

  15. Interaction of single-walled carbon nanotubes with poly(propyl ether imine) dendrimers

    NASA Astrophysics Data System (ADS)

    Jayamurugan, G.; Vasu, K. S.; Rajesh, Y. B. R. D.; Kumar, S.; Vasumathi, V.; Maiti, P. K.; Sood, A. K.; Jayaraman, N.

    2011-03-01

    We study the complexation of nontoxic, native poly(propyl ether imine) dendrimers with single-walled carbon nanotubes (SWNTs). The interaction was monitored by measuring the quenching of inherent fluorescence of the dendrimer. The dendrimer-nanotube binding also resulted in the increased electrical resistance of the hole doped SWNT, due to charge-transfer interaction between dendrimer and nanotube. This charge-transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. We also report the effect of acidic and neutral pH conditions on the binding affinities. Experimental studies were supplemented by all atom molecular dynamics simulations to provide a microscopic picture of the dendrimer-nanotube complex. The complexation was achieved through charge transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen, and n-propyl moieties of the dendrimer.

  16. Design of poly(ether block amide)/polyacrylonitrile composite membrane for carbon dioxide capture

    NASA Astrophysics Data System (ADS)

    Wang, Lianjun; Ji, Pengfei; Li, Yang; di, Mingming; Lv, Quan; Li, Shuguang

    2015-03-01

    In this study, poly(ether block amide) was used as coating material to develop a novel composite polymer membrane for CO2 capture. Polyacrylonitrile (PAN) ultrafiltration membrane was applied as substrate. Between them, a gutter layer prepared from cross-linked polydimethylsiloxane (PDMS) blending with amino silicone was introduced to improve separation performance of the composite membrane. The separation properties of resultant triple layer composite membrane was characterized using pure CO2 and N2 gases. It was found that the crosslinking degree of the gutter layer had great influence on membrane performance, which could be significantly improved with the help of amino-PDMS gutter layer compared with that of the membrane having Pebax coating directly onto PAN substrate. Using 2 wt.% Pebax coating solution and properly cross-linked gutter layer, the designed Pebax/amino-PDMS/PAN composite membrane showed CO2 permeance of 147 GPU and CO2/N2 selectivity of 62.

  17. Hierarchical porous poly (ether sulfone) membranes with excellent capacity retention for vanadium flow battery application

    NASA Astrophysics Data System (ADS)

    Chen, Dongju; Li, Dandan; Li, Xianfeng

    2017-06-01

    A hierarchical poly (ether sulfone) (PES) porous membrane is facilely fabricated via a hard template method for vanadium flow battery (VFB) application. The construction of this hierarchical porous membrane is prepared via removing templates (phenolphthalein). The pore size can be well controlled by optimizing the template content in the cast solution, ensuring the membrane conductivity and selectively. The prepared hierarchical porous membrane can combine high ion selectivity with high proton conductivity, which renders a good electrochemical performance in a VFB. The optimized hierarchical porous membrane shows a columbic efficiency of 94.52% and energy efficiency of 81.66% along with a superior ability to maintain stable capacity over extended cycling at a current density of 80 mA cm-2. The characteristics of low cost, proven chemical stability and high electrochemical performance afford the hierarchical PES porous membrane great prospect in VFB application.

  18. Controlled molecular weight poly(arylene ether benzimidazole)s endcapped with benzimidazole and acetylene groups

    SciTech Connect

    Smith, J.G. Jr.; Connell, J.W.; Hergenrother, P.M.

    1993-12-31

    As a continuation of work on poly(arylene ether benzimidazole)s (PAEBIs), a series of controlled molecular weight polymers endcapped with benzimidazole, ethynyl, and phenylethynyl groups were prepared at stoichiometric imbalances of 7 and 10 mole percent and characterized. Earlier work with benzimidazole endcapped PAEBIs prepared at stoichiometric imbalances as high as 7 mole percent has shown very good retention of thin film properties up to 232{degrees}C. Ethynyl and phenylethynyl endcapped PAEBIs, air cured to 330{degrees}C, exhibited increases in Tgs of {approximately}20-30{degrees}C with respect to benzimidazole endcapped PAEBIs. Thin film properties for the ethynyl and phenylethynyl endcapped PAEBIs were similar to benzimidazole endcapped PAEBIs up to 232{degrees}C. Ethynyl and phenylethynyl endcapped PAEBI films tested at 250{degrees}C exhibited good retention of tensile properties.

  19. Novel polymer electrolyte from poly(carbonate-ether) and lithium tetrafluoroborate for lithium-oxygen battery

    NASA Astrophysics Data System (ADS)

    Lu, Qi; Gao, Yonggang; Zhao, Qiang; Li, Ji; Wang, Xianhong; Wang, Fosong

    2013-11-01

    Novel polymer electrolyte based on low-molecular weight poly(carbonate-ether) and lithium tetrafluoroborate has been prepared and used in lithium-oxygen battery for the first time, the electrolyte with approximate 17% of LiBF4 showed ionic conductivity of 1.57 mS cm-1. Infrared spectra analysis indicates that obvious interaction between the lithium ions and partial oxygen atoms in the host polymer exists, and the lithium salt and the host polymer have good miscibility. The lithium-oxygen battery from this polymer electrolyte shows similar cyclic stability to traditional liquid electrolyte observed by FT-IR, AFM and electrochemical measurements, which may provide a new choice for fabrication of all-solid-state high-capacity rechargeable lithium-oxygen battery with better safety.

  20. Chemistry and properties of poly(arylene ether benzoxazole)s

    NASA Technical Reports Server (NTRS)

    Smith, J. G., Jr.; Connell, J. W.; Hergenrother, P. M.

    1992-01-01

    Several new poly(arylene ether benzoxazole)s (PAEBs) were prepared by the nucleophilic displacement reaction of activated aromatic difluorides with two novel bis(hydroxyphenyl benzoxazole), using potassium carbonate. The 6F-containing PAEBs exhibited better solubility and higher Tgs than did the 6,6'-bis-(2-(4-hydroxyphenyl)benzoxazole)-derived polymers. Several of the 6,6'bis(2-(4-hydroxyphenyl)benzoxazole)-derived polymers exhibited crystallinity by DSC and wide-angle X-ray diffraction. Unorientated thin film properties of the 6F-containing PAEBs were comparable to those of other 6F-containing PAEBS that were previously reported. The chemistry and the physical and mechanical properties of the above polymers are discussed.

  1. Interaction of single-walled carbon nanotubes with poly(propyl ether imine) dendrimers

    SciTech Connect

    Jayamurugan, G.; Rajesh, Y. B. R. D.; Jayaraman, N.; Vasu, K. S.; Kumar, S.; Sood, A. K.; Vasumathi, V.; Maiti, P. K.

    2011-03-14

    We study the complexation of nontoxic, native poly(propyl ether imine) dendrimers with single-walled carbon nanotubes (SWNTs). The interaction was monitored by measuring the quenching of inherent fluorescence of the dendrimer. The dendrimer-nanotube binding also resulted in the increased electrical resistance of the hole doped SWNT, due to charge-transfer interaction between dendrimer and nanotube. This charge-transfer interaction was further corroborated by observing a shift in frequency of the tangential Raman modes of SWNT. We also report the effect of acidic and neutral pH conditions on the binding affinities. Experimental studies were supplemented by all atom molecular dynamics simulations to provide a microscopic picture of the dendrimer-nanotube complex. The complexation was achieved through charge transfer and hydrophobic interactions, aided by multitude of oxygen, nitrogen, and n-propyl moieties of the dendrimer.

  2. Zero-birefringence photosensitive poly(arylene ether) for optical waveguides

    NASA Astrophysics Data System (ADS)

    Li, Xiang-Dan; Zhong, Zhen-Xin; Kim, Jang Joo; Lee, Myong-Hoon

    2005-01-01

    Novel photosensitive fluorinated poly(arylene ether) containing chalcone unit (F-PAECh) in the main chain was synthesized from decafluorinated chalcone and fluorinated bisphenol at low temperature for polymer optical waveguide application. Upon UV irradiation on the resulting polymer film, [2+2] cycloaddition of chalocone moiety induced the anisotropic decrease of the refractive indices (nTE and nTM) accompanied with crosslinking of polymer film. The decrease was more significant in in-plane direction than out-of-plane direction, and consequently, zero birefringence was obtained with 4.5 min of exposure. Zero-birefringence as well as its excellent optical properties of F-PAECh makes it a promising candidate material for use in high-performance wavelength division multiplexing components such as polarization-independent arrayed waveguide gratings and Bragg wavelength filters.

  3. Development of an AMBER-compatible transferable force field for poly(ethylene glycol) ethers (glymes).

    PubMed

    Barbosa, Nathalia S V; Zhang, Yong; Lima, Eduardo R A; Tavares, Frederico W; Maginn, Edward J

    2017-06-01

    An all-atom force field consistent with the general AMBER force field (GAFF) format for poly(ethylene glycol) dimethyl ether (diglyme or G2) was developed by fitting to experimental liquid densities and dielectric constants. Not surprisingly, the new force field gives excellent agreement with experimental liquid phase densities and dielectric constants over a wide temperature range. Other dynamic and thermodynamic properties of liquid G2 such as its self-diffusion coefficient, shear viscosity, and vaporization enthalpy were also calculated and compared to experimental data. For all of the properties studied, the performance of the proposed new force field is better than that of the standard GAFF force field. The force field parameters were transferred to model two other poly(ethylene glycol) ethers: monoglyme (G1) and tetraglyme (G4). The predictive ability of the modified force field for G1 and G4 was significantly better than that of the original GAFF force field. The proposed force field provides an alternative option for the simulation of mixtures containing glymes using GAFF-compatible force fields, particularly for electrochemical applications. The accuracy of a previously published force field based on the OPLS-AA format and the accuracies of two modified versions of that force field were also examined for G1, G2, and G4. It was found that the original OPLS-AA force field is superior to the modified versions of it, and that it has a similar accuracy to the proposed new GAFF-compatible force field. Graphical abstract Transferability of an AMBER-compatible force field parameterized for G2 to other glymes.

  4. Biophysical Characterization of the Strong Stabilization of the RNA Triplex poly(U)•poly(A)*poly(U) by 9-O-(ω-amino) Alkyl Ether Berberine Analogs

    PubMed Central

    Hossain, Maidul; Haq, Lucy; Suresh Kumar, Gopinatha

    2012-01-01

    Background Binding of two 9-O-(ω-amino) alkyl ether berberine analogs BC1 and BC2 to the RNA triplex poly(U)•poly(A)*poly(U) was studied by various biophysical techniques. Methodology/Principal Findings Berberine analogs bind to the RNA triplex non-cooperatively. The affinity of binding was remarkably high by about 5 and 15 times, respectively, for BC1 and BC2 compared to berberine. The site size for the binding was around 4.3 for all. Based on ferrocyanide quenching, fluorescence polarization, quantum yield values and viscosity results a strong intercalative binding of BC1 and BC2 to the RNA triplex has been demonstrated. BC1 and BC2 stabilized the Hoogsteen base paired third strand by about 18.1 and 20.5°C compared to a 17.5°C stabilization by berberine. The binding was entropy driven compared to the enthalpy driven binding of berbeine, most likely due to additional contacts within the grooves of the triplex and disruption of the water structure by the alkyl side chain. Conclusions/Significance Remarkably higher binding affinity and stabilization effect of the RNA triplex by the amino alkyl berberine analogs was achieved compared to berberine. The length of the alkyl side chain influence in the triplex stabilization phenomena. PMID:22666416

  5. Synthesis and self-assembly of brush-type poly[poly(ethylene glycol)methyl ether methacrylate]-block-poly(pentafluorostyrene) amphiphilic diblock copolymers in aqueous solution.

    PubMed

    Tan, B H; Hussain, H; Liu, Y; He, C B; Davis, T P

    2010-02-16

    Well-defined fluorinated brush-like amphiphilic diblock copolymers of poly[poly(ethylene glycol)methyl ether methacrylate] (P(PEGMA)) and poly(pentafluorostyrene) (PPFS) have been successfully synthesized via atom transfer radical polymerization (ATRP). The self-assembly behavior of these polymers in aqueous solutions was studied using (1)H NMR, fluorescence spectrometry, static and dynamic light scattering and transmission electron microscopy techniques. The micellar structure comprised of PPFS as the core and brush-like (hydrophobic main chain and hydrophilic branches) polymers as the coronas. The hydrodynamic radius (R(h)) of the micelles in aqueous solution was in the nanometer range, independent of the polymer concentration, consistent with a closed association model. Diblock copolymers with a longer P(PEGMA) block formed micelles with smaller R(h) and lower aggregation numbers consistent with an improved solubilization of the core. The micelles possessed a thick hydration layer as verified by the ratio of the radius of gyration, R(g) to the hydrodynamic radius, R(h). The aggregation number and ratio of R(g) to R(h) were observed to increase with temperature (20-50 degrees C), while the R(h) of the micelle decreased slightly over the same temperature range. An increase in temperature induced the brush-like PEG segments in the corona to dehydrate and shrink while forming micelles with larger aggregation numbers.

  6. Positively charged and bipolar layered poly(ether imide) nanofiltration membranes for water softening applications

    NASA Astrophysics Data System (ADS)

    Gassara, S.; Abdelkafi, A.; Quémener, D.; Amar, R. Ben; Deratani, A.

    2015-07-01

    Poly(ether imide) (PEI) ultrafiltration membranes were chemically modified with branched poly(ethyleneimine) to obtain nanofiltration (NF) membrane Cat PEI with a positive charge in the pH range below 9. An oppositely charged polyelectrolyte layer was deposited on the resulting membrane surface by using sodium polystyrene sulfonate (PSSNa) and sodium polyvinyl sulfonate (PVSNa) to prepare a bipolar layered membrane NF Cat PEI_PSS and Cat PEI_PVS having a negatively charged surface and positively charged pores. Cat PEI exhibited good performance to remove multivalent cations (more than 90% of Ca2+) from single salt solutions except in presence of sulfate ions. Adding an anionic polyelectrolyte layer onto the positively charged surface resulted in a significant enhancement of rejection performance even in presence of sulfate anions. Application of the prepared membranes in water softening of natural complex mixtures was successful for the different studied membranes and a large decrease of hardness was obtained. Moreover, Cat PEI_PSS showed a good selectivity for nitrate removal. Fouling experiments were carried out with bovine serum albumin, as model protein foulant. Cat PEI_PSS showed much better fouling resistance than Cat PEI with a quantitative flux recovery ratio.

  7. The Use of a Modified Poly-Ether-Ether-Ketone (PEEK) as an Alternative Framework Material for Removable Dental Prostheses. A Clinical Report.

    PubMed

    Zoidis, Panagiotis; Papathanasiou, Ioannis; Polyzois, Gregory

    2016-10-01

    This clinical report presents a modified poly-ether-ether-ketone (PEEK) as an alternative material for the fabrication of distal extension removable dental prosthesis (RDP) frameworks. This material can be used for patients allergic to metals, or who dislike the metallic taste, the weight, and the unpleasant metal display of the denture framework and retentive clasps. This modified PEEK material, known as BioHPP, is a biocompatible, nonallergic, rigid material, with flexibility comparable to bone, high polishing and low absorption properties, low plaque affinity, and good wear resistance. It has been used for years in orthopedics and medical technology. BioHPP frameworks can be constructed either via CAD/CAM manufacturing or via the conventional lost wax technique. The clinical use of a BioHPP RDP framework is presented as an alternative for the treatment of a distal extension case.

  8. Shifting from hydrogen bond network to π-π stacking: a key mechanism for reversible thermochromic sulfonated poly(ether ether ketone).

    PubMed

    Jarumaneeroj, Chatchai; Tashiro, Kohji; Chirachanchai, Suwabun

    2014-08-01

    Sulfonated poly(ether ether ketone) (SPEEK) thin film performs reversible thermochromic property by developing the color to be yellowish at the temperature above 190 °C. The detailed analyses based on temperature-dependent techniques suggest the thermal treatment inducing the shifting of the hydrogen bond network between the sulfonated group and the hydrated water molecules to the π-π stacking among aromatic rings in SPEEK chains. Although it is general that the polymer chain packing is unfavorable at high temperature, the present work shows a good example that when the polymer chains can form specific molecular interaction, such as π-π stacking, even in harsh thermal treatment, a rearrangement will effectively occur, which leads to an external stimuli-responsive property.

  9. Surface modification of poly(ether sulfone) membrane with a synthesized negatively charged copolymer.

    PubMed

    Zou, Wen; Qin, Hui; Shi, Wenbin; Sun, Shudong; Zhao, Changsheng

    2014-11-18

    In this study, we provide a new method to modify poly(ether sulfone) (PES) membrane with good biocompatibility, for which diazotized PES (PES-N2(+)) membrane is covalently coated by a negatively charged copolymer of sodium sulfonated poly(styrene-alt-maleic anhydride) (NaSPS-MA). First, aminated PES (PES-NH2) is synthesized by nitro reduction reaction of nitro-PES (PES-NO2), and then blends with pristine PES to prepare PES/PES-NH2 membrane; then the membrane is treated with NaNO2 aqueous solution at acid condition; after surface diazo reaction, surface positively charged PES/PES-N2(+) membrane is prepared. Second, poly(styrene-alt-maleic anhydride) (PS-alt-MA) is synthesized, then sulfonated and treated by sodium hydroxide solution to obtain sodium sulfonated (PS-alt-MA) (NaSPS-MA). Finally, the negatively charged NaSPS-MA copolymer is coated onto the surface positively charged PES/PES-N2(+) membrane via electrostatic interaction; after UV-cross-linking, the linkage between the PES-N2(+) and NaSPS-MA changes to a covalent bond. The surface-modified PES membrane is characterized by FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS) analyses, and surface zeta potential analyses. The modified membrane exhibits good hemocompatibility and cytocompatibility, and the improved biocompatibility might have resulted from the existence of the hydrophilic groups (sodium carboxylate (-COONa) and sodium sulfonate (-SO3Na)). Moreover, the stability of the modified membrane is also investigated. The results indicated that the modified PES membrane using negatively charged copolymers had a lot of potential in blood purification fields and bioartificial liver supports for a long time.

  10. Pullout performance comparison of novel expandable pedicle screw with expandable poly-ether-ether-ketone shells and cement-augmented pedicle screws.

    PubMed

    Aycan, Mehmet Fatih; Tolunay, Tolga; Demir, Teyfik; Yaman, Mesut Emre; Usta, Yusuf

    2017-02-01

    Aim of this study is to assess the pullout performance of various pedicle screws in different test materials. Polyurethane foams (Grade 10 and Grade 40) produced in laboratory and bovine vertebrae were instrumented with normal, cannulated (cemented), novel expandable and normal (cemented) pedicle screws. Test samples were prepared according to the ASTM F543 standard testing protocols and surgical guidelines. To examine the screw placement and cement distribution, anteriosuperior and oblique radiographs were taken from each sample after insertion process was completed. Pullout tests were performed in an Instron 3369 testing device. Load versus displacement graphs were recorded and the ultimate pullout force was defined as the maximum load (pullout strength) sustained before failure of screw. Student's t-test was performed on each group whether the differences between pullout strength of pedicle screws were significant or not. While normal pedicle screws have the lowest pullout strength in all test materials, normal pedicle screws cemented with polymethylmethacrylate exhibit significantly higher pullout performance than others. For all test materials, there is a significant improvement in pullout strength of normal screws by augmentation. While novel expandable pedicle screws with expandable poly-ether-ether-ketone shells exhibited lower pullout performance than normal screws cemented with polymethylmethacrylate, their pullout performances in all groups were higher than the ones of normal and cannulated pedicle screws. For all test materials, although cannulated pedicle screws exhibit higher pullout strength than normal pedicle screws, there are no significant differences between the two groups. The novel expandable pedicle screws with expandable poly-ether-ether-ketone shells may be used instead of normal and cannulated pedicle screws cemented with polymethylmethacrylate due to their good performances.

  11. Low cost hydrogen/novel membrane technology for hydrogen separation from synthesis gas, Phase 1. [Poly(etherimide) and poly(ether-ester-amide) membranes

    SciTech Connect

    Not Available

    1986-01-01

    During the last quarter several high performance membranes for the separation of hydrogen from nitrogen, carbon monoxide, hydrogen sulfide and carbon dioxide. The heat-resistant resin poly(etherimide) has been selected as the polymer with the most outstanding properties for the separation of hydrogen from nitrogen and carbon monoxide. Flat sheet and hollow fiber poly(etherimide) membranes have been prepared and evaluated with pure gases and gas mixtures at elevated pressures and temperatures. Multilayer composite poly(ether-ester-amide) membranes were also developed. These membranes are useful for the separation of carbon dioxide and hydrogen sulfide hydrogen. They have very high selectivities and extremely high normalized carbon dioxide and hydrogen sulfide fluxes. Separation of carbon dioxide/hydrogen streams is a key problem in hydrogen production from coal. The development of the two membranes now gives us two approaches to separate these gas streams, depending on the stream's composition. If the stream contains small quantities of hydrogen, the hydrogen- permeable poly(etherimide) membrane would be used to produce a hydrogen-enriched permeate. If the stream contains small quantities of carbon dioxide or hydrogen sulfide, the poly(ether-ester-amide) membrane would be used to produce a carbon dioxide/hydrogen sulfide-free, hydrogen-enriched residue stream. 6 fig., 4 tabs.

  12. Thermoresponsive poly(glycidyl ether) brushes on gold: Surface engineering parameters and their implication for cell sheet fabrication.

    PubMed

    Heinen, Silke; Cuéllar-Camacho, José Luis; Weinhart, Marie

    2017-09-01

    Thermoresponsive polymer coatings, optimized for cell adhesion and thermally-triggered cell detachment, allow the fabrication of confluent cell sheets with intact extracellular matrix. However, rational design guidelines for such coatings are rare, since temperature-triggered cell adhesion and detachment from thermoresponsive surfaces are mechanistically not well understood. Herein, we investigated the impact of molecular weight (2, 9, 24kDa), grafting density (0.04-1.4 chains nm(-2)), morphology, and roughness of well-characterized thermoresponsive poly(glycidyl ether) brushes on the cell response at 37 and 20°C. NIH 3T3 mouse fibroblasts served as a model cell line for adhesion, proliferation, and cell sheet detachment. The cell response was correlated with serum protein adsorption from cell culture medium containing 10% fetal bovine serum. Intact cell sheets could be harvested from all the studied poly(glycidyl ether) coated surfaces, irrespective of the molecular weight, provided that the morphology of the coating was homogenous and the surface was fully shielded by the hydrated brush. The degree of chain overlap was estimated by the ratio of twice the polymer's Flory radius in a theta solvent to its interchain distance, which should be located in the strongly overlapping brush regime (2 Rf/l>1.4). In contrast, dense PNIPAM (2.5kDa) control monolayers did not induce protein adsorption from cell culture medium at 37°C and, as a result, did not allow a significant cell adhesion. These structural design parameters of functional poly(glycidyl ether) coatings on gold will contribute to future engineering of these thermoresponsive coatings on more common, cell culture relevant substrates. Cell sheet engineering as a scaffold-free approach towards tissue engineering resembles a milestone in regenerative medicine. The fabrication of confluent cell sheets maintains the extracellular matrix of cells which serves as the physiological cell scaffold. Thermoresponsive poly

  13. Functional Aromatic Poly(1,3,4-Oxadiazole-Ether)s with Benzimidazole Pendants: Synthesis, Thermal and Dielectric Studies

    PubMed Central

    Ganesh, Shimoga D.; Pai, Vasantakumar K.; Kariduraganavar, Mahadevappa Y.; Jayanna, Madhu B.

    2014-01-01

    Poly(1,3,4-oxadiazole-ether) with reactive carboxylic acid pendants was synthesized from solution polymerization via nucleophilic displacement polycondensation among 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole (BFPOx) and 4,4′-bis(4-hydroxyphenyl) valeric acid (BHPA). Without altering the polymeric segments, benzimidazole modified poly(1,3,4-oxadiazole-ether)s were prepared by varying stoichiometric ratios of 1,2-phenylenediamine. The molecular structural characterization of these polymers was achieved by, FT-IR, NMR, TGA, elemental analysis, and analytical techniques. The weight-average molecular weight of virgin polymer with carboxylic acid functionality was determined by gel permeation chromatography (GPC) and was found to be 22400 (Mw/Mn = 2.07). All the synthesized polyethers were compressed into pellets and electrical contacts were established to perform dielectric properties. PMID:27437448

  14. Fabrication and characterization of amine terminated poly(arylene ether sulfone) modified epoxy-carbon fiber composites

    NASA Technical Reports Server (NTRS)

    Cecere, James A.; Senger, James S.; Mcgrath, James E.; Steiner, Paul A.; Wong, Raymond S.

    1987-01-01

    Multifunctional epoxy resin networks were chemically modified with thermoplastic amine terminated poly(arylene ether sulfones) of controlled molecular weights. This system was then examined as both neat resin and as a matrix resin for carbon fiber composites. The neat resin displayed a significant increase in both fracture toughness and energy release rate values. This was attributed to the altered morphology, which could be varied from particles of polysulfone in an epoxy matrix to that of a quasi-continuous polysulfone phase.

  15. Fabrication and characterization of amine terminated poly(arylene ether sulfone) modified epoxy-carbon fiber composites

    NASA Technical Reports Server (NTRS)

    Cecere, James A.; Senger, James S.; Mcgrath, James E.; Steiner, Paul A.; Wong, Raymond S.

    1987-01-01

    Multifunctional epoxy resin networks were chemically modified with thermoplastic amine terminated poly(arylene ether sulfones) of controlled molecular weights. This system was then examined as both neat resin and as a matrix resin for carbon fiber composites. The neat resin displayed a significant increase in both fracture toughness and energy release rate values. This was attributed to the altered morphology, which could be varied from particles of polysulfone in an epoxy matrix to that of a quasi-continuous polysulfone phase.

  16. Hydrolyzable Poly[Poly(Ethylene Glycol) Methyl Ether Acrylate]-Colistin Prodrugs through Copper-Mediated Photoinduced Living Radical Polymerization.

    PubMed

    Zhu, Chongyu; Schneider, Elena K; Nikolaou, Vasiliki; Klein, Tobias; Li, Jian; Davis, Thomas P; Whittaker, Michael R; Wilson, Paul; Kempe, Kristian; Velkov, Tony; Haddleton, David M

    2017-07-19

    Through the recently developed copper-mediated photoinduced living radical polymerization (CP-LRP), a novel and well-defined polymeric prodrug of the antimicrobial lipopeptide colistin has been developed. A colistin initiator (Boc5-col-Br2) was synthesized through the modification of colistin on both of its threonine residues using a cleavable initiator linker, 2-(2-bromo-2-methylpropanoyloxy) acetic acid (BMPAA), and used for the polymerization of acrylates via CP-LRP. Polymerization proceeds from both sites of the colistin initiator, and through the polymerization of poly(ethylene glycol) methyl ether acrylate (PEGA480), three water-soluble polymer-colistin conjugates (col-PPEGA, having degrees of polymerization of 5, 10, and 20) were achieved with high yield (conversion of ≥93%) and narrow dispersities (Đ < 1.3) in 2-4 h. Little or no effect on the structure and activity of the colistin was observed during the synthesis, and most of the active colistin can be recovered from the conjugates in vitro within 2 days. Furthermore, in vitro biological analyses including disk diffusion, broth microdilution, and time-kill studies suggested that all of the conjugates have the ability to inhibit the growth of multidrug-resistant (MDR) Gram-negative bacteria, of which col-PPEGA DP5 and DP10 showed similar or better antibacterial performance compared to the clinically relevant colistin prodrug CMS, indicating their potential as an alternative antimicrobial therapy. Moreover, considering the control over the polymerization, the CP-LRP technique has the potential to provide an alternative platform for the development of polymer bioconjugates.

  17. Toughening of BIS maleimide resins: Synthesis and characterization of maleimide terminated poly(arylene ether) oligomers and polymers

    NASA Technical Reports Server (NTRS)

    Mcgrath, J. E.; Lyle, G. D.; Jurek, M. J.; Mohanty, D.; Hedrick, J. C.

    1986-01-01

    Amine functional poly(arylene ether) sulfones were previously reported. Herein, the chemistry was extended to amorphous poly(arylene ether) ketones because of their higher fracture toughness values, relative to the polysulfones. It was demonstrated that the amino functional oligomers undergo a self-crosslinking reaction at temperatures above about 220 C. This produces an insoluble, but ductile network that has excellent resistance. A ketamine structure hypothesis was proposed and verified using solid state magic angle NMR. In most cases, the water generated upon ketamine formation is too low to produce porosity and solid networks are obtained. The stability of the ketamine networks towards hydrolysis is excellent. The chemistry was further demonstrated to be able to crosslink preformed nonfunctional poly(arylene ether) ketones if a difunctional amine was utilized. This concept has the possibility of greatly improving the creep resistance of thermoplastics. Also, a new technique was developed for converting the amine functional oligomers cleanly into maleimide structures. This method involves reacting maleic anhydride with monomeric aminophenols in the presence of solvent mixtures.

  18. Pendant dual sulfonated poly(arylene ether ketone) proton exchange membranes for fuel cell application

    NASA Astrophysics Data System (ADS)

    Nguyen, Minh Dat Thinh; Yang, Sungwoo; Kim, Dukjoon

    2016-10-01

    Poly(arylene ether ketone) (PAEK) possessing carboxylic groups at the pendant position is synthesized, and the substitution degree of pendant carboxylic groups is controlled by adjusting the ratio of 4,4-bis(4-hydroxyphenyl)valeric acid and 2,2-bis(4-hydroxyphenyl)propane. Dual sulfonated 3,3-diphenylpropylamine (SDPA) is grafted onto PAEK as a proton-conducting moiety via the amidation reaction with carboxylic groups. The transparent and flexible membranes with different degrees of sulfonation are fabricated so that we can test and compare their structure and properties with a commercial Nafion® 115 membrane for PEMFC applications. All prepared PAEK-SDPA membranes exhibit good oxidative and hydrolytic stability from Fenton's and high temperature water immersion test. SAXS analysis illustrates an excellent phase separation between the hydrophobic backbone and hydrophilic pendant groups, resulting in big ionic clusters. The proton conductivity was measured at different relative humidity, and its behavior was analyzed by hydration number of the membrane. Among a series of membranes, some samples (including B20V80-SDPA) show not only higher proton conductivity, but also higher integrated cell performance than those of Nafion® 115 at 100% relative humidity, and thus we expect these to be good candidate membranes for proton exchange membrane fuel cells (PEMFCs).

  19. Electrospun sulfonated poly(ether ketone) nanofibers as proton conductive reinforcement for durable Nafion composite membranes

    NASA Astrophysics Data System (ADS)

    Klose, Carolin; Breitwieser, Matthias; Vierrath, Severin; Klingele, Matthias; Cho, Hyeongrae; Büchler, Andreas; Kerres, Jochen; Thiele, Simon

    2017-09-01

    We show that the combination of direct membrane deposition with proton conductive nanofiber reinforcement yields highly durable and high power density fuel cells. Sulfonated poly(ether ketone) (SPEK) was directly electrospun onto gas diffusion electrodes and then filled with Nafion by inkjet-printing resulting in a 12 μm thin membrane. The ionic membrane resistance (30 mΩ*cm2) was well below that of a directly deposited membrane reinforced with chemically inert (PVDF-HFP) nanofibers (47 mΩ*cm2) of comparable thickness. The power density of the fuel cell with SPEK reinforced membrane (2.04 W/cm2) is 30% higher than that of the PVDF-HFP reinforced reference sample (1.57 W/cm2). During humidity cycling and open circuit voltage (OCV) hold, the SPEK reinforced Nafion membrane showed no measurable degradation in terms of H2 crossover current density, thus fulfilling the target of 2 mA/cm2 of the DOE after degradation. The chemical accelerated stress test (100 h OCV hold at 90 °C, 30% RH, H2/air, 50/50 kPa) revealed a degradation rate of about 0.8 mV/h for the fuel cell with SPEK reinforced membrane, compared to 1.0 mV/h for the PVDF-HFP reinforced membrane.

  20. Effect of silica nanoparticles on reinforcement of poly(phenylene ether) based thermoplastic elastomer.

    PubMed

    Gupta, Samik; Maiti, Parnasree; Krishnamoorthy, Kumar; Krishnamurthy, Raja; Menon, Ashok; Bhowmick, Anil K

    2008-04-01

    Reinforcement of a novel poly(phenylene ether) (PPE) based thermoplastic elastomer (TPE), i.e., styrene-ethylene-butylene-styrene (SEBS)/ethylene vinyl acetate (EVA) and PPE-polystyrene (PS), was studied to develop a reinforced thermoplastic elastomer or thermoplastic vulcanizate (TPV). An effort was made to reinforce selectively the elastomeric dispersed phase of EVA by silica nanoparticles and silica sol-gel precursors, like alkoxy orthosilanes, using twin-screw extrusion and injection molding processes. Improvement of tensile strength and percent elongation at break was observed both with silica nanoparticles and tetraethoxy orthosilane (TEOS). Addition of TEOS transformed the dispersed EVA lamellar morphology into semispherical domains as a consequence of possible crosslinking. Soxhlet extraction was done on the silica and TEOS reinforced materials. The insoluble residues collected from both the silica and TEOS reinforced samples were analyzed in detail using both morphological and spectroscopic studies. This extensive study also provided an in-depth conceptual understanding of the PPE based TPE behavior upon reinforcement with silica nanoparticles and silica sol-gel precursors and the effect of reinforcement on recycling behavior.

  1. Radiation crosslinking and scission of poly(vinyl methyl ether) in aqueous solution

    NASA Astrophysics Data System (ADS)

    Janik, Ireneusz; Rosiak, Janusz M.

    2002-03-01

    For a wide range of poly(vinyl methyl ether) (PMVE) concentrations (1-16 g dm -3), in anoxic conditions, polymer-derived radicals recombine in two major pathways: (i) crosslinking and (ii) disproportionation. Both these processes proceed inter- and intramolecularly. The radiation-chemical yields and kinetics of crosslinking have been studied by pulse radiolysis with light scattering intensity detection (LSI). In the absence of oxygen, G-values of intermolecular crosslinking were determined on the basis of LSI changes versus applied dose and compared with the results obtained previously for γ-irradiated samples. It has been found that the first half-life time of intermolecular crosslinking decreases with increasing dose per pulse. Addition of small amounts of macroradical scavenger (cysteamine hydrochloride) decreases, drastically, the increase of LSI signal. On increasing the PVME concentration, intermolecular crosslinking becomes more efficient. In the presence of oxygen, for diluted PVME solution (0.1 g dm -3), decrease of LSI signal consisting of the kinetic of a first-order reaction was observed. The rate constant of LSI decrease was found to be 1.1×10 3 s -1 and it was attributed to the main-chain scission.

  2. Adsorption capacity of poly(ether imide) microparticles to uremic toxins.

    PubMed

    Tetali, Sarada D; Jankowski, Vera; Luetzow, Karola; Kratz, Karl; Lendlein, Andreas; Jankowski, Joachim

    2016-01-01

    Uremia is a phenomenon caused by retention of uremic toxins in the plasma due to functional impairment of kidneys in the elimination of urinary waste products. Uremia is presently treated by dialysis techniques like hemofiltration, dialysis or hemodiafiltration. However, these techniques in use are more favorable towards removing hydrophilic than hydrophobic uremic toxins. Hydrophobic uremic toxins, such as hydroxy hipuric acid (OH-HPA), phenylacetic acid (PAA), indoxyl sulfate (IDS) and p-cresylsulfate (pCRS), contribute substantially to the progression of chronic kidney disease (CKD) and cardiovascular disease. Therefore, objective of the present study is to test adsorption capacity of highly porous microparticles prepared from poly(ether imide) (PEI) as an alternative technique for the removal of uremic toxins. Two types of nanoporous, spherically shaped microparticles were prepared from PEI by a spraying/coagulation process.PEI particles were packed into a preparative HPLC column to which a mixture of the four types of uremic toxins was injected and eluted with ethanol. Eluted toxins were quantified by analytical HPLC. PEI particles were able to adsorb all four toxins, with the highest affinity for PAA and pCR. IDS and OH-HPA showed a partially non-reversible binding. In summary, PEI particles are interesting candidates to be explored for future application in CKD.

  3. Influence of nanoporous poly(ether imide) particle extracts on human aortic endothelial cells (HAECs).

    PubMed

    Kumar, Reddi K; Basu, Sayantani; Lemke, Horst-Dieter; Jankowski, Joachim; Kratz, Karl; Lendlein, Andreas; Tetali, Sarada D

    2016-01-01

    Accumulated uremic toxins like indoxyl sulphate, hippuric acid and p-cresyl sulphates in renal failure patients stimulate proinflammatory effects, and consequently kidney and cardiovascular diseases. Low clearance rate of these uremic toxins from the blood of uremic patients by conventional techniques like hemodialysis is due to their strong covalent albumin binding (greater than 95%) and hydrophobic nature, which led to alternatives like usage of hydrophobic adsorber's in removing these toxins from the plasma of kidney patients. Polymers like polyethylene, polyurethane, polymethylmethacrylate, cellophane and polytetrafluoroethylene were already in use as substitutes for metal devices as dialysis membranes. Among new synthetic polymers, one such ideal adsorber material are highly porous microparticles of poly(ether imide) (PEI) with diameters in the range from 50-180μm and a porosity around 88±2% prepared by a spraying and coagulation process.It is essential to make sure that these synthetic polymers should not evoke any inflammatory or apoptotic response during dialysis. Therefore in our study we evaluated in vitro effect of PEI microparticle extracts in human aortic endothelial cells (HEACs) concerning toxicity, inflammation and apoptosis. No cell toxicity was observed when HAECs were treated with PEI extracts and inflammatory/apoptotic markers were not upregulated in presence of PEI extracts. Our results ensure biocompatibility of PEI particles and further hemocompatibility of particles will be tested.

  4. Correlating electronic structure and chemical durability of sulfonated poly(arylene ether sulfone)s

    NASA Astrophysics Data System (ADS)

    Lawrence, Jimmy; Yamashita, Koichi; Yamaguchi, Takeo

    2015-04-01

    Many different proton-conducting polymeric materials have been developed for polymer electrolyte membrane fuel cells (PEMFCs). The development of perfluorosulfonic acid-based, polymer electrolyte membranes (PFSA-PEMs) was followed by aromatic hydrocarbon-based PEMs (HC-PEMs), which allow for tailored design and optimization of their molecular structures. Although many new PFSA-PEMs and HC-PEMs have shown promising proton conductivity and thermal stability, chemical degradation of these materials in an oxidizing environment remains a significant technical barrier in PEMFC development. Here, we used accelerated degradation tests and electronic structure analysis to examine the chemical stability of sulfonated poly(arylene ether sulfone) (SPES) copolymers, a highly thermally stable HC-PEM. HOMO levels, the presence of main chain-protecting steric groups, and HOMO-LUMO location along the main chain have significant effects on the chain scission modes and degradation rate of SPES copolymers. Rational design of HC-PEMs to suppress midpoint scission can open many opportunities in the development of highly robust polymer electrolytes for fuel cell and other energy storage applications.

  5. Local Structure and Dynamics of Water Absorbed in Poly(ether imide): A Hydrogen Bonding Anatomy.

    PubMed

    de Nicola, Antonio; Correa, Andrea; Milano, Giuseppe; La Manna, Pietro; Musto, Pellegrino; Mensitieri, Giuseppe; Scherillo, Giuseppe

    2017-04-13

    Hydrogen bonding (HB) interactions play a major role in determining the behavior of macromolecular systems absorbing water. In fact, functional and structural properties of polymer-water mixtures are affected by the amount and type of these interactions. This contribution aims at a molecular level understanding of the interactional scenario for the technologically relevant case of the poly(ether imide)-water system. The problem has been tackled by combining different experimental and theoretical approaches which, taken together, provide a comprehensive physical picture. Relevant experimental data were gathered by in situ FTIR spectroscopy, while molecular dynamics (MD) and statistical thermodynamics approaches were used as modeling theoretical tools. It was found that, among the possible configurations, some are strongly prevailing. In particular, water molecules preferentially establish water bridges with two carbonyl groups of the same PEI repeating unit. Water self-interactions were also detected, giving rise to a "second shell" species in the prevalent form of dimers. The population of the different water species was evaluated spectroscopically, and a remarkable agreement with theoretical predictions was found.

  6. Characterization methods for radiation crosslinked poly(vinyl methyl ether) hydrogels

    NASA Astrophysics Data System (ADS)

    Schmidt, Thomas; Querner, Claudia; Arndt, Karl-Friedrich

    2003-08-01

    The paper reviews recent results of radiation crosslinking of poly(vinyl methyl ether) (PVME). It will give an overview of possible characterization methods for both, soluble and crosslinked PVME. The irradiation of aqueous low concentrated PVME solutions with γ-rays of low doses results in structural changes of PVME molecules. We are able to monitor changes in the chemical structure by spectroscopic methods (IR, NMR) as well as the changes of molecular parameters (e.g. molecular weight, molecular weight distribution, branches) by classical methods for polymer characterization (size exclusion chromatography with diverse detector systems, SLS, viscosimetry). The characterization of the network parameters (crosslinking density νc, molecular weight of the network chains Mc) of PVME bulkgels crosslinked by irradiation at high dose values by classical methods (swelling and compression measurements) provides incorrect results because of the high porosity of the gels. PVME microgel particles can be prepared by irradiation of a phase separated diluted aqueous PVME solution above their lower critical solution temperature. These microgels with decreased dimensions were characterized by SLS, DLS and field emission scanning electron microscopy.

  7. Radiation crosslinking and scission parameters for poly(vinyl methyl ether) in aqueous solution

    NASA Astrophysics Data System (ADS)

    Janik, I.; Kasprzak, E.; Al-Zier, A.; Rosiak, J. M.

    2003-08-01

    In oxygen-free aqueous solutions, poly(vinyl methyl ether) (PVME) was subjected to gamma irradiation. In such conditions PVME radicals recombine by way of crosslinking. The major result of crosslinking is an increase in the average molecular weight of the polymer, which close to the gelation point tends to infinity. Further irradiation increases the amount of formed gel, while the soluble fraction - sol decreases. The basic parameters related to the radiation processing are gelation dose - Dg, as well as radiation yield of intermolecular crosslinking and scission, GX and GS, respectively. There are three general approaches for estimation of those parameters. The first method is based on the study of molecular weight changes before the gelation point. The second method combines the gel-sol as well as the swelling analysis results. The third one allows one to calculate the yield of crosslinking from the value of Dg. All of these methods of calculation were used in this work for determination of radiation parameters and results obtained are discussed.

  8. Covalent enzyme immobilization by poly(ethylene glycol) diglycidyl ether (PEGDE) for microelectrode biosensor preparation.

    PubMed

    Vasylieva, Natalia; Barnych, Bogdan; Meiller, Anne; Maucler, Caroline; Pollegioni, Loredano; Lin, Jian-Sheng; Barbier, Daniel; Marinesco, Stéphane

    2011-06-15

    Poly(ethylene glycol) diglycidyl ether (PEGDE) is widely used as an additive for cross-linking polymers bearing amine, hydroxyl, or carboxyl groups. However, the idea of using PEGDE alone for immobilizing proteins on biosensors has never been thoroughly explored. We report the successful fabrication of microelectrode biosensors based on glucose oxidase, d-amino acid oxidase, and glutamate oxidase immobilized using PEGDE. We found that biosensors made with PEGDE exhibited high sensitivity and a response time on the order of seconds, which is sufficient for observing biological processes in vivo. The enzymatic activity on these biosensors was highly stable over several months when they were stored at 4 °C, and over at least 3d at 37 °C. Glucose microelectrode biosensors implanted in the central nervous system of anesthetized rats reliably monitored changes in brain glucose levels induced by sequential administration of insulin and glucose. PEGDE provides a simple, low cost, non-toxic alternative for the preparation of in vivo microelectrode biosensors.

  9. Attachment and proliferation of bovine aortic endothelial cells onto additive modified poly(ether urethane ureas)

    SciTech Connect

    Brunstedt, M.R.; Ziats, N.P.; Rose-Caprara, V.; Hiltner, P.A.; Anderson, J.M. ); Lodoen, G.A.; Payet, C.R. E.I. du Pont de Nemours and Co., Wilmington, DE )

    1993-04-01

    To better understand endothelial cell interactions with poly(ether urethane urea) (PEUU) materials, and to assess bovine aortic endothelial cell attachment, films were incubated for 24 h with BAEC in media containing 5% fetal bovine serum. Other films were allowed to incubate for 4 more days in media containing 5% fetal bovine serum without cells to assess BAEC proliferation. The assay was performed on PEUU films modified with acrylate and methacrylate polymer and copolymer additives that spanned a wide range on the hydrophobicity/hydrophilicity scale. Tissue culture polystyrene (TCPS) was used as a control. The assay showed that PEUU films loaded with Methacrol 2138F [copoly(diisopropylaminoethyl methacrylate [DIPAM]/decyl methacrylate [DM]) (3/1)] or with its hydrophilic component, DIPAM, in homopolymer form (i.e., h-DIPAM), significantly enhanced BAEC attachment and proliferation when compared to unloaded PEUU films or to PEUU films loaded with the more hydrophobic acrylate or methacrylate polymer additives. The assay also showed that PEUU films coated with homopoly(diisopropylaminoethyl acrylate) (h-DIPAA) significantly enhanced BAEC attachment and proliferation when compared to PEUU films coated with h-decyl acrylate films coated with the copolymer of these two acrylates showed intermediate behavior.

  10. Interaction of thrombocytes with poly(ether imide): The influence of processing.

    PubMed

    Braune, S; Lange, M; Richau, K; Lützow, K; Weigel, T; Jung, F; Lendlein, A

    2010-01-01

    The processing of polymers for blood contacting devices can have a major influence on surface properties. In this study, we fabricated poly(ether imide) (PEI) membranes and films to investigate the effects of the processing on physicochemical surface properties by atomic force microscopy (AFM), scanning electron microscopy, contact angle as well as zeta potential measurements. A static platelet adhesion test was performed to analyze the thrombogenicity of both devices. While contact angle measurements showed similar levels of hydrophobicity and zeta potential values were equivalent, mean surface roughness as well as surface energies in the dispersive part were found to be increased for the PEI membrane. The static platelet adhesion test showed a significantly decreased number of adherent platelets per surface area on the PEI film (178.98 ± 102.70/45000 μm2) compared to the PEI membrane (504 ± 314.27/45000μm2) and, consequently, revealed evidence for higher thrombogenicity of the PEI membrane. This study shows that processing can have a significant effect on platelet adhesion to biomaterials, even though, molar weight was identical. Thrombogenicity of polymer-based cardiovascular devices, therefore, have to be evaluated at the final product level, following the entire processing procedure.

  11. Electrospun nanofiber enhanced sulfonated poly(arylene ether nitriles)-based proton conducting membrane

    NASA Astrophysics Data System (ADS)

    Feng, Mengna; Huang, Yumin; Liu, Xiaobo

    2017-01-01

    To study the effect of electrospun nanofiber on proton conductivity of sulfonated poly(arylene ether nitriles) (SPEN), the nanofiber mats were prepared by the electrospinning technology and the nanofiber/SPEN proton conducting membranes with different SHQ content were fabricated via impregnation method. For comparison, the casting SPEN membrane was also prepared by the solution-casting method. The scanning electron microscope (SEM) was used to observe the morphologies of electrospinning nanofiber mats. The water uptake, thermal and oxidative stability of casting SPEN and the nanofiber/SPEN membranes were also detailed studied. Besides, the nanofiber/SPEN membranes possess the higher proton conductivity than that of casting SPEN. The SPEN composite membrane with 5 wt% SHQ nanofiber exhibits the highest proton conductivity of 0.044 S/cm and 0.0865 S/cm at 20 °C and 80 °C, respectively. However, after second times water treatment, the conductivities of nanofiber/SPEN membranes are all lower than that of original value due to the shift loss of dissociative sulfonic acid group. Therefore, although the electrospinning is a good method to improve proton conductivity, it is also a great challenge to avoid the shift loss of sulfonic acid group for the nanofiber/SPEN.

  12. Nitrile functionalized halloysite nanotubes/poly(arylene ether nitrile) nanocomposites: Interface control, characterization, and improved properties

    NASA Astrophysics Data System (ADS)

    Wan, Xinyi; Zhan, Yingqing; Zeng, Guangyong; He, Yi

    2017-01-01

    To develop high-performance halloysite nanotube (HNT)-based nanocomposites, the two key issues need to be considered: precise interface control and the dispersal of HNTs. This study presents an efficient way to functionalize halloysite nanotubes with 3-aminophenoxy-phthalonitrile, followed by compounding with poly(arylene ether nitrile) (PEN), to prepare functional nanocomposite films. The surface functionalization of HNTs was characterized and confirmed by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). Compared with neat PEN, the tensile strength and modulus of the resulting PEN nanocomposites with 3 wt% functionalized HNTs were found to increase by 25.7% and 20.7%, respectively. The good dispersion and high capacitance of the dielectric layer resulted in PEN/HNTs nancomposites with enhanced dielectric permittivity and relatively low dielectric loss. Moreover, the addition of functional HNTs greatly improved the thermal stability of PEN, which could be further enhanced through the chemical cross-linking reaction between the functional HNTs and the PEN matrix. This work provides a new path toward obtaining advanced polymer-based nanocomposites with functional properties.

  13. The chromatography of poly(phenylene ether) on a porous graphitic carbon sorbent.

    PubMed

    Moyses, Stephan; Ginzburg, Anton

    2016-10-14

    A Porous Graphitic Carbon (PGC) column was evaluated for the analysis of poly(phenylene ether) (PPE). This column appears particularly well-suited for the separation of this polymer. Conditions for the elution of PPE either in adsorption mode with chloroform or size exclusion with 1,2,4-trichlorobenzene (TCB) as eluent were established. Elution of homologous species is obtained in chloroform that follows Martin's rule. A separation based on a gradient consisting of a sequence of non-solvent (acetonitrile), solvent/adsorli (chloroform) provided the highest peak capacity. In TCB, it is possible to obtain rapid size-based separation: with a flow rate of 0.7ml/min, the run time is less than two minutes for a series of polystyrene standards. The PGC column performs remarkably well in this mode and may be a viable solution when a short analysis time is critical such as in a combinatorial laboratory or in a two-dimensional chromatograph. In addition to its value as a sorbent for polymer separation, this column also deserves the attention of the materials engineer. Indeed, the PGC sorbent can be used as a model to probe the interaction between polymers and graphitic fillers such as carbon nanotubes or graphite nanosheets.

  14. Hydrophilic modification of poly(ether sulfone) ultrafiltration membrane surface by self-assembly of TiO 2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Luo, Ming-Liang; Zhao, Jian-Qing; Tang, Wu; Pu, Chun-Sheng

    2005-08-01

    Membrane fouling is one of the major obstacles for reaching the ultimate goal, which realizes high flux over a prolonged period of ultrafiltration (UF) operation. In this paper, TiO 2 nanoparticles of a quantum size (40 nm or less) in anatase crystal structure were prepared from the controlled hydrolysis of titanium tetraisopropoxide and characterized by X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM). The hydrophilic modification of poly(ether sulfone) UF membrane was performed by self-assembly of the hydroxyl group of TiO 2 nanoparticle surface and the sulfone group and ether bond in poly(ether sulfone) structure through coordination and hydrogen bond interaction, which was ascertained by X-ray photoelectron spectroscopy (XPS). The morphology and hydrophilicity were characterized by scanning electron microscopy (SEM) and contact angle test, respectively. The composite UF membrane was also characterized in terms of separation behavior for polyethylene glycol-5000 solute. The experimental results show that the composite UF membrane has good separation performance and offers a strong potential for possible use as a new type of anti-fouling UF membrane.

  15. Poly[tri(ethylene glycol) ethyl ether methacrylate]-coated surfaces for controlled fibroblasts culturing.

    PubMed

    Dworak, Andrzej; Utrata-Wesołek, Alicja; Szweda, Dawid; Kowalczuk, Agnieszka; Trzebicka, Barbara; Anioł, Jacek; Sieroń, Aleksander L; Klama-Baryła, Agnieszka; Kawecki, Marek

    2013-03-01

    Well-defined thermosensitive poly[tri(ethylene glycol) monoethyl ether methacrylate] (P(TEGMA-EE)) brushes were synthesized on a solid substrate by the surface-initiated atom transfer radical polymerization of TEGMA-EE. The polymerization reaction was initiated by 2-bromo-2-methylpropionate groups immobilized on the surface of the wafers. The changes in the surface composition, morphology, philicity, and thickness that occurred at each step of wafer functionalization confirmed that all surface modification procedures were successful. Both the successful modification of the surface and bonding of the P(TEGMA-EE) layer were confirmed by X-ray photoelectron spectroscopy (XPS) measurements. The thickness of the obtained P(TEGMA-EE) layers increased with increasing polymerization time. The increase of environmental temperature above the cloud point temperature of P(TEGMA-EE) caused the changes of surface philicity. A simultaneous decrease in the polymer layer thickness confirmed the thermosensitive properties of these P(TEGMA-EE) layers. The thermosensitive polymer surfaces obtained were evaluated for the growth and harvesting of human fibroblasts (basic skin cells). At 37 °C, seeded cells adhered to and spread well onto the P(TEGMA-EE)-coated surfaces. A confluent cell sheet was formed within 24 h of cell culture. Lowering the temperature to an optimal value of 17.5 °C (below the cloud point temperature of the polymer, TCP, in cell culture medium) led to the separation of the fibroblast sheet from the polymer layer. These promising results indicate that the surfaces produced may successfully be used as substrate for engineering of skin tissue, especially for delivering cell sheets in the treatment of burns and slow-healing wounds.

  16. Excellent Biofouling Alleviation of Thermoexfoliated Vermiculite Blended Poly(ether sulfone) Ultrafiltration Membrane.

    PubMed

    Orooji, Yasin; Liang, Feng; Razmjou, Amir; Li, Sha; Mofid, Mohammad Reza; Liu, Quan; Guan, Kecheng; Liu, Zhengkun; Jin, Wanqin

    2017-09-06

    Flux and antifouling properties of mixed matrix membranes (MMMs) are yet to attain satisfactory status. The objective of this study is to find a method for mitigating the biofouling of poly(ether sulfone) (PES) ultrafiltration membranes via blending of thermoexfoliated vermiculite (VMT). Flow cytometry analysis shows that the behaviors of Bacillus subtilis 168 as a Gram-positive bacterium and Escherichia coli DH5 alpha as a Gram-negative bacterium were different. Hence, cell property is a suspected contributory factor in biofilm formation. Accordingly, considering the local predominant bacterial strains, a regionally customized membrane could scientifically be an expert solution for biofouling mitigation. Fabricated composite membranes have shown a higher flux compared to control PES membrane. Among all composite membranes, the PES-VMT0.10 had the highest flux of 476.4 L/(m(2) h) (LMH) before fouling, and the highest flux of 210.7 LMH after three cycles of usage. In addition, the rejection rate of the PES-VMT0.15 The bovine serum albumin (BSA) sample was >77%, while that of the PES-VMT0.10 was >84%. The results of the static BSA adsorption test and the bacterial attachment test indicated that the membranes with macro-roughness on their surface showed better antibiofouling resistance. The antifouling properties of the modified membranes were also improved, because of their optimal wettability. On one hand, the hydrophilicity of membranes caused damaging both Gram-positive and Gram-negative bacteria and bacteriocidal effect. On the other hand, BSA adsorption and bacterial attachment on the membrane surface were affected by pore diameter.

  17. Preparation and characterization of poly (arylene ether isoxazole)s by fluoride ion-mediated aromatic nucleophilic displacement reactions

    NASA Technical Reports Server (NTRS)

    Herbert, C. G.; Bass, R. G.

    1994-01-01

    As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether isoxazole)s have been prepared by fluoride ion-catalyzed aromatic nucleophilic substitution reactions with bis(trimethylsiloxyphenyl) isoxazoles and activated bisarylhalides in diphenyl sulfone. Initial investigation involving the preparation of these materials with isoxazole bisphenols and activated bisarylhalides in the presence of potassium carbonate indicated that, under reaction conditions necessary to prepare high-molecular-weight materials, the isoxazole monomer was converted to an enamino ketone. This side reaction was avoided by using fluoride as a base. However, trimethylsilyl ether derivatives of the isoxazole bisphenols were required in these polymerizations for the preparation of high-molecular-weight materials. Moderate to high inherent viscosity eta(sub inh): 0.43-0.87 dl/g) materials with good thermal stability (air: 409-477 C, helium: 435-512 C) can be prepared by the silyl ether method. Glass transition temperatures ranged from 182 to 225 C for polymers with phenyl pendants and from 170 to 214 C for those without. Molecular weight control by 2% endcapping and the incorporation of a phenyl pendant at the 4 position of the isoxazole is necessary to yield polymers soluble in polar aprotic solvents at room temperature. There is evidence, however, indicating the existence of crosslinks between the polymer chains when the silyl ether approach is utilized.

  18. Preparation and characterization of poly (arylene ether isoxazole)s by fluoride ion-mediated aromatic nucleophilic displacement reactions

    NASA Technical Reports Server (NTRS)

    Herbert, C. G.; Bass, R. G.

    1994-01-01

    As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether isoxazole)s have been prepared by fluoride ion-catalyzed aromatic nucleophilic substitution reactions with bis(trimethylsiloxyphenyl) isoxazoles and activated bisarylhalides in diphenyl sulfone. Initial investigation involving the preparation of these materials with isoxazole bisphenols and activated bisarylhalides in the presence of potassium carbonate indicated that, under reaction conditions necessary to prepare high-molecular-weight materials, the isoxazole monomer was converted to an enamino ketone. This side reaction was avoided by using fluoride as a base. However, trimethylsilyl ether derivatives of the isoxazole bisphenols were required in these polymerizations for the preparation of high-molecular-weight materials. Moderate to high inherent viscosity eta(sub inh): 0.43-0.87 dl/g) materials with good thermal stability (air: 409-477 C, helium: 435-512 C) can be prepared by the silyl ether method. Glass transition temperatures ranged from 182 to 225 C for polymers with phenyl pendants and from 170 to 214 C for those without. Molecular weight control by 2% endcapping and the incorporation of a phenyl pendant at the 4 position of the isoxazole is necessary to yield polymers soluble in polar aprotic solvents at room temperature. There is evidence, however, indicating the existence of crosslinks between the polymer chains when the silyl ether approach is utilized.

  19. Conjugation of salmon calcitonin to a combed-shaped end functionalized poly(poly(ethylene glycol) methyl ether methacrylate) yields a bioactive stable conjugate.

    PubMed

    Ryan, Sinéad M; Wang, Xuexuan; Mantovani, Guiseppe; Sayers, Claire T; Haddleton, David M; Brayden, David J

    2009-04-02

    Salmon calcitonin (sCT) was conjugated via its N-terminal cysteine to a comb-shaped end-functionalized poly(poly(ethylene glycol) methyl ether methacrylate) (PolyPEG, 6.5 kDa), and to linear PEG (5 kDa). Conjugate molecular weight and purity was assessed by SEC-HPLC and MALDI-TOF MS. Bioactivity of conjugates was measured by cyclic AMP assay in T47D cells. Calcium and calcitonin levels were measured in rats following intravenous injections. Stability of conjugates was tested against serine proteases, intestinal and liver homogenates and serum. Cytotoxicity of conjugates was assessed by lactate dehydrogenase (LDH) assay and by haemolytic assay of rat red blood cells. Results showed that the two conjugates were of high purity with molecular weights similar to predictions. Both conjugates retained more than 85% bioactivity in vitro and had nanomolar EC(50) values similar to sCT. While both sCT-PolyPEG(6.5 K) and sCT-PEG(5 K) were resistant to metabolism by serine proteases, homogenates and serum, PolyPEG (6.5 K) was more so. Although both conjugates reduced serum calcium to levels similar to those achieved with sCT, PolyPEG(6.5 K) extended the T(1/2) and AUC of serum sCT over values achieved with sCT-PEG and sCT itself. None of PolyPEG, PEG or methacrylic acid displayed significant cytotoxicity. PolyPEG may therefore have potential to improve pharmacokinetic profiles of injected peptides.

  20. Morphological Changes During Secondary Crystallization and Melting in Poly(ether ether ketone) as Studied by Small Angle X-Ray Scattering

    NASA Astrophysics Data System (ADS)

    Verma, Ravi; Marand, Herve; Hsiao, Benjamin

    1996-03-01

    Poly(aryl ether ether ketone) [PEEK] is a semicrystalline polymer which exhibits the double endothermic melting behavior. Most authors are of the opinion that the origin of the low endotherm lies in the melting of thinner crystals, although some argue in favor of a melting-recrystallization model. It is now established that the low endotherm develops linearly with logarithm of crystallization time. However, all morphological studies conducted to date on the origin of the low endotherm have been limited to short times. As a result, the exact morphological changes associated with the low endotherm are not fully understood. We have monitored the morphological changes during long time melt crystallization and subsequent melting in PEEK. Morphological changes were monitored via real time small angle X-ray scattering [SAXS] using synchrotron radiations. Our novel analysis of the SAXS data indicates that the development of the low endotherm is accompanied by the formation of! secondary lamellar stacks compris ed of thinner lamellae (average thickness 70 A vs 120 A for primary lamallae). Further, our analysis suggests that during melting, the low endotherm is accompanied by the melting of these secondary lamellar stacks.

  1. Development of a cheap and accessible carbon fibers-in-poly(ether ether ketone) tube with high stability for online in-tube solid-phase microextraction.

    PubMed

    Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

    2016-02-01

    Carbon fibers (CFs) are one kind of important industrial materials that can be obtained commercially at low price. Based on the high extraction efficiency of carbon sorbents, a cheap and accessible carbon fibers-in-poly(ether ether ketone) (PEEK) tube was developed for online in-tube solid-phase microextraction (SPME) method. Coupled to high performance liquid chromatography (HPLC), the CFs-in-tube SPME was applied to analyze eight polycyclic aromatic hydrocarbons (PAHs) in environmental aqueous samples. Extraction conditions (sampling rate, extraction time, methanol content) and desorption time were investigated for optimization of conditions. Under the optimum conditions, the CFs-in-tube SPME-HPLC method provided high extraction efficiency with enrichment factors up to 1748. Good linearity (0.05-50 μg L(-1), 0.5-50 μg L(-1)) and low detection limits (0.01-0.1 μg L(-1)) were also obtained. The online analysis method was finally applied to determine several model PAHs analytes in real environmental aqueous samples. Some target analytes were detected and relative recoveries were in the range of 92.3-111%. Due to natural chemical stability of carbon fibers and PEEK tube, the CFs-in-tube device exhibited high resistance to organic solvent, acid and alkaline conditions.

  2. Pitch-based carbon-fibre-reinforced poly (ether-ether-ketone) OPTIMA assessed as a bearing material in a mobile bearing unicondylar knee joint.

    PubMed

    Scholes, S C; Unsworth, A

    2009-01-01

    The introduction of unicondylar knee prostheses has allowed the preservation of the non-diseased compartment of the knee while replacing the diseased or damaged compartment. In an attempt to reduce the likelihood of aseptic loosening, new material combinations have been investigated within the laboratory. Tribological tests (friction, lubrication, and wear) were performed on metal-on-carbon-fibre-reinforced (CFR) poly (ether-ether-ketone) (PEEK) (pitch-based) mobile unicondylar knee prostheses up to 5 x 10(6) cycles. Both a loaded soak control and an unloaded soak control (both medial and lateral components) were used to compensate for weight change due to lubricant absorption. For this material combination the loaded soak control gave slightly lower wear for both the medial and the lateral components than did the unloaded soak control. The medial components gave higher steady state wear than the lateral components (1.70 mm3 per 10(6) cycles compared with 1.02 mm3 per 10(6) cycles with the loaded soak control). The results show that the CFR PEEK unicondylar knee joints performed well in these wear tests. They gave lower volumetric wear rates than conventional metal-on-ultra-high-molecular-weight polyethylene prostheses have given in the past when tested under similar conditions. The friction tests showed that, at physiological viscosities, these joints operated in the boundary-mixed-lubrication regime. The low wear produced by these joints seems to be a function of the material combination and not of the lubrication regime.

  3. Imidazolium-functionalized poly(ether ether ketone) as membrane and electrode ionomer for low-temperature alkaline membrane direct methanol fuel cell

    NASA Astrophysics Data System (ADS)

    Yan, Xiaoming; Gu, Shuang; He, Gaohong; Wu, Xuemei; Benziger, Jay

    2014-03-01

    A series of imidazolium-functionalized poly(ether ether ketone)s (PEEK-ImOHs) were successfully synthesized by a two-step chloromethylation-Menshutkin reaction followed by hydroxide exchange. PEEK-ImOH membranes with ion exchange capacity (IEC) ranging from 1.56 to 2.24 mmol g-1 were prepared by solution casting. PEEK-ImOHs show selective solubility in aqueous solutions of acetone and tetrahydrofuran, but are insoluble in lower alcohols. PEEK-ImOH membranes with IEC of 2.03 mmol g-1 have high hydroxide conductivity (52 mS cm-1 at 20 °C), acceptable water swelling ratio (51% at 60 °C), and great tensile strength (78 MPa), and surprising flexibility (elongation-to-break of 168%), and high thermal stability (Decomposition temperature: 193 °C). In addition, PEEK-ImOH membranes show low methanol permeability (1.3-6.9 × 10-7 cm2 s-1). PEEK-ImOH membrane was tested in methanol/O2 fuel cell as both the HEM and the ionomer impregnated into the catalyst layer; the open circuit voltage is 0.84 V and the peak power density is 31 mW cm-2.

  4. Properties investigation of sulfonated poly(ether ether ketone)/polyacrylonitrile acid-base blend membrane for vanadium redox flow battery application.

    PubMed

    Li, Zhaohua; Dai, Wenjing; Yu, Lihong; Liu, Le; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

    2014-11-12

    Acid-base blend membrane prepared from sulfonated poly(ether ether ketone) (SPEEK) and polyacrylonitrile (PAN) was detailedly evaluated for vanadium redox flow battery (VRFB) application. SPEEK/PAN blend membrane exhibited dense and homogeneous cross-section morphology as scanning electron microscopy and energy-dispersive X-ray spectroscopy images show. The acid-base interaction of ionic cross-linking and hydrogen bonding between SPEEK and PAN could effectively reduce water uptake, swelling ratio, and vanadium ion permeability, and improve the performance and stability of blend membrane. Because of the good balance of proton conductivity and vanadium ion permeability, blend membrane with 20 wt % PAN (S/PAN-20%) showed higher Coulombic efficiency (96.2% vs 91.1%) and energy efficiency (83.5% vs 78.4%) than Nafion 117 membrane at current density of 80 mA cm(-2) when they were used in VRFB single cell. Besides, S/PAN-20% membrane kept a stable performance during 150 cycles at current density of 80 mA cm(-2) in the cycle life test. Hence the SPEEK/PAN acid-base blend membrane could be used as promising candidate for VRFB application.

  5. Novel melt-processable poly(ether ether ketone)(PEEK)/inorganic fullerene-like WS(2) nanoparticles for critical applications.

    PubMed

    Naffakh, Mohammed; Díez-Pascual, Ana M; Marco, Carlos; Gómez, Marián A; Jiménez, Ignacio

    2010-09-09

    The combination of high-performance thermoplastic poly(ether ether ketone) (PEEK) with inorganic fullerene-like tungsten disulfide (IF-WS(2)) nanoparticles offers an attractive way to combine the merits of organic and inorganic materials into novel polymer nanocomposite materials. Here, we report the processing of novel PEEK/IF-WS(2) nanocomposites, which overcome the nanoparticle agglomerate formation and provide PEEK-particle interactions. The IF-WS(2) nanoparticles do not require exfoliation or modification, making it possible to obtain stronger, lighter materials without the complexity and processing cost associated with these treatments. The nanocomposites were fabricated by melt blending, after a predispersion step based on ball milling and mechanical treatments in organic solvent, which leads to the dispersion of individually IF-WS(2) nanoparticles in the PEEK matrix as confirmed by scanning electron microscopy. In order to determine the performance of the PEEK/IF-WS(2) nanocomposites for potential critical applications, particularly for the aircraft industry, we have extensively investigated these materials with a wide range of structural, thermal, and mechanical techniques using time-resolved synchrotron X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, dynamic-mechanical analysis, and tensile and impact tests as well as thermal measurements. Modulus, tensile strengh, thermal stability, and thermal conductivity of PEEK exhibited remarkable improvement with the addition of IF-WS(2).

  6. Dual cross-linked organic-inorganic hybrid polymer electrolyte membranes based on quaternized poly(ether ether ketone) and (3-aminopropyl)triethoxysilane

    NASA Astrophysics Data System (ADS)

    Zhang, Na; Wang, Baolong; Zhao, Chengji; Zhang, Yurong; Bu, Fanzhe; Cui, Ying; Li, Xuefeng; Na, Hui

    2015-02-01

    Quaternized poly(ether ether ketone)s (QPEEKs) are synthesized to absorb phosphoric acid (PA) and used as high temperature proton exchange membranes (HTPEMs). In order to improve their oxidative and mechanical stability without sacrificing proton conductivities, a series of dual cross-linked organic-inorganic hybrid membranes are prepared using (3-aminopropyl)triethoxysilane (APTES) as a cross-linker. The amine of APTES reacts with two benzyl bromide groups to build the primary cross-linking network. The Si-O-Si network generated by the hydrolysis of triethoxysilane in APTES is the secondary cross-linking network. The dual cross-linking hybrid networks improve the mechanical and oxidative stability of PA doped membranes. They can endure up to 15.3 h in 3 wt.% H2O2, 4 ppm Fe2+ Fenton solution at 80 °C. During the hydrolysis of triethoxysilane, the release of small molecules (H2O and C2H5OH) forms many pores in surfaces and interior of membranes. These pores and the resulted Si-OH groups corporately enhance the PA absorbing ability and proton conductivity. The highest proton conductivity is 61.7 mS cm-1 for PA-QPEEK-10%APTES at 200 °C under anhydrous condition. These membranes show great potential to be used in HTPEM fuel cell.

  7. Reduced platelets and bacteria adhesion on poly(ether ether ketone) by photoinduced and self-initiated graft polymerization of 2-methacryloyloxyethyl phosphorylcholine.

    PubMed

    Tateishi, Takaharu; Kyomoto, Masayuki; Kakinoki, Sachiro; Yamaoka, Tetsuji; Ishihara, Kazuhiko

    2014-05-01

    Aromatic poly(ether ether ketone) (PEEK) is a super engineering plastic, which has good mechanical properties and is resistant to physical and chemical stimuli. We have, therefore, attempted to use PEEK in cardiovascular devices. Synthetic cardiovascular devices require both high hemocompatibility and anti-inflammatory activity in addition to the mechanical properties. We modified the PEEK surface by photoinduced and self-initiated graft polymerization with 2-methacryloyloxyethyl phosphorylcholine (MPC; PMPC-grafted PEEK) for obtaining good antithrombogenicity. Polymerization was carried out on the surface of PEEK under radiation of ultraviolet (UV) light during which we controlled monomer concentrations, temperatures, and UV intensities. The biological performance of the PMPC-grafted PEEK was examined and compared with that of unmodified PEEK. With increase in the thickness of the PMPC layer, the amount of fibrinogen adsorption decreased significantly in comparison to that in the case of unmodified PEEK. When placed in contact with human platelet-rich plasma, surface of the PMPC-grafted PEEK clearly showed inhibition of platelet adhesion and activation. Also, bacterial adhesion was reduced dramatically on the PMPC-grafted PEEK. Thus, the PMPC grafting on PEEK improved the antithrombogenicity.

  8. Tribological assessment of a flexible carbon-fibre-reinforced poly(ether-ether-ketone) acetabular cup articulating against an alumina femoral head.

    PubMed

    Scholes, S C; Inman, I A; Unsworth, A; Jones, E

    2008-04-01

    New material combinations have been introduced as the bearing surfaces of hip prostheses in an attempt to prolong their life by overcoming the problems of failure due to wear-particle-induced osteolysis. This will hopefully reduce the need for revision surgery. The study detailed here used a hip simulator to assess the volumetric wear rates of large-diameter carbon-fibre-reinforced pitch-based poly(ether-ether-ketone) (CFR-PEEK) acetabular cups articulating against alumina femoral heads. The joints were tested for 25 x 10(6) cycles. Friction tests were also performed on these joints to determine the lubrication regime under which they operate. The average volumetric wear rate of the CFR-PEEK acetabular component of 54 mm diameter was 1.16 mm(3)/10(6) cycles, compared with 38.6 mm(3)/10(6) cycles for an ultra-high-molecular-weight polyethylene acetabular component of 28 mm diameter worn against a ceramic head. This extremely low wear rate was sustained over 25 x 10(6) cycles (the equivalent of up to approximately 25 years in vivo). The frictional studies showed that the joints worked under the mixed-boundary lubrication regime. The low wear produced by these joints showed that this novel joint couple offers low wear rates and therefore may be an alternative material choice for the reduction of osteolysis.

  9. A new strategy for designing high-performance sulfonated poly(ether ether ketone) polymer electrolyte membranes using inorganic proton conductor-functionalized carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Gong, Chunli; Zheng, Xuan; Liu, Hai; Wang, Guangjin; Cheng, Fan; Zheng, Genwen; Wen, Sheng; Law, Wing-Cheung; Tsui, Chi-Pong; Tang, Chak-Yin

    2016-09-01

    Remarkable progress has been made on the use of polymer electrolyte membranes (PEMs) for renewable-energy-related research. In particular, carbon nanotubes (CNTs) have emerged as versatile nanomaterials to modify PEMs. However, the inert ionic conduction ability and possible short-circuiting risk are the two major obstacles to their further development. In this work, CNTs are firstly functionalized with an inorganic proton conductor, boron phosphate (BPO4), using a facile polydopamine-assisted sol-gel method to yield BPO4@CNTs. This new additive is then used to modify sulfonated poly(ether ether ketone) (SPEEK). Polydopamine coating layer can act as an extraordinary glue to homogeneously adhere BPO4 nanoparticles on CNTs, thereby not only reducing the risk of short-circuiting, but also fabricating new proton-conducting pathways in the composite membranes. A comprehensive characterization reveals that the thermal stability, tensile properties, and dimensional stability of PEMs are significantly improved. Compared with pure SPEEK, the proton conductivity of SPEEK/BPO4@CNTs-2 is improved by 45% and 150% at 20 °C and at 80 °C, respectively. Furthermore, the H2/O2 cell performance of SPEEK/BPO4@CNTs-2 membrane exhibits a peak power density of 340.7 mW cm-2 at 70 °C, which is significantly better than that of pure SPEEK (254.2 mW cm-2), demonstrating the great potential of proton conductors-functionalized CNTs in PEMs.

  10. Preparation of main-chain-type and side-chain-type sulfonated poly(ether ether ketone) membranes for direct methanol fuel cell applications

    NASA Astrophysics Data System (ADS)

    Tsai, Jie-Cheng; Lin, Chien-Kung

    Novel main-chain-type and side-chain-type sulphonated poly(ether ether ketone)s (MS-SPEEKs) are synthesised by reacting the sulphonic acid groups of pristine SPEEKs with 2-aminoethanesulphonic acid to improve the nano-phase separated morphology of the material. 1H NMR and FT-IR spectroscopy are employed to determine the structure and composition of main-chain-type and side-chain-type sulphonated polymers. Flexible and tough membranes with reasonable thermal properties are obtained. The MS-SPEEKs show good hydrolytic stability, and water uptake values ranging from 15% to 30% are observed. Compared to Nafion 117 ®, the methanol permeability of the MS-SPEEKs is dramatically reduced to 8.83 × 10 -8 cm 2 s -1 to 3.31 × 10 -7 cm 2 s -1. The proton conductivity increases with increasing temperature, reaching 0.013-0.182 S cm -1. A maximum power density and open circuit voltage of 115 mW cm -2 and 0.830 V are obtained at 80 °C, respectively, which is significantly greater than the values generated with Nafion 117 ®. The introduction of pendent side-chain-type sulphonic acid groups increases the single-cell performance by more than approximately 20%; thus, the lower water diffusivity, methanol permeability, electro-osmotic drag coefficient and high cell performance indicated that MS-SPEEK is a promising candidate for DMFC applications.

  11. Molecular modeling of the morphology and transport properties of two direct methanol fuel cell membranes: phenylated sulfonated poly(ether ether ketone ketone) versus Nafion

    SciTech Connect

    Devanathan, Ramaswami; Idupulapati, Nagesh B.; Dupuis, Michel

    2012-08-14

    We have used molecular dynamics simulations to examine membrane morphology and the transport of water, methanol and hydronium in phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) and Nafion membranes at 360 K for a range of hydration levels. At comparable hydration levels, the pore diameter is smaller, the sulfonate groups are more closely packed, the hydronium ions are more strongly bound to sulfonate groups, and the diffusion of water and hydronium is slower in Ph-SPEEKK relative to the corresponding properties in Nafion. The aromatic carbon backbone of Ph-SPEEKK is less hydrophobic than the fluorocarbon backbone of Nafion. Water network percolation occurs at a hydration level ({lambda}) of {approx}8 H{sub 2}O/SO{sub 3}{sup -}. At {lambda} = 20, water, methanol and hydronium diffusion coefficients were 1.4 x 10{sup -5}, 0.6 x 10{sup -5} and 0.2 x 10{sup -5} cm{sup 2}/s, respectively. The pore network in Ph-SPEEKK evolves dynamically and develops wide pores for {lambda} > 20, which leads to a jump in methanol crossover and ion transport. This study demonstrates the potential of aromatic membranes as low-cost challengers to Nafion for direct methanol fuel cell applications and the need to develop innovative strategies to combat methanol crossover at high hydration levels.

  12. Modeling the Nanophase Structural Dynamics of Phenylated Sulfonated Poly Ether Ether Ketone Ketone (Ph-SPEEKK) Membranes as a Function of Hydration

    SciTech Connect

    Lins, Roberto D.; Devanathan, Ramaswami; Dupuis, Michel

    2011-03-03

    Solvated phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) membranes in the presence of hydronium ions were modeled by classical molecular dynamics simulations. The characterization of the nanophase structure and dynamics of such membranes was carried out as a function of the water content lambda, where lambda is the number of water molecules per sulfonate group, for lambda values of 3.5, 6, 11, 25, and 40. Analysis of pair correlation functions supports the experimental observation of membrane swelling upon hydration as well the increase in water and hydronium ion diffusion with increasing lambda. While the average number of hydrogen bonds between hydronium ions and sulfonate groups is dramatically affected by the hydration level, the average lifetime of the hydrogen bonds remains essentially constant. The membrane is found to be relatively rigid and its overall flexibility shows little dependence on water content. Compared to Nafion, water and ion diffusion coefficients are considerably smaller at lower hydration levels and room temperature. However, at higher lambda values of 25 and 40 these coefficients are comparable to those in Nafion at a lambda value of 16. This study also shows that water diffusion in Ph-SPEEKK membranes at low hydration levels can be significantly improved by raising the temperature with important implications for proton conductivity.

  13. Advances in membrane materials: desalination membranes based on directly copolymerized disulfonated poly(arylene ether sulfone) random copolymers.

    PubMed

    Xie, Wei; Park, Ho-Bum; Cook, Joseph; Lee, Chang Hyun; Byun, Gwangsu; Freeman, Benny D; McGrath, James E

    2010-01-01

    The water and salt transport properties of chlorine tolerant disulfonated poly(arylene ether sulfone) (BPS) copolymers have been characterized. Cast BPS membranes of both salt form and acid form with sulfonation levels from 20% to 40% were investigated. Water permeability of BPS films increases more than one order of magnitude as sulfonation level increases from 20% to 40%, while the salt permeability of the corresponding membranes increases two orders of magnitude. Moderate salt rejection (98.2%) was achieved by a BPS salt form membrane with a sulfonation level of 20%.

  14. Catalytic Reduction of Noble Metal Salts by Sodium Hypophosphite Promoted by the Film Poly-(p-Allyl Ether Benzenesulfonic Acid)

    PubMed Central

    Costa, M. I. C. F.; Steter, J. R.; Purgato, F. L. S.; Romero, J. R.

    2011-01-01

    Glassy carbon electrodes were coated with the film poly-(p-allyl ether benzenesulfonic acid) by an anodic procedure. Nickel, platinum, and palladium ions were introduced into the film by ion exchange of H+ with the corresponding salts. These ions were catalytically reduced to their corresponding metals using the known electroless reducing agent sodium hypophosphite. Scanning electron microcopy and energy dispersive X-ray spectroscopy were carried out to demonstrate the occurrence of the catalytic process. To compare this method with another one carried out in our laboratory, the electrocatalytic reduction of H+ was studied using the same modified electrodes. A suggested mechanism for the catalysis is proposed. PMID:24052832

  15. Study of novel nonlinear optical material based on Poly(aryl ether ketone) and its application in SHG imaging

    NASA Astrophysics Data System (ADS)

    Liu, Yi; Liu, Hui; Qin, Guangjiong; Gui, Zhiguo; Yang, Zhimao; Liu, Jialei

    2017-10-01

    Novel nonlinear optical polymer based on poly(aryl ether ketone) was designed and prepared. Such kind of materials showed excellent water solubility and thermal properties, its onset decomposition temperature can reach 314 °C; glass transition temperature can reach 170 °C. Though the nonlinear optical coefficients (d33) is not very large at 1310 nm, just about 13.9 pm/V; such kind of materials show us a low absorption spectral window at red and infrared light area (wavelength longer than 650 nm). Under the laser of 1310 nm, the morphology of the poled films can be detected by second harmonic generation (SHG) scanning microscopy.

  16. Plasma graft of poly(ethylene glycol) methyl ether methacrylate (PEGMA) on RGP lens surface for reducing protein adsorption

    NASA Astrophysics Data System (ADS)

    Shiheng, Yin; Li, Ren; Yingjun, Wang

    2017-01-01

    Poly(ethylene glycol) methyl ether methacrylate (PEGMA) was grafted on fluorosilicone acrylate rigid gas permissible contact lens surface by means of argon plasma induced polymerization to improve surface hydrophilicity and reduce protein adsorption. The surface properties were characterized by contact angle measurement, x-ray photoelectron spectroscopy (XPS) and atomic force microscopy respectively. The surface protein adsorption was evaluated by lysozyme solution immersion and XPS analysis. The results indicated that a thin layer of PEGMA was successfully grafted. The surface hydrophilicity was bettered and surface free energy increased. The lysozyme adsorption on the lens surface was reduced greatly. The study was supported by National Natural Science Foundation of China (No. 51273072).

  17. Plasma graft of poly(ethylene glycol) methyl ether methacrylate (PEGMA) on RGP lens surface for reducing protein adsorption

    NASA Astrophysics Data System (ADS)

    Yin, Shiheng; Ren, Li; Wang, Yingjun

    2017-01-01

    Poly(ethylene glycol) methyl ether methacrylate (PEGMA) was grafted on fluorosilicone acrylate rigid gas permissible contact lens surface by means of argon plasma induced polymerization to improve surface hydrophilicity and reduce protein adsorption. The surface properties were characterized by contact angle measurement, x-ray photoelectron spectroscopy (XPS) and atomic force microscopy respectively. The surface protein adsorption was evaluated by lysozyme solution immersion and XPS analysis. The results indicated that a thin layer of PEGMA was successfully grafted. The surface hydrophilicity was bettered and surface free energy increased. The lysozyme adsorption on the lens surface was reduced greatly. The study was supported by National Natural Science Foundation of China (No. 51273072).

  18. New Poly(amide-imide)/Nanocomposites Reinforced Silicate Nanoparticles Based on N-pyromellitimido-L-phenyl Alanine Containing Ether Moieties

    NASA Astrophysics Data System (ADS)

    Faghihi, Khalil; Shabanian, Meisam; Dadfar, Ehsan

    2012-02-01

    A series of Poly(amide-imide)/montmorillonite nanocomposites containing N-pyromellitimido-L-phenyl alanine moiety in the main chain were synthesized by a convenient solution intercalation technique. Poly(amide-imide) (PAI) 5 as a source of polymer matrix was synthesized by the direct polycondensation reaction of N-pyromellitimido-L-phenyl alanine 3 with 4,4'-diamino diphenyl ether 4 in the presence of triphenyl phosphite (TPP), CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP). The resulting nanocomposite films were characterized by Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The results showed that organo-modified clay was dispersed homogeneously in PAI matrix. TGA indicated an enhancement of thermal stability of new nanocomposites compared with the pure polymer.

  19. Structure and mechanical properties of poly(benzyl ether) monodendron Langmuir films

    NASA Astrophysics Data System (ADS)

    Kampf, James Patrick

    2000-10-01

    The Langmuir technique combined with a traditional polymer science approach has been used to investigate the monolayer properties of poly(benzyl ether) monodendrons modified with linear oligo(ethylene glycol) chains at the air-water interface. Film balance measurements have been used to probe the relation between the amphiphilic balance of the monodendrons and the stability and structure of the monolayer. Analysis of the surface pressure-area (pi- A) isotherms indicates that the linear hydrophilic chain controls the adhesion to the interface, while the hydrophobic monodendron determines the molecular shape, monolayer compressibility, and film cohesion. A novel interpretation of the pi-A isotherm as a stress-strain curve allows for a more detailed analysis of the monolayer mechanical properties. The pseudo-2D monolayers behave in a manner analogous to many bulk polymers, showing a yield point and a region of plastic flow. Within the plastic flow region, the stress-strain behavior can be quantitatively captured using a constitutive law that assumes both a power law stress dependence and an Arrhenius temperature dependence for the strain rate. Constant strain rate and dilational creep experiments have been used to determine the stress exponent and the creep activation energy, respectively. Analysis of the isotherms suggests the existence of a monolayer glass transition within the temperature range studied. Compressibility experiments provide further evidence of a monolayer glass transition, the temperature for which lies more than 15°C below the bulk value. Dynamic mechanical analysis has been performed using an interfacial stress rheometer to study the viscoelasticity of the monolayer near the glass transition. A master curve of the frequency dependence of the shear modulus produced using time-temperature superposition also implies that the monolayer approaches a glass transition. As an extension of the work at the air-water interface, we have completed a

  20. Triblock copolymers encapsulated poly (aryl benzyl ether) dendrimer zinc(II) phthalocyanine nanoparticles for enhancement in vitro photodynamic efficacy.

    PubMed

    Huang, Yide; Yu, Huizhen; Lv, Huafei; Zhang, Hong; Ma, Dongdong; Yang, Hongqin; Xie, Shusen; Peng, Yiru

    2016-12-01

    A novel series of nanoparticles formed via an electrostatic interaction between the periphery of negatively charged 1-2 generation aryl benzyl ether dendrimer zinc (II) phthalocyanines and positively charged poly(L-lysin) segment of triblock copolymer, poly(L-lysin)-block-poly(ethylene glycol)-block-poly(L-lysin), was developed for the use as an effective photosensitizers in photodynamic therapy. The dynamic light scattering, atomic force microscopy showed that two nanoparticles has a relevant size of 80-150nm. The photophysical properties and singlet oxygen quantum yields of free dendrimer phthalocyanines and nanoparticles exhibited generation dependence. The intracellular uptake of dendrimer phthalocyanines in Hela cells was significantly elevated as they were incorporated into the micelles, but was inversely correlated with the generation of dendrimer phthalocyanines. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles induced efficient cell death. Using a mitochondrial-sepcific dye rhodamine 123 (Rh123), our fluorescence microscopic result indicated that nanoparticles localized to the mitochondria.

  1. Adjustable degradation and drug release of a thermosensitive hydrogel based on a pendant cyclic ether modified poly(ε-caprolactone) and poly(ethylene glycol)co-polymer.

    PubMed

    Wang, Weiwei; Deng, Liandong; Liu, Shasha; Li, Xu; Zhao, Xiumei; Hu, Renjie; Zhang, Jianhua; Han, Haijie; Dong, Anjie

    2012-11-01

    The convenient and precise fabrication of drug-hydrogel formulations with satisfactory degradability and a well-controlled drug release profile are crucial factors for injectable hydrogel formulations in clinical applications. Here a new injectable thermosensitive hydrogel formed from poly(ε-caprolactone) (PCL)-poly(ethylene glycol)-poly(ε-caprolactone) amphiphilicco-polymers with 1,4,8-trioxa[4.6]spiro-9-undecanone (TOSUO) moieties incorporated in the poly(ε-caprolactone) (PCL)block (PECT) was constructed to provide a route to tailor the degradation and drug release behavior. The effect of hydrophilic cyclic ether moieties on the degradation of and drug release by PECT hydrogels were evaluated in vitro and in vivo. The results indicated that a freeze-dried powder of paclitaxel-loaded PECT nanoparticles rapidly dissolved in water at ambient temperature with slightly shaking and formed a stable injectable in situ drug-hydrogel formulation at body temperature, which is convenient for clinical operations because it avoids the need for pre-quenching or long-term incubation. The paclitaxel distribution was also more quantitative and homogeneous on entrapping paclitaxel in PECT nanoparticles. Further, the small number of pendant cyclic ether groups in PCL could decrease the cystallinity and hydrophobicity and, as a result, the in vitro and in vivo retention time of PECT hydrogels and the release of entrapped paclitaxel could be tuned from a few weeks to months by varying the amount of PTOSUO in the hydrophobic block. Significantly, paclitaxel-loaded PECT nanoparticles and free paclitaxel could be simultaneously released during the in vitro paclitaxel release from PECT hydrogels. A histopathological evaluation indicated that in vivo injected PECT hydrogels produced only a modest inflammatory response. Thus pendant cyclic ether modification of PCL could be an effective way to achieve the desired degradation and drug release profiles of amphiphilicco

  2. Influence of chemical structure on hydration and gas transport mechanisms of sulfonated poly(aryl ether ketone) membranes.

    PubMed

    Simon, Sandra; Espuche, Eliane; Gouanvé, Fabrice; Chauveau, Edouard; Marestin, Catherine; Mercier, Régis

    2012-10-25

    This work reports the influence of the chemical structure of two sulfonated poly(aryl ether ketone)s (SPAEK) on the hydration and gas transport mechanism of thin membranes made thereupon. For this purpose, two sulfonated poly(aryl ether ketone)s having the same ionic exchange capacity (IEC) but bearing a different repartition of the sulfonic acid groups along the polymer backbone were prepared. These polymers were synthesized by direct copolymerization of two specific sulfonated precursors, bisphenol AF and 4,4'-difluorobenzophenone. The morphology of the membranes was studied by transmission electron microscopy, and the thermal properties of the ionomers were determined from differential scanning calorimetry and thermogravimetric analyses. A detailed analysis of the water sorption isotherms and kinetics was performed. The gas transport properties were also determined for He, H(2), and CO(2) in the full range of water activity. From the detailed analysis of the water sorption isotherm and of the relative contributions of the Fickian diffusion and relaxation phenomena, a water sorption mechanism was proposed in relation with the SPAEK architectures and polymers' chain mobility. This mechanism allowed explaining the different evolution of the gas transport properties observed as a function of the gas nature and hydration rate.

  3. Synthesis and characterization of sulfonated poly(ether sulfone)s containing mesonaphthobifluorene for polymer electrolyte membrane fuel cell.

    PubMed

    Lim, Youngdon; Seo, Dongwan; Lee, Soonho; Hossain, Md Awlad; Lim, Jinseong; Lee, Sangyoung; Hong, Taehoon; Kim, Whangi

    2014-10-01

    The novel sulfonated poly(ether sulfone)s containing mesonaphthobifluorene (MNF) moiety were synthesized and characterized their properties. The prepared polymers have highly conjugated aromatic structure due to the MNF group which is an allotrope of carbon and one atom thick planar sheets of sp2-bonded carbon atoms. Poly(ether sulfone)s bearing tetraphenylethylene on polymer backbone were synthesized by polycondensation and followed intra-cyclization from tetraphenylethylene to form MNF by Friedel-craft reaction with Lewis acid (FeCl3). The sulfonation was performed selectively on MNF units with conc. sulfuric acid. The structural properties of the sulfonated polymers were investigated by 1H-NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, and proton conductivity. The synthesized polymer electrolyte membranes showed better thermal and dimensional stabilities owing to the inducted highly conjugated aromatic structure in the polymer backbone. The water uptake of the synthesized membranes ranged from 23-52%, compared with 32.13% for Nafion 211 at 80 degrees C. The synthesized membranes exhibited proton conductivities (80 degrees C, RH 90%) of 74.6-100.4 mS/cm, compared with 102.7 mS/cm for Nafion 211.

  4. Preparation of Poly(Dinitropropyl Vinyl Ether) with Crosslinking Sites, for Use as a Castable Binder

    DTIC Science & Technology

    1978-12-01

    GPC of Modified and Unmodified Poly-DNPVE ............. 7 3 100 MHz NMR Spectrum of Poly-DNPVE (M.W. 4,000) ...... 18 4 220 MHz NMR Spectrum of Poly...DNPVE in d 6- Acetone/DCl/D 2 0 .................. 19 5 100 MHz NMR Spectrum of Poly-DNPVE (M.W. 4,000), Partially Reduced...20 6 100 MHz NMR Spectrum of Poly-DNPVE (M.W. 4,000), Partially Reduced and Hydroxymethylated .............. 21 TABLES Table Page 1 Reaction

  5. Preparation and characterization of polymer blend based on sulfonated poly (ether ether ketone) and polyetherimide (SPEEK/PEI) as proton exchange membranes for fuel cells

    SciTech Connect

    Hashim, Nordiana; Ali, Ab Malik Marwan; Lepit, Ajis; Rasmidi, Rosfayanti; Subban, Ri Hanum Yahaya; Yahya, Muhd Zu Azhan

    2015-08-28

    Blends of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios using N-methyl-2-pyrrolidone (NMP) as solvent by the solution cast technique. The degree of sulfonation (DS) of the sulfonated PEEK was determined from deuterated dimethyl sulfoxide (DMSO-d{sub 6}) solution of the purified polymer using {sup 1}H NMR method. The properties studied in the present investigation includes conductivity, water uptake, thermal stability and structure analysis of pure SPEEK as well as SPEEK-PEI polymer blend membranes. The experimental results show that the conductivity of the membranes increased with increase in temperature from 30 to 80°C, except for that of pure SPEEK membrane which increased with temperature from 30 to 60°C while its conductivity decreased with increasing temperature from 60 to 80°C. The conductivity of 70wt.%SPEEK-30wt.%PEI blend membrane at 80% relative humidity (RH) is found to be 1.361 × 10{sup −3} Scm{sup −1} at 30°C and 3.383 × 10{sup −3} Scm{sup −1} at 80°C respectively. It was also found that water uptake and thermal stability of the membranes slightly improved upon blending with PEI. Structure analysis was carried out using Fourier Transform Infrared (FTIR) spectroscopy which revealed considerable interactions between sulfonic acid group of SPEEK and imide groups of PEI. Modification of SPEEK by blending with PEI shows good potential for improving the electrical and physical properties of proton exchange membranes.

  6. Proton conductivity and fuel cell property of composite electrolyte consisting of Cs-substituted heteropoly acids and sulfonated poly(ether-ether ketone)

    NASA Astrophysics Data System (ADS)

    Oh, S. Y.; Yoshida, T.; Kawamura, G.; Muto, H.; Sakai, M.; Matsuda, A.

    Inorganic-organic composite electrolytes were fabricated from partially Cs +-substituted heteropoly acids (Cs-HPAs) and sulfonated poly(ether-ether ketone) (SPEEK) for application in fuel cells. Heteropoly acids, such as phosphotungstic acid (H 3PW 12O 40:WPA), and silicotungstic acid (H 4SiW 12O 40:WSiA), were mechanochemically treated with cesium hydrogen sulfate (CsHSO 4) to obtain the form of Cs-HPAs. SPEEK was prepared from PEEK by sulfonation using concentrated sulfuric acid. Water durability and surface structure of HPAs were modified by introducing Cs + into HPAs. Flexible and hot water stable composite electrolytes were obtained, and their electrochemical properties were markedly improved with the addition of Cs-HPAs into the SPEEK matrix. Maximum power densities of 245 and 247 mW cm -2 were obtained for 50WPA·50CsHSO 4 and 50WSiA·50CsHSO 4 in SPEEK (1/5 by weight) composite electrolytes, respectively, from single cell tests at 80 °C and 80 RH%. These results suggest that a three-dimensional proton-conductive path was formed among homogeneously distributed Cs-HPAs particles in the SPEEK matrix. The Cs-HPAs incorporated into the SPEEK matrix increased the number of protonate sites in the electrolyte. These observations imply that the mechanochemically synthesized Cs-HPAs, which consist of hydrogen bondings between Cs-HPAs and -HSO 4 -, dissociated from CsHSO 4, are promising materials as inorganic fillers in inorganic-organic composite.

  7. Porous titanium-6 aluminum-4 vanadium cage has better osseointegration and less micromotion than a poly-ether-ether-ketone cage in sheep vertebral fusion.

    PubMed

    Wu, Su-Hua; Li, Yi; Zhang, Yong-Quan; Li, Xiao-Kang; Yuan, Chao-Fan; Hao, Yu-Lin; Zhang, Zhi-Yong; Guo, Zheng

    2013-12-01

    Interbody fusion cages made of poly-ether-ether-ketone (PEEK) have been widely used in clinics for spinal disorders treatment; however, they do not integrate well with surrounding bone tissue. Ti-6Al-4V (Ti) has demonstrated greater osteoconductivity than PEEK, but the traditional Ti cage is generally limited by its much greater elastic modulus (110 GPa) than natural bone (0.05-30 GPa). In this study, we developed a porous Ti cage using electron beam melting (EBM) technique to reduce its elastic modulus and compared its spinal fusion efficacy with a PEEK cage in a preclinical sheep anterior cervical fusion model. A porous Ti cage possesses a fully interconnected porous structure (porosity: 68 ± 5.3%; pore size: 710 ± 42 μm) and a similar Young's modulus as natural bone (2.5 ± 0.2 GPa). When implanted in vivo, the porous Ti cage promoted fast bone ingrowth, achieving similar bone volume fraction at 6 months as the PEEK cage without autograft transplantation. Moreover, it promoted better osteointegration with higher degree (2-10x) of bone-material binding, demonstrated by histomorphometrical analysis, and significantly higher mechanical stability (P < 0.01), shown by biomechanical testing. The porous Ti cage fabricated by EBM could achieve fast bone ingrowth. In addition, it had better osseointegration and superior mechanical stability than the conventional PEEK cage, demonstrating great potential for clinical application. © 2013 Wiley Periodicals, Inc. and International Center for Artificial Organs and Transplantation.

  8. Preparation and characterization of polymer blend based on sulfonated poly (ether ether ketone) and polyetherimide (SPEEK/PEI) as proton exchange membranes for fuel cells

    NASA Astrophysics Data System (ADS)

    Hashim, Nordiana; Ali, Ab Malik Marwan; Lepit, Ajis; Rasmidi, Rosfayanti; Subban, Ri Hanum Yahaya; Yahya, Muhd Zu Azhan

    2015-08-01

    Blends of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios using N-methyl-2-pyrrolidone (NMP) as solvent by the solution cast technique. The degree of sulfonation (DS) of the sulfonated PEEK was determined from deuterated dimethyl sulfoxide (DMSO-d6) solution of the purified polymer using 1H NMR method. The properties studied in the present investigation includes conductivity, water uptake, thermal stability and structure analysis of pure SPEEK as well as SPEEK-PEI polymer blend membranes. The experimental results show that the conductivity of the membranes increased with increase in temperature from 30 to 80°C, except for that of pure SPEEK membrane which increased with temperature from 30 to 60°C while its conductivity decreased with increasing temperature from 60 to 80°C. The conductivity of 70wt.%SPEEK-30wt.%PEI blend membrane at 80% relative humidity (RH) is found to be 1.361 × 10-3 Scm-1 at 30°C and 3.383 × 10-3 Scm-1 at 80°C respectively. It was also found that water uptake and thermal stability of the membranes slightly improved upon blending with PEI. Structure analysis was carried out using Fourier Transform Infrared (FTIR) spectroscopy which revealed considerable interactions between sulfonic acid group of SPEEK and imide groups of PEI. Modification of SPEEK by blending with PEI shows good potential for improving the electrical and physical properties of proton exchange membranes.

  9. Study on the pretreatment of poly(ether ether ketone)/multiwalled carbon nanotubes composites through environmentally friendly chemical etching and electrical properties of the chemically metallized composites.

    PubMed

    Zhai, Tong; Di, Lizhi; Yang, De'an

    2013-12-11

    The high-volume resistivity and surface resistance of poly(ether ether ketone)/multiwalled carbon nanotubes (PEEK/MWCNT) composites restrict their use in an electronic field. To decrease the volume resistivity and surface resistance, we metalized the composites by electroless plating. The composites and metal coatings were characterized by SEM, XPS, AFM, EDX, and XRD spectroscopy. The swelling ratio of the composites, volume resistivity of two-side-coated composites, sheet resistance of plated composites, and adhesion between the coating and PEEK/MWCNT were tested. The results are as follows. A high roughness and a small swelling ratio were obtained by swelling in 18 mol/L H2SO4 for 3 min. Most of the MWCNT on the surface were still wrapped with PEEK after swelling. To expose the MWCNT, an environmentally friendly and effective etchant (MnO2-NaH2PO4-H2SO4) was used. After etching, not only were high roughness and partially exposed MWCNT obtained but also the percentage of hydrophilic groups on the surface was increased. A dense cauliflower-like Ni-P coating was produced, and the exposed MWCNT were embedded in the metal coating after electroless plating for 20 min. The coating exhibited an amorphous structure with a phosphorus content of 11.21 wt %. The volume resistivity of two-side-coated PEEK/MWCNT dropped sharply to 38 Ω·m after electroless plating for 5 min. The sheet resistance decreased with increasing the electroless-plating time, and it dropped to 0.88 Ω/square after electroless plating for 40 min. The adhesion of the coating reached the highest 5 B scale (ASTM D3359) and could even undergo the test 20 times.

  10. Block copolymers encapsulated poly (aryl benzyl ether) dendrimer silicon (IV) phthalocyanine for in vivo and in vitro photodynamic efficacy of choroidal neovascularization

    NASA Astrophysics Data System (ADS)

    Wang, Xiongwei; Chen, Kuizhi; Huang, Zheng; Peng, Yiru

    2015-03-01

    A novel series of poly (aryl benzyl ether) dendrimer silicon phthalocyanines loaded block copolymers ethoxypoly(ethylene glycol)-poly (lactic-co-glycolic acid) (MPEG-PLGA)were formed. The time-dependent intracellular uptake of nanoparticles in HUVECs cells increased as they were incorporated into nanoparticles. With its highly effective selective accumulation on choroidal neovascularization(CNV). This treatment resulted in a efficacious choroidal neovascularization (CNV) occlusion with minimal unfavorable phototoxicity.

  11. Computational and experimental investigations of one-step conversion of poly(carbonate)s into value-added poly(aryl ether sulfone)s.

    PubMed

    Jones, Gavin O; Yuen, Alexander; Wojtecki, Rudy J; Hedrick, James L; García, Jeannette M

    2016-07-12

    It is estimated that ∼2.7 million tons poly(carbonate)s (PCs) are produced annually worldwide. In 2008, retailers pulled products from store shelves after reports of bisphenol A (BPA) leaching from baby bottles, reusable drink bottles, and other retail products. Since PCs are not typically recycled, a need for the repurposing of the PC waste has arisen. We report the one-step synthesis of poly(aryl ether sulfone)s (PSUs) from the depolymerization of PCs and in situ polycondensation with bis(aryl fluorides) in the presence of carbonate salts. PSUs are high-performance engineering thermoplastics that are commonly used for reverse osmosis and water purification membranes, medical equipment, as well as high temperature applications. PSUs generated through this cascade approach were isolated in high purity and yield with the expected thermal properties and represent a procedure for direct conversion of one class of polymer to another in a single step. Computational investigations performed with density functional theory predict that the carbonate salt plays two important catalytic roles in this reaction: it decomposes the PCs by nucleophilic attack, and in the subsequent polyether formation process, it promotes the reaction of phenolate dimers formed in situ with the aryl fluorides present. We envision repurposing poly(BPA carbonate) for the production of value-added polymers.

  12. Computational and experimental investigations of one-step conversion of poly(carbonate)s into value-added poly(aryl ether sulfone)s

    PubMed Central

    Yuen, Alexander; Wojtecki, Rudy J.; Hedrick, James L.; García, Jeannette M.

    2016-01-01

    It is estimated that ∼2.7 million tons poly(carbonate)s (PCs) are produced annually worldwide. In 2008, retailers pulled products from store shelves after reports of bisphenol A (BPA) leaching from baby bottles, reusable drink bottles, and other retail products. Since PCs are not typically recycled, a need for the repurposing of the PC waste has arisen. We report the one-step synthesis of poly(aryl ether sulfone)s (PSUs) from the depolymerization of PCs and in situ polycondensation with bis(aryl fluorides) in the presence of carbonate salts. PSUs are high-performance engineering thermoplastics that are commonly used for reverse osmosis and water purification membranes, medical equipment, as well as high temperature applications. PSUs generated through this cascade approach were isolated in high purity and yield with the expected thermal properties and represent a procedure for direct conversion of one class of polymer to another in a single step. Computational investigations performed with density functional theory predict that the carbonate salt plays two important catalytic roles in this reaction: it decomposes the PCs by nucleophilic attack, and in the subsequent polyether formation process, it promotes the reaction of phenolate dimers formed in situ with the aryl fluorides present. We envision repurposing poly(BPA carbonate) for the production of value-added polymers. PMID:27354514

  13. Tailor-made pore controlled poly (arylene ether ketone) membranes as a lithium-ion battery separator

    NASA Astrophysics Data System (ADS)

    Le Mong, Anh; Kim, Dukjoon

    2016-02-01

    Porous poly(arylene ether ketone) (PAEK) membranes are prepared by selective removal of poly(lactic acid) (PLA) molecules from self-assembled PAEK-PLA block copolymers. The pore size and porosity of the membranes are precisely controlled by adjusting PLA concentration. The synthesis of the PAEK-PLA copolymer is confirmed by FTIR and NMR spectroscopies and the morphology of the membrane is examined by scanning electron microscopy (SEM). Several important properties such as liquid electrolyte uptake, contact angle, thermal and mechanical stability, and lithium ion conductivity are measured and compared with those of commercial poly(propylene) (PP) membranes to investigate their application feasibility as a separator. The porous PAEK membrane shows improved thermal and dimensional stability compared to the PP membrane. The EC/DEC/EMC (1:1:1, v/v/v) soaked PAEK membrane with a pore diameter of 50 nm shows the highest lithium ion conductivity, higher than that of PP membrane. More importantly, the porous PAEK membranes show superior liquid electrolyte holding capacity to the PP membrane.

  14. Anhydrous state proton and lithium ion conducting solid polymer electrolytes based on sulfonated bisphenol-A-poly(arylene ethers)

    NASA Astrophysics Data System (ADS)

    Guha Thakurta, Soma

    Sulfonated polymer based solid polymer electrolytes (SPEs) have received considerable interest in recent years because of their wide variety of applications particularly in fuel cells, batteries, supercapacitors, and electrochromic devices. The present research was focused on three interrelated subtopics. First, two different bisphenol-A-poly(arylene ethers), polyetherimide (PEI) and polysulfone (PSU) were sulfonated by a post sulfonation method to various degrees of sulfonation, and their thermal and mechanical properties were examined. The effects of poly(arylene ether) chemical structure, reaction time, concentration, and types of sulfonating agents on sulfonation reaction were investigated. It was found that deactivation of bisphenol A unit caused by the electron withdrawing imide, retarded the sulfonation of PEI compared to PSU. Sulfonation conducted with a high concentration of sulfonating agent and/or prolonged reaction time exhibited evidence of degradation at the isopropylidene unit. The degradation occurred through the same mechanistic pathway with the two different sulfonating agents, chlorosulfonic acid (CSA) and trimethylsilyl chlorosulfonate (TMSCS). The degradation was faster with CSA than its silyl ester, TMSCS, and was evident even at low acid concentration. Second, novel anhydrous proton conducting solid polymer electrolytes (SPEs) were prepared by the incorporation of 1H-1,2,4-triazole (Taz) as a proton solvent in sulfonated polyetherimide (SPEI) matrix. The size, shape, and state of dispersion (crystal morphology) of triazole crystals in SPEI were examined as a function of degree of sulfonation and triazole concentration. Increasing sulfonic acid content caused reduction of triazole crystallite size, hence the depression of melting temperature and their uniform distribution throughout the sulfonated polymer matrix. The increased rate of structure diffusion within the smaller size crystals due to the improved molecular mobility contributed

  15. 40 CFR 721.7700 - Poly(oxy-1,2-ethanediyl), α-hydro-ω-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Poly(oxy-1,2-ethanediyl), α-hydro-Ï-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1). 721.7700 Section 721.7700 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL...

  16. Colloidal Properties of Aqueous Poly(vinyl acetate)-Borate Dispersions with Short-Chain Glycol Ethers.

    PubMed

    Duncan, Teresa T; Berrie, Barbara H; Weiss, Richard G

    2016-08-18

    We report the influence of adding five short-chain glycol ethers (SCGEs) on the structure, stability, and viscoelastic properties of aqueous dispersions of partially hydrolyzed poly(vinyl acetate) and borax. The properties of these gel-like materials have been investigated as a function of the structure of the added SCGE both below and above the critical aggregation (or micellar) concentrations using (11) B and (13) C NMR, rheology, and small-angle neutron scattering. The results indicate that the SCGE aggregation behavior is not affected by incorporation into the gel-like network. However, changes in the viscoelasticity and structural properties of the dispersions were detected that can be correlated to the nature of the solvent system. Also, the ability of these materials to clean an unvarnished acrylic paint surface coated with synthetic soil has been evaluated using colorimetery, and the surface of the dispersion after cleaning was visualized with scanning electron microscopy.

  17. Characterization of a poly(ether urethane)-based controlled release membrane system for delivery of ketoprofen

    NASA Astrophysics Data System (ADS)

    Macocinschi, Doina; Filip, Daniela; Vlad, Stelian; Oprea, Ana Maria; Gafitanu, Carmen Anatolia

    2012-10-01

    A poly(ether urethane) based on polytetrahydrofuran containing hydroxypropyl cellulose for biomedical applications was tested for its biocompatibility. Ketoprofen was incorporated (3% and 6%) in the polyurethane matrix as an anti-inflammatory drug. Kinetic and drug release mechanisms were studied. The pore size and pore size distribution of the polyurethane membranes were investigated by scanning electron microscopy. Surface tension characteristics as well as moisture sorption properties such as diffusion coefficients and equilibrium moisture contents of the membrane material were studied. It was found that kinetics and release mechanisms are in function of medium pH, composition of polymer-drug system, pore morphology and pore size distribution. Prolonged nature of release of ketoprofen is assured by low amount of drug in polyurethane membrane and physiological pH.

  18. Enhanced proton conductivity of sulfonated poly(p-phenylene-co-aryl ether ketone) proton exchange membranes with controlled microblock structure

    NASA Astrophysics Data System (ADS)

    He, Qingyi; Xu, Tong; Qian, Huidong; Zheng, Jifu; Shi, Ce; Li, Yunqi; Zhang, Suobo

    2015-03-01

    A new series of sulfonated poly(p-phenylene-co-aryl ether ketone)s (s, m, l-SPP-co-PAEKs) microblock polymers containing different hydrophobic units with precisely defined lengths have been prepared via the nickel (0) catalyzed coupling copolymerization and characterized to act as proton exchange membranes. By controlling the length and chemical structure of the hydrophobic units in the copolymers, these novel microblock polymers can exhibit well-developed nanophase morphologies and large length-scale of the ionic channels, resulting in the improvement of the proton conductivity in both the wet and dry state. Moreover, the membrane l-SPP-co-PAEK 1.80 with the largest hydrophobic micro-block length shows high proton conductivity, excellent dimensional stability, low glass-transition temperature (Tg), good oxidative stability and superior cell performance.

  19. Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

    NASA Technical Reports Server (NTRS)

    Siochi, Emilie

    1995-01-01

    Gel Permeation Chromatography (GPC) was used to analyze poly(arylene ether phosphine oxide)s whose backbones were identical except for the ketone content and placement. These samples were exposed to low Earth orbit environment (predominantly atomic oxygen) on space shuttle flights. The materials and their unexposed controls were then characterized by GPC to investigate the effect of atomic oxygen on the molecular weight distributions. Analysis of the soluble portion of the samples revealed that there was significant loss of high molecular weight species. The presence of insoluble material also suggested that crosslinking was induced by the atomic oxygen exposure and that this very likely occurred at the high molecular weight portion of the molecular weight distribution.

  20. Nanocomposites Derived from Carbon Nanofibers and a Hyperbranched Poly(Ether-Ketone): In Situ Polymerization, Chain-End Modification, and Properties (Preprint)

    DTIC Science & Technology

    2007-05-01

    an A2B monomer, was easily polymerized via a Friedel - Crafts acylation in poly(phosphoric acid)/phosphorus pentoxide (PPA/P2O5; 1:4 w/w) medium to...Poly(ether- ketone):: In-situ Polymerization, Chain-end Modification & Properties Friedel - Crafts polymerization of 5- phenoxyisophthalic acid (AB2...easily polymerized via a Friedel - Crafts acylation in poly(phosphoric acid)/phosphorus pentoxide (PPA/P2O5; 1:4 w/w) medium to form a CO2H-terminated

  1. Aromatic poly(arylene ether urea) with high dipole moment for high thermal stability and high energy density capacitors

    NASA Astrophysics Data System (ADS)

    Cheng, Zhaoxi; Lin, Minren; Wu, Shan; Thakur, Yash; Zhou, Yue; Jeong, Dae-Yong; Shen, Qundong; Zhang, Q. M.

    2015-05-01

    Developing dielectric polymers with higher dielectric constant without sacrificing loss and thermal stability is of great importance for next generation of high energy density capacitors. We show here that by replacing the CH2 group in the aromatic polyurea (ArPU) with the polar ether group, thus raising the dipole moment of the molecular unit, poly(arylene ether urea) (PEEU) shows an increased dielectric constant of 4.7, compared with 4.2 of ArPU. Moreover, PEEU maintains the low dielectric loss and is thermally stable up to 250 °C. As a result, the polymer delivers 13 J/cm3 discharged energy density at room temperature and 9 J/cm3 at 120 °C. The high quality films perform well in terms of both breakdown strength (at 700 MV/m at room temperature) and leakage current from room temperature to elevated temperature. At 120 °C, the breakdown strength is 600 MV/m and the conductivity is 1.58 × 10-14 S/cm measured under 100 MV/m.

  2. Artificial extracellular matrix for biomedical applications: biocompatible and biodegradable poly (tetramethylene ether) glycol/poly (ε-caprolactone diol)-based polyurethanes.

    PubMed

    Shahrousvand, Mohsen; Mir Mohamad Sadeghi, Gity; Salimi, Ali

    2016-12-01

    The cells as a tissue component need to viscoelastic, biocompatible, biodegradable, and wettable extracellular matrix for their biological activity. In this study, in order to prepare biomedical polyurethane elastomers with good mechanical behavior and biodegradability, a series of novel polyester-polyether- based polyurethanes (PUs) were synthesized using a two-step bulk reaction by melting pre-polymer method, taking 1,4-Butanediol (BDO) as chain extender, hexamethylene diisocyanate as the hard segment, and poly (tetramethylene ether) glycol (PTMEG) and poly (ε-caprolactone diol) (PCL-Diol) as the soft segment without a catalyst. The soft to the hard segment ratio was kept constant in all samples. Polyurethane characteristics such as thermal and mechanical properties, wettability and water adsorption, biodegradability, and cellular behavior were changed by changing the ratio of polyether diol to polyester diol composition in the soft segment. Our present work provides a new procedure for the preparation of engineered polyurethanes in surface properties and biodegradability, which could be a good candidate for bone, cartilage, and skin tissue engineering.

  3. Inorganic-organic polymer electrolytes based on poly(vinyl alcohol) and borane/poly(ethylene glycol) monomethyl ether for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Aydın, Hamide; Şenel, Mehmet; Erdemi, Hamit; Baykal, Abdülhadi; Tülü, Metin; Ata, Ali; Bozkurt, Ayhan

    In this study, poly(vinyl alcohol) (PVA) was modified with poly(ethylene glycol) monomethyl ether (PEGME) using borane-tetrahydrofuran (BH 3/THF) complex. Molecular weights of both PVA and PEGME were varied prior to reaction. Boron containing comb-branched copolymers were produced and abbreviated as PVA1PEGMEX and PVA2PEGMEX. Then polymer electrolytes were successfully prepared by doping of the host matrix with CF 3SO 3Li at several stoichiomeric ratios with respect to EO to Li. The materials were characterized via nuclear magnetic resonance (1H NMR and 11B NMR), Fourier transform infrared spectroscopy (FT-IR), Thermogravimetry (TG) and differential scanning calorimeter (DSC). The ionic conductivity of these novel polymer electrolytes were studied by dielectric-impedance spectroscopy. Li-ion conductivity of these polymer electrolytes depends on the length of the side units as well as the doping ratio. Such electrolytes possess satisfactory ambient temperature ionic conductivity (>10 -4 S cm -1). Cyclic voltammetry results illustrated that the electrochemical stability domain extends over 4 V.

  4. Anti-fouling behavior of hyperbranched polyglycerol-grafted poly(ether sulfone) hollow fiber membranes for osmotic power generation.

    PubMed

    Li, Xue; Cai, Tao; Chung, Tai-Shung

    2014-08-19

    To sustain high performance of osmotic power generation by pressure-retarded osmosis (PRO) processes, fouling on PRO membranes must be mitigated. This is especially true for the porous support of PRO membranes because its porous structure is very prone to fouling by feeding river water. For the first time, we have successfully designed antifouling PRO thin-film composite (TFC) membranes by synthesizing a dendritic hydrophilic polymer with well-controlled grafting sites, hyperbranched polyglycerol (HPG), and then grafting it on poly(ether sulfone) (PES) hollow fiber membrane supports. Compared to the pristine PES membranes, polydopamine modified membranes, and conventional poly(ethylene glycol) (PEG)-grafted membranes, the HPG grafted membranes show much superior fouling resistance against bovine serum albumin (BSA) adsorption, E. coli adhesion, and S. aureus attachment. In high-pressure PRO tests, the PES TFC membranes are badly fouled by model protein foulants, causing a water flux decline of 31%. In comparison, the PES TFC membrane grafted by HPG not only has an inherently higher water flux and a higher power density but also exhibits better flux recovery up to 94% after cleaning and hydraulic pressure impulsion. Clearly, by grafting the properly designed dendritic polymers to the membrane support, one may substantially sustain PRO hollow fiber membranes for power generation.

  5. Chemical grafting of poly(ethylene glycol) methyl ether methacrylate onto polymer surfaces by atmospheric pressure plasma processing.

    PubMed

    D'Sa, Raechelle A; Meenan, Brian J

    2010-02-02

    This article reports the use of atmospheric pressure plasma processing to induce chemical grafting of poly(ethylene glycol) methyl ether methacrylate (PEGMA) onto polystyrene (PS) and poly(methyl methacrylate) (PMMA) surfaces with the aim of attaining an adlayer conformation which is resistant to protein adsorption. The plasma treatment was carried out using a dielectric barrier discharge (DBD) reactor with PEGMA of molecular weights (MW) 1000 and 2000, PEGMA(1000) and PEGMA(2000), being grafted in a two step procedure: (1) reactive groups are generated on the polymer surface followed by (2) radical addition reactions with the PEGMA. The surface chemistry, coherency, and topography of the resulting PEGMA grafted surfaces were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM), respectively. The most coherently grafted PEGMA layers were observed for the 2000 MW PEGMA macromolecule, DBD processed at an energy dose of 105.0 J/cm(2) as indicated by ToF-SIMS images. The effect of the chemisorbed PEGMA layer on protein adsorption was assessed by evaluating the surface response to bovine serum albumin (BSA) using XPS. BSA was used as a model protein to determine the grafted macromolecular conformation of the PEGMA layer. Whereas the PEGMA(1000) surfaces showed some protein adsorption, the PEGMA(2000) surfaces appeared to absorb no measurable amount of protein, confirming the optimum surface conformation for a nonfouling surface.

  6. Preparation and properties of biomedical segmented polyurethanes based on poly(ether ester) and uniform-size diurethane diisocyanates.

    PubMed

    Yin, Shengnan; Xia, Yiran; Jia, Qi; Hou, Zhao-Sheng; Zhang, Na

    2017-01-01

    This study describes the preparation and properties of a novel aliphatic cost-effective segmented polyurethanes (SPUs) based on poly(ether ester) (poly-(ε-caprolactone-co-l-lactide)-poly(ethylene glycol)-poly-(ε-caprolactone-co-l-lactide), PECLA) and uniform-size diurethane diisocyanates (HDI-BDO-HDI). PECLA was synthesized via bulk ring-opening polymerization with poly(ethylene glycol) (PEG) as an initiator and ε-caprolactone, l-lactide as monomers. By chain extension of PECLA diol with HDI-BDO-HDI, three SPUs with different hydrophilic segments content and hard segments content were obtained. The chemical structures of the chain extender, PECLA and SPUs were confirmed by (1)H NMR, (13)C NMR, FT-IR, HR-TOF-MS and GPC. The influences of PEG content and uniform-size hard segments on in vitro degradability and mechanical properties of SPU films were researched. Similar thermostability observed in TGA curves of SPU films indicated that the hard segments and PEG content had little influence on the thermostability. The formation of microsphase-separated morphologies, which were demonstrated by the results of DSC and XRD, and physical-linking (H-bonds) network structures led to better mechanical properties of SPU films (ultimate stress: 23.1-17.9 MPa; elongation at break: 840-1130%). The results of water absorption and water contact angle showed that the bulk and surface hydrophilicity were closely related with the hydrophilic PEG content in SPU backbone. And the water absorption being less than 10 wt% indicated that the SPU films had low swelling property. In vitro hydrolytic degradation studies showed that the time of the SPU films becoming fragments was 34-19 days and the degradation rate increased with the increasing content of hydrophilic segments in SPUs, indicating that the degradation rate of SPU films could be controlled by adjusting PEG content. Cytotoxicity test of film extracts were conducted using L929 cells, and the relative growth rate exceeded 90

  7. [Experience with Poly Ether Ether Ketone (PEEK) cages and locking plate for anterior cervical fusion in the treatment of spine trauma without cord injury].

    PubMed

    Delépine, F; Jund, S; Schlatterer, B; de Peretti, F

    2007-12-01

    The purpose of this study was to determine whether spinal fusion using radiotransparent cages can be an appropriate treatment for traumatic injury of the cervical spine. This series included 30 patients aged 17-84 years (average 46 years) treated between October 1999 and June 2003 for traumatic injury of the cervical spine without neurological deficit or cord injury. There were two bifocal cases so that the study concerned 32 fusions. Injuries were: tear drop (n=1), serious flexion sprain (n=8), biarticular dislocation (n=4), serous hyperextension sprain (n=4), dislocation-fracture (n=1), uniarticular fracture (n=7), fracture-separation of the facet joints (n=4), post-traumatic herniation (n=3). For each injury, we measured pre and postoperatively and at last follow-up: the intersomatic angle, anterior displacement, and height of the intersomatic space at the center of the intervertebral disc. All x-rays were read twice, by two independent investigators. In the event of disagreement, the x-rays were read again by a senior surgeon and the main author of this article. Anterior fusion was achieved using a Poly Ether Ether Ketone (PEEK) (32%) and knitted carbon (68%) cage (cologne, Ostapek, Nexis) filled with cancellous bone harvested percutaneously from the iliac crest. The cage was associated with an anterior titanium plate fixation (Senegas, Euros and Orion, Medtronic). A posterior approach was associated if further stability was required (n=4 fusions). All patients were reviewed at minimum five months follow-up. Intersomatic fusion was verified on the standard x-rays (plus stress images and computed tomography at three months). Fusion was considered to be achieved if continuous bone lines crossed the graft and angle measurements remained stable, with the cage in the same position on successive examinations. One patient died from lung cancer five months after spinal fusion. All other patients survived with a mean follow-up of 24 months. Fusion was achieved in all

  8. Free Volume in Glassy Poly(arylene Ether Ketone)s

    NASA Technical Reports Server (NTRS)

    Hinkley, J. A.; Eftekhari, A.; Crook, R. A.; Jensen, B. J.; Singh, J. J.

    1996-01-01

    Amorphous polyarylene ether ketones were examined in the glassy state by positron annihilation lifetime spectroscopy ( PALS ) and in the melt by standard rheological techniques. Specimens were well-characterized fractions of two isomeric structures. PALS clearly shows that the polymer with meta linkages in its backbone contains larger voids (greater than 0.25 nm radius). Thus despite their similar bulk densities, the two materials must pack very differently on a local scale. On the other hand, the free volumes inferred from the WLF treatment of melt viscosity data are practically identical in both materials ca. 4% at T(sub g). The comparison between techniques sheds some light on the distribution of free volume.

  9. In vitro evaluation of poly(ethylene glycol)-block-poly(ɛ-caprolactone) methyl ether copolymer coating effects on cells adhesion and proliferation

    NASA Astrophysics Data System (ADS)

    Rusen, Laurentiu; Neacsu, Patricia; Cimpean, Anisoara; Valentin, Ion; Brajnicov, Simona; Dumitrescu, L. N.; Banita, Janina; Dinca, Valentina; Dinescu, Maria

    2016-06-01

    Understanding and controlling natural and synthetic biointerfaces is known to be the key to a wide variety of application within cell culture and tissue engineering field. As both material characteristics and methods are important in tailoring biointerfaces characteristics, in this work we explore the feasibility of using Matrix Assisted Pulsed Laser Evaporation technique for obtaining synthetic copolymeric biocoatings (i.e. poly(ethylene glycol)-block-poly(ɛ-caprolactone) methyl ether) for evaluating in vitro Vero and MC3T3-E1 pre-osteoblasts cell response. Characterization and evaluation of the coated substrates were carried out using different techniques. The Fourier transform infrared spectroscopy data demonstrated that the main functional groups in the MAPLE-deposited films remained intact. Atomic Force Microscopy images showed the coatings to be continuous, with the surface roughness depending on the deposition parameters. Moreover, the behaviour of the coatings in medium mimicking the pH and temperature of the human body was studied and corelated to degradation. Spectro-ellipsometry (SE) and AFM measurements revealed the degradation trend during immersion time by the changes in coating thickness and roughness. In vitro biocompatibility was studied by indirect contact tests on Vero cells in accordance with ISO 10993-5/2009. The results obtained in terms of cell morphology (phase contrast microscopy) and cytotoxicity (LDH and MTT assays) proved biocompatibility. Furthermore, direct contact assays on MC3T3-E1 pre-osteoblasts demonstrated the capacity of all analyzed specimens to support cell adhesion, normal cellular morphology and growth.

  10. Novel RAFT amphiphilic brush copolymer steric stabilisers for cubosomes: poly(octadecyl acrylate)-block-poly(polyethylene glycol methyl ether acrylate).

    PubMed

    Chong, Josephine Y T; Mulet, Xavier; Postma, Almar; Keddie, Daniel J; Waddington, Lynne J; Boyd, Ben J; Drummond, Calum J

    2014-09-21

    Copolymers, particularly Pluronics®, are typically used to sterically stabilise colloidal nanostructured particles composed of a lyotropic liquid crystalline bicontinuous cubic phase (cubosomes). There is a need to design and assess new functionalisable stabilisers for these colloidal drug delivery systems. Six amphiphilic brush copolymers, poly(octadecyl acrylate)-block-poly(polyethylene glycol methyl ether acrylate) (P(ODA)-b-P(PEGA-OMe)), synthesised by reversible addition-fragmentation chain transfer (RAFT), were assessed as novel steric stabilisers for cubosomes. It was found that increasing the density of PEG on the nanostructured particle surface by incorporating a PEG brush design (i.e., brush copolymer), provided comparable and/or increased stabilisation effectiveness compared to a linear PEG structure, Pluronic® F127, which is extensively used for steric stabilisation of cubosomes. Assessment was conducted both prior to and following the removal of the dodecyl trithiocarbonate end-group, by free radical-induced reduction. The reduced (P(ODA)-b-P(PEGA-OMe) copolymers were more effective steric stabilisers for phytantriol and monoolein colloidal particle dispersions than their non-reduced analogues. High throughput characterisation methodologies, including an accelerated stability assay (ASA) and synchrotron small angle X-ray scattering (SAXS), were implemented in this study for the rapid assessment of steric stabiliser effectiveness and lyotropic liquid crystalline phase identification. Phytantriol cubosomes stabilised with P(ODA)-b-P(PEGA-OMe) copolymers exhibited a double diamond cubic phase (Q(2)(D)), whilst monoolein cubosomes exhibited a primitive cubic phase (Q(2)(P)), analogous to those formed using Pluronic® F127.

  11. High strength of physical hydrogels based on poly(acrylic acid)-g-poly(ethylene glycol) methyl ether: role of chain architecture on hydrogel properties.

    PubMed

    Yang, Jun; Gong, Cheng; Shi, Fu-Kuan; Xie, Xu-Ming

    2012-10-04

    This investigation was to study the connections between polymer branch architecture of physical hydrogels and their properties. The bottle-brush-like polymer chains of poly(acrylic acid)-g-poly(ethylene glycol) methyl ether (PAA-g-mPEG) with PAA as backbones and mPEG as branch architecture were synthesized and in situ grafted from silica nanoparticles (SNs) to construct hydrogels cross-linked networks in aqueous solutions. The structural variables to be discussed included molecular weight and molar ratio of branch chains, and new aspects of the formation mechanism of physical hydrogels with branch structure in the absence of organic cross-links were present. The results indicated that the differences of polymer chain architecture could be distinguished via their different interactions that are present by gelation process and mature gel properties, such as gel strength and swelling ratio. The gelation occurred at the critical polymer concentration and molecular weight, respectively, and the inorganic/organic (SNs/PAA-g-mPEG) nanoparticles began to entangle and construct the cross-linking networks afterward. The gel-to-sol transition temperature (T(g-s)) and radii of SNs that were encapsulated by polymer chains as a function of time for chains' disentanglement were monitored according to the observation of the dissolution process, and the molecular weight between two consecutive entanglements (M(e)) was calculated thereafter. This study showed that the introduction of branch chain onto the linear backbone significantly promoted the chain interactions and increased entanglement density, which contributed to the hydrogels' network integrity and rigidity, thus illustrating greater elongation at break and tensile strength than the hydrogels formulated with linear polymer chains.

  12. Self-assembly of brush-like poly[poly(ethylene glycol) methyl ether methacrylate] synthesized via aqueous atom transfer radical polymerization.

    PubMed

    Hussain, Hazrat; Mya, Khine Yi; He, Chaobin

    2008-12-02

    Self-assembly of brush-like well-defined poly[poly(ethylene glycol) methyl ether methacrylate] homopolymers, abbreviated as P(PEGMA-475) and P(PEGMA-1100) is investigated in aqueous solution by employing dynamic/static light scattering (DLS/SLS) and transmission electron microscopy (TEM), whereas 475 and 1100 is molar mass of the respective PEGMA macromonomer. The mentioned brush-like homopolymers are synthesized by aqueous ATRP at room temperature. The critical association concentration (CAC) of the synthesized polymers in water depends on the length of the PEG side chains but not on the overall molar mass of the polymer. Thus, approximately the same CAC of approximately 0.35 mg/mL is estimated for various P(PEGMA-1100) samples, and approximately 0.7 mg/mL is estimated for P(PEGMA-475) series. All the investigated P(PEGMA-1100) samples form multimolecular micelles in aqueous solution, where the hydrodynamic size (Rh) and the aggregation number (Nagg) of micelles decreases as the molecular weight of P(PEGMA-1100) increases. This can be attributed to the increased steric hindrances between the PEG side chains in corona of micelles formed by higher molar mass P(PEGMA-1100). The tendency of micelle formation by samples of P(PEGMA-475) series is significantly lower than that of P(PEGMA-1100) series, as demonstrated by their significantly higher CAC and micelles of lower Nagg. The Rh of micelles does not depend strongly on polymer concentration, which suggests that these micelles are formed via the closed association model. Micelles formed by P(PEGMA-1100) series slightly shrink with increase in temperature from 25 to 60 degrees C, while those of P(PEGMA-475) series are found to be insensitive to the same temperature variation. Finally, TEM is carried out to visualize the formed micelles after transferring the aqueous solution to carbon film.

  13. Poly(benzyl ether) Dendrimers Functionalized at the Core with Palladium Bis(N-Heterocyclic Carbene) Complexes as Catalysts for the Heck Coupling Reaction.

    PubMed

    Ortiz, Alba M; Sánchez-Méndez, Alberto; de Jesús, Ernesto; Flores, Juan C; Gómez-Sal, Pilar; Mendicuti, Francisco

    2016-02-01

    Bis(imidazolylidene)palladium complexes 9-12 containing a sterically hindered aryl group (mesityl or 2,6-diisopropylphenyl) and a poly(benzyl ether) dendron as N-substituents of the NHC ligand are accessible up to the third generation by transmetalation of the corresponding silver complexes. Complexes 9-12 are soluble, active, and very stable catalysts under Heck reaction conditions. The NHC ligand appears to be stably coordinated to the Pd during catalysis. The catalytic activity increases with generation number, although irregularly. The palladium site is not significantly congested in the reaction solvent by the increasing size of the dendritic substituents, as corroborated by X-ray diffraction, fluorescence and DOSY-NMR spectroscopy, and MD simulation studies. This is a consequence of the conformational semiflexibility of the poly(benzyl ether) dendrons and the benzylic link between these dendrons and the N-heterocyclic ligands.

  14. The Distribution of mixtures of dodecyl ether of poly(23)ethylene glycol with sodium dodecyl sulfate and dodecyltrimethylammonium bromide in the water/octane system

    NASA Astrophysics Data System (ADS)

    Soboleva, O. A.; Pronchenko, K. S.; Chernysheva, M. G.; Badun, G. A.

    2012-03-01

    The scintillation phase and tensiometry methods were used to study the mutual influence of dodecyl ether of poly(23)ethylene glycol (Brij-35) with sodium dodecyl sulfate and Brij-35 with dodecyltrimethylammonium bromide on the distribution in the water/octane system and adsorption at the liquid/liquid interface. The composition of mixed adsorption layers was determined and interaction parameters between molecules were calculated according to the Rosen model.

  15. Magnetoresponsive Poly(ether sulfone)-Based Iron Oxide cum Hydrogel Mixed Matrix Composite Membranes for Switchable Molecular Sieving.

    PubMed

    Lin, Xi; Nguyen Quoc, Bao; Ulbricht, Mathias

    2016-10-11

    Stimuli-responsive membranes that can adjust mass transfer and interfacial properties "on demand" have drawn large interest over the last few decades. Here, we designed and prepared a novel magnetoresponsive separation membrane with remote switchable molecular sieving effect by simple one-step and scalable nonsolvent induced phase separation (NIPS) process. Specifically, poly(ether sulfone) (PES) as matrix for an anisotropic membrane, prefabricated poly(N-isopropylacrylamide) (PNIPAAm) nanogel (NG) particles as functional gates, and iron oxide magnetic nanoparticles (MNP) as localized heaters were combined in a synergistic way. Before membrane casting, the properties of the building blocks, including swelling property and size distribution for NG, and magnetic property and heating efficiency for MNP, were investigated. Further, to identify optimal film casting conditions for membrane preparation by NIPS, in-depth rheological study of the effects of composition and temperature on blend dope solutions was performed. At last, a composite membrane with 10% MNP and 10% NG blended in a porous PES matrix was obtained, which showed a large, reversible, and stable magneto-responsivity. It had 9 times higher water permeability at the "on" state of alternating magnetic field (AMF) than at the "off"-state. Moreover, the molecular weight cutoff of such membrane could be reversibly shifted from ∼70 to 1750 kDa by switching off or on the external AMF, as demonstrated in dextran ultrafiltration tests. Overall, it has been proved that the molecular sieving performance of the novel mixed matrix composite membrane can be controlled by the swollen/shrunken state of PNIPAAm NG embedded in the nanoporous barrier layer of a PES-based anisotropic porous matrix, via the heat generation of nearby MNP. And the structure of such membrane can be tailored by the NIPS process conditions. Such membrane has potential as enabling material for remote-controlled drug release systems or devices for

  16. Oxidation-Responsive and "Clickable" Poly(ethylene glycol) via Copolymerization of 2-(Methylthio)ethyl Glycidyl Ether.

    PubMed

    Herzberger, Jana; Fischer, Karl; Leibig, Daniel; Bros, Matthias; Thiermann, Raphael; Frey, Holger

    2016-07-27

    Poly(ethylene glycol) (PEG) is a widely used biocompatible polymer. We describe a novel epoxide monomer with methyl-thioether moiety, 2-(methylthio)ethyl glycidyl ether (MTEGE), which enables the synthesis of well-defined thioether-functional poly(ethylene glycol). Random and block mPEG-b-PMTEGE copolymers (Mw/Mn = 1.05-1.17) were obtained via anionic ring opening polymerization (AROP) with molecular weights ranging from 5 600 to 12 000 g·mol(-1). The statistical copolymerization of MTEGE with ethylene oxide results in a random microstructure (rEO = 0.92 ± 0.02 and rMTEG E = 1.06 ± 0.02), which was confirmed by in situ (1)H NMR kinetic studies. The random copolymers are thermoresponsive in aqueous solution, with a wide range of tunable transition temperatures of 88 to 28 °C. In contrast, mPEG-b-PMTEGE block copolymers formed well-defined micelles (Rh ≈ 9-15 nm) in water, studied by detailed light scattering (DLS and SLS). Intriguingly, the thioether moieties of MTEGE can be selectively oxidized into sulfoxide units, leading to full disassembly of the micelles, as confirmed by detection of pure unimers (DLS and SLS). Oxidation-responsive release of encapsulated Nile Red demonstrates the potential of these micelles as redox-responsive nanocarriers. MTT assays showed only minor effects of the thioethers and their oxidized derivatives on the cellular metabolism of WEHI-164 and HEK-293T cell lines (1-1000 μg·mL(-1)). Further, sulfonium PEG polyelectrolytes can be obtained via alkylation or alkoxylation of MTEGE, providing access to a large variety of functional groups at the charged sulfur atom.

  17. Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications

    NASA Astrophysics Data System (ADS)

    Zhang, Bengui; Zhang, Shouhai; Weng, Zhihuan; Wang, Guosheng; Zhang, Enlei; Yu, Ping; Chen, Xiaomeng; Wang, Xinwei

    2016-09-01

    Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes (QADMPEK) are prepared and investigated for vanadium redox flow batteries (VRFB) application. The bulky, rigid and highly hydrophobic adamantane segment incorporated into the backbone of membrane material makes QADMPEK membranes have low water uptake and swelling ratio, and the as-prepared membranes display significantly lower permeability of vanadium ions than that of Nafion117 membrane. As a consequence, the VRFB cell with QADMPEK-3 membrane shows higher coulombic efficiency (99.4%) and energy efficiency (84.0%) than those for Nafion117 membrane (95.2% and 80.5%, respectively) at the current density of 80 mA cm-2. Furthermore, at a much higher current density of 140 mA cm-2, QADMPEK membrane still exhibits better coulombic efficiency and energy efficiency than Nafion117 membrane (coulombic efficiency 99.2% vs 96.5% and energy efficiency 76.0% vs 74.0%). Moreover, QADMPEK membranes show high stability in in-situ VRFB cycle test and ex-situ oxidation stability test. These results indicate that QADMPEK membranes are good candidates for VRFB applications.

  18. Effects of electron beam irradiation on the property behaviour of poly(ether-block-amide) blended with various stabilisers

    NASA Astrophysics Data System (ADS)

    Murray, Kieran A.; Kennedy, James E.; Barron, Valerie; McEvoy, Brian; Vrain, Olivier; Ryan, Damien; Cowman, Richard; Higginbotham, Clement L.

    2015-05-01

    Radiosterilisation can induce modifications and/or degradation to transpire in poly(ether-block-amide) (PEBA) following irradiation. The current investigation utilises combined synergistic mixtures of stabilisers to minimise these effects, by melt blending them with the PEBA material. Hindered amine stabilisers (HAS), primary antioxidants and secondary antioxidants were the stabilisers incorporate to reduce/eliminate the effects of 50 kGy electron beam irradiation dose on the material. Results were discussed by comparing the stabilising efficiency of mixtures on the PEBA material in contrast to the control sample. Dynamic frequency sweeps demonstrated the formation of crosslinks, where the degree of crosslinking was dependent on the combination of stabilisers mixed in the base material (PEBA). The storage modulus displayed that PEBA blended with Irganox 565 had very slight changes in contrast to all other samples following irradiation. However, since this sample is a phenol containing system, severe discolouration was observed in comparison to other samples due to the oxidation of the hindered phenol. Overall, this study provides compelling evidence that a combined synergistic mixture of Irganox 565 (multifunctional phenolic antioxidant) and Tinuvin 783 (hindered amide light stabiliser) with PEBA, resulted in the best radiation stability.

  19. Degradation of poly(ether sulfone)/polyvinylpyrrolidone membranes by sodium hypochlorite: insight from advanced electrokinetic characterizations.

    PubMed

    Hanafi, Yamina; Szymczyk, Anthony; Rabiller-Baudry, Murielle; Baddari, Kamel

    2014-11-18

    Poly(ether sulfone) (PES)/polyvinylpyrrolidone (PVP) membranes are widely used in various industrial fields such as drinking water production and in the dairy industry. However, the use of oxidants to sanitize the processing equipment is known to impair the integrity and lifespan of polymer membranes. In this work we showed how thorough electrokinetic measurements can provide essential information regarding the mechanism of degradation of PES/PVP membranes by sodium hypochlorite. Tangential streaming current measurements were performed with ultrafiltration and nanofiltration PES/PVP membranes for various aging times. The electrokinetic characterization of membranes was complemented by FTIR-ATR spectroscopy. Results confirmed that sodium hypochlorite induces the degradation of both PES and PVP. This latter is easily oxidized by sodium hypochlorite, which leads to an increase in the negative charge density of the membrane due to the formation of carboxylic acid groups. The PVP was also found to be partly released from the membrane with aging time. Thanks to the advanced electrokinetic characterization implemented in this work it was possible for the first time to demonstrate that two different mechanisms are involved in the degradation of PES. Phenol groups were first formed as a result of the oxidation of PES aromatic rings by substitution of hydrogen by hydroxyl radicals. For more severe aging conditions, this membrane degradation mechanism was followed by the formation of sulfonic acid functions, thus indicating a second degradation process through scission of PES chains.

  20. Sulfonated poly (fluorenyl ether ketone) membrane with embedded silica rich layer and enhanced proton selectivity for vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Chen, Dongyang; Wang, Shuanjin; Xiao, Min; Han, Dongmei; Meng, Yuezhong

    A series of novel organic-inorganic hybrid membranes with special microstructure, based on sulfonated poly (fluorenyl ether ketone) ionomer (SFPEK, IEC = 1.92 mequiv. g -1) and SiO 2 or sulfonic acid group containing SiO 2 (SiO 2-SO 3H), has been successfully designed and prepared for vanadium redox flow battery (VRB) application. The SiO 2-SO 3H is synthesized by co-condensation of tetraethoxysilane and γ-propyl mercaptotrimethoxysilane via sol-gel process to control the same IEC with neat SPFEK. The hybrid membranes are prepared by simply adding the inorganic particles into the SPFEK solution in N, N‧-dimethylacetamide, followed by ultrasonic dispersion, casting and profiled temperature drying process. The morphology is examined by SEM-EDX which is applied to the top surface, bottom surface and cross-section of the hybrid membranes. The water uptake, oxidative stability, thermal property, mechanical property, proton conductivity, VO 2+ permeability and single cell performance are investigated in detail in order to understand the relationship between morphology and property of the membranes. All the hybrid membranes show dramatically improved proton selectivity at 20 °C and 40 °C when compared with Nafion117. The VRB assembled with the SPFEK/3%SiO 2 and SPFEK/9%SiO 2 membranes exhibit higher coulombic efficiency and average discharge voltage than the VRB assembled with the SPFEK membrane at all the tested current densities.

  1. Poly(oligo(ethylene glycol) methyl ether methacrylate) Brushes on High-κ Metal Oxide Dielectric Surfaces for Bioelectrical Environments.

    PubMed

    Joh, Daniel Y; McGuire, Felicia; Abedini-Nassab, Roozbeh; Andrews, Joseph B; Achar, Rohan K; Zimmers, Zackary; Mozhdehi, Darush; Blair, Rebecca; Albarghouthi, Faris; Oles, William; Richter, Jacob; Fontes, Cassio M; Hucknall, Angus M; Yellen, Benjamin B; Franklin, Aaron D; Chilkoti, Ashutosh

    2017-02-15

    Advances in electronics and life sciences have generated interest in "lab-on-a-chip" systems utilizing complementary metal oxide semiconductor (CMOS) circuitry for low-power, portable, and cost-effective biosensing platforms. Here, we present a simple and reliable approach for coating "high-κ" metal oxide dielectric materials with "non-fouling" (protein- and cell-resistant) poly(oligo(ethylene glycol) methyl ether methacrylate (POEGMA) polymer brushes as biointerfacial coatings to improve their relevance for biosensing applications utilizing advanced electronic components. By using a surface-initiated "grafting from" strategy, POEGMA films were reliably grown on each material, as confirmed by ellipsometric measurements and X-ray photoelectron spectroscopy (XPS) analysis. The electrical behavior of these POEGMA films was also studied to determine the potential impact on surrounding electronic devices, yielding information on relative permittivity and breakdown field for POEGMA in both dry and hydrated states. We show that the incorporation of POEGMA coatings significantly reduced levels of nonspecific protein adsorption compared to uncoated high-κ dielectric oxide surfaces as shown by protein resistance assays. These attributes, combined with the robust dielectric properties of POEGMA brushes on high-κ surfaces open the way to incorporate this protein and cell resistant polymer interface into CMOS devices for biomolecular detection in a complex liquid milieu.

  2. Prolonged Hypocalcemic Effect by Pulmonary Delivery of Calcitonin Loaded Poly(Methyl Vinyl Ether Maleic Acid) Bioadhesive Nanoparticles

    PubMed Central

    Varshosaz, J.; Minaiyan, M.; Forghanian, M.

    2014-01-01

    The purpose of the present study was to design a pulmonary controlled release system of salmon calcitonin (sCT). Therefore, poly(methyl vinyl ether maleic acid) [P(MVEMA)] nanoparticles were prepared by ionic cross-linking method using Fe2+ and Zn2+ ions. Physicochemical properties of nanoparticles were studied in vitro. The stability of sCT in the optimized nanoparticles was studied by electrophoretic gel method. Plasma calcium levels until 48 h were determined in rats as pulmonary-free sCT solution or nanoparticles (25 μg·kg−1), iv solution of sCT (5 μg·kg−1), and pulmonary blank nanoparticles. The drug remained stable during fabrication and tests on nanoparticles. The optimized nanoparticles showed proper physicochemical properties. Normalized reduction of plasma calcium levels was at least 2.76 times higher in pulmonary sCT nanoparticles compared to free solution. The duration of hypocalcemic effect of pulmonary sCT nanoparticles was 24 h, while it was just 1 h for the iv solution. There was not any significant difference between normalized blood calcium levels reduction in pulmonary drug solution and iv injection. Pharmacological activity of nanoparticles after pulmonary delivery was 65% of the iv route. Pulmonary delivery of P(MVEMA) nanoparticles of sCT enhanced and prolonged the hypocalcemic effect of the drug significantly. PMID:24701588

  3. In Situ Formation of Polysulfonamide Supported Poly(ethylene glycol) Divinyl Ether Based Polymer Electrolyte toward Monolithic Sodium Ion Batteries.

    PubMed

    Zhang, Jianjun; Wen, Huijie; Yue, Liping; Chai, Jingchao; Ma, Jun; Hu, Pu; Ding, Guoliang; Wang, Qingfu; Liu, Zhihong; Cui, Guanglei; Chen, Liquan

    2017-01-01

    Sodium ion battery is one of the promising rechargeable batteries due to the low-cost and abundant sodium sources. In this work, a monolithic sodium ion battery based on a Na3 V2 (PO4 )3 cathode, MoS2 layered anode, and polyether-based polymer electrolyte is reported. In addition, a new kind of polysulfonamide-supported poly(ethylene glycol) divinyl ether based polymer electrolyte is also demonstrated for monolithic sodium ion battery via in situ preparation. The resultant polymer electrolyte exhibits relatively high ionic conductivity (1.2 mS cm(-1) ) at ambient temperature, wide electrochemical window (4.7 V), and favorable mechanical strength (25 MPa). Moreover, such a monolithic Na3 V2 (PO4 )3 /MoS2 sodium ion battery using this polymer electrolyte delivers outstanding rate capability (up to 10 C) and superior cyclic stability (84%) after 1000 cycles at 0.5 C. What is more essential, such a polymer electrolyte based soft-package monolithic sodium ion cell can still power a red light emitting diode lamp and run finite times without suffering from any internal short-circuit failures, even in the case of a bended and wrinkled state. Considering these aspects, this work no doubt provides a new approach for the design of a high-performance polymer electrolyte toward monolithic sodium ion battery with exceptional rate capability and high safety. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Preparation and properties of sulfonated poly(fluorenyl ether ketone) membrane for vanadium redox flow battery application

    NASA Astrophysics Data System (ADS)

    Chen, Dongyang; Wang, Shuanjin; Xiao, Min; Meng, Yuezhong

    In order to develop novel membranes for vanadium redox flow battery (VRB) with low self-discharge rate and low cost, sulfonated poly(fluorenyl ether ketone) (SPFEK) was synthesized directly via aromatic nucleophilic polycondensation of bisphenol fluorene with 60% sulfonated difluorobenzophenone and 40% difluorobenzophenone. The SPFEK membrane shows the lower permeability of vanadium ions. The open circuit voltage evaluation demonstrates that the SPFEK membrane is superior to Nafion 117 membrane in self-discharge test. Both energy efficiencies (EE) and power densities of the VRB single cell based on the SPFEK membrane are higher than those of the VRB with Nafion 117 membrane at the same current densities. The highest coulombic efficiency (CE) of VRB with SPFEK membrane is 80.3% while the highest CE of the VRB with Nafion 117 membrane is 77.0%. The SPFEK membrane shows the comparative stability to Nafion 117 membrane in VO 2 + electrolyte. The experimental results suggest that SPFEK membrane is a promising ion exchange membrane for VRB.

  5. Poly(methyl vinyl ether-alt-maleic acid)-functionalized porous silicon nanoparticles for enhanced stability and cellular internalization.

    PubMed

    Shahbazi, Mohammad-Ali; Almeida, Patrick V; Mäkilä, Ermei; Correia, Alexandra; Ferreira, Mónica P A; Kaasalainen, Martti; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A

    2014-03-01

    Currently, developing a stable nanocarrier with high cellular internalization and low toxicity is a key bottleneck in nanomedicine. Here, we have developed a successful method to covalently conjugate poly(methyl vinyl ether-co-maleic acid) (PMVE-MA) copolymer on the surface of (3-aminopropyl)triethoxysilane-functionalized thermally carbonized porous silicon nanoparticles (APSTCPSi NPs), forming a surface negatively charged nanovehicle with unique properties. This polymer conjugated NPs could modify surface smoothness, charge, and hydrophilicity of the developed NPs, leading to considerable improvement in the colloidal and plasma stabilities via enhanced suspensibility and charge repulsion. Furthermore, despite the surface negative charge of the polymer-conjugated NPs, the cellular internalization was increased in both MDA-MB-231 and MCF-7 breast cancer cells. These results provide a proof-of-concept evidence that such polymer-based PSi nanocomposite can be extensively used as a promising candidate for intracellular drug delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Highly branched sulfonated poly(fluorenyl ether ketone sulfone)s membrane for energy efficient vanadium redox flow battery

    NASA Astrophysics Data System (ADS)

    Yin, Bibo; Li, Zhaohua; Dai, Wenjing; Wang, Lei; Yu, Lihong; Xi, Jingyu

    2015-07-01

    A series of highly branched sulfonated poly (fluorenyl ether ketone sulfone)s (HSPAEK) are synthesized by direct polycondensation reactions. The HSPAEK with 8% degree of branching is further investigated as membrane for vanadium redox flow battery (VRFB). The HSPAEK membrane prepared by solution casting method exhibits smooth, dense and tough morphology. It possesses very low VO2+ permeability and high ion selectivity compared to those of Nafion 117 membrane. When applied to VRFB, this novel membrane shows higher coulombic efficiency (CE, 99%) and energy efficiency (EE, 84%) than Nafion 117 membrane (CE, 92% and EE, 78%) at current density of 80 mA cm-2. Besides, the HSPAEK membrane shows super stable CE and EE as well as excellent discharge capacity retention (83%) during 100 cycles life test. After being soaked in 1.5 mol L-1 VO2+ solution for 21 days, the weight loss of HSPAEK membrane and the amount of VO2+ reduced from VO2+ are only 0.26% and 0.7%, respectively, indicating the superior chemical stability of the membrane.

  7. Poly(ether imide)-silica hybrid coatings for tunable corrosion behavior and improved biocompatibility of magnesium implants.

    PubMed

    Kang, Min-Ho; Jang, Tae-Sik; Jung, Hyun-Do; Kim, Sae-Mi; Kim, Hyoun-Ee; Koh, Young-Hag; Song, Juha

    2016-05-05

    Magnesium (Mg) and its alloys have gained considerable attention as a promising biomaterial for bioresorbable orthopedic implants, but the corrosion behavior of Mg-based implants is still the major issue for clinical use. In order to improve the corrosion stability and implant-tissue interfaces of these implants, methods for coating Mg have been actively investigated. In this study, poly(ether imide) (PEI)-silica hybrid material was coated on Mg, for the tunable degradation and enhanced biological behavior. Homogeneous PEI-silica hybrid materials with various silica contents were coated on Mg substrates without any cracks, where silica nanoparticles were well dispersed in the PEI matrix without significant particle agglomeration up the 30 vol% silica. The hybrid coatings maintained good adhesion strength of PEI to Mg. The corrosion rate of hybrid-coated Mg was increased along with the increment of the silica content, due to improved hydrophilicity of the hybrid coating layers. Moreover, the biocompatibility of the hybrid-coated Mg specimens was significantly improved, mainly due to the higher Mg ion concentrations associated with faster corrosion, compared to PEI-coated Mg. Therefore, PEI-silica hybrid systems have significant potential as a coating material of Mg for load-bearing orthopedic applications by providing tunable corrosion behavior and enhanced biological performance.

  8. Investigation of phonon transport and thermal boundary conductance at the interface of functionalized SWCNT and poly (ether-ketone)

    SciTech Connect

    Huang, Haoxiang; Kumar, Satish; Chen, Liang; Varshney, Vikas; Roy, Ajit K.

    2016-09-07

    Carbon nanostructures such as carbon nanotube (CNT), graphene, and carbon fibers can be used as fillers in amorphous polymers to improve their thermal properties. In this study, the effect of covalent bonding of CNT with poly(ether ketone) (PEK) on interfacial thermal interactions is investigated using non-equilibrium molecular dynamics simulations. The number of covalent bonds between (20, 20) CNT and PEK is varied in the range of 0–80 (0%–6.25%), and the thermal boundary conductance is computed. The analysis reveals that covalent functionalization of CNT atoms can enhance the thermal boundary conductance by an order of magnitude compared to the non-functionalized CNT-PEK interface at a high degree of CNT functionalization. Besides strengthening the thermal coupling, covalent functionalization is also shown to modify the phonon spectra of CNT. The transient spectral energy analysis shows that the crosslinks cause faster energy exchange from CNT to PEK in different frequency bands. The oxygen atom of hydroxyl group of PEK contributes energy transfer in the low frequency band, while aromatic and carbonyl carbon atoms play a more significant role in high frequency bands. In addition, by analyzing the relaxation time of the spectral temperature of different frequency bands of CNT, it is revealed that with increasing number of bonds, both lower frequency vibrational modes and higher frequency modes efficiently couple across the CNT-PEK interface and contribute in thermal energy transfer from CNT to the matrix.

  9. Thermoresponsive poly[tri(ethylene glycol) monoethyl ether methacrylate]-peptide surfaces obtained by radiation grafting-synthesis and characterisation.

    PubMed

    Adamus, A; Komasa, J; Kadłubowski, S; Ulański, P; Rosiak, J M; Kawecki, M; Klama-Baryła, A; Dworak, A; Trzebicka, B; Szweda, R

    2016-09-01

    This report demonstrates the feasibility of radiation grafting for the preparation of polymer layers functionalised with short peptide ligands which promote cell adhesion. Thermoresponsive poly [tri(ethylene glycol) monoethyl ether methacrylate] (PTEGMA) layers were synthesised on a polypropylene substrate by post-irradiation grafting. A cell adhesion moiety, the CF-IKVAVK peptide modified with a methacrylamide function and a fluorescent label were introduced to the surface during the polymerisation process. The amount of CF-IKVAVK was easily controlled by changing its concentration in the reaction mixture. The changes in the surface composition, morphology, philicity and thickness at each step of the polypropylene functionalisation confirmed that the surface modification procedures were successful. The increase in environmental temperature above the cloud point temperature of PTEGMA caused a decrease in surface philicity. The obtained PTEGMA and PTEGMA-peptide surfaces above TCP were tested as scaffolds for fibroblast sheet culture and temperature induced detachment. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Drug release from interpenetrating polymer networks based on poly(ethylene glycol) methyl ether acrylate and gelatin.

    PubMed

    Ding, Frank; Hsu, S-H; Wu, D-H; Chiang, W-Y

    2009-01-01

    In order to develop new materials for biomedical and pharmaceutical applications, interpenetrating polymer networks (IPNs) based on poly(ethylene glycol) methyl ether acrylate (PEGMEA) and gelatin were synthesized. These two materials were cross-linked sequentially using N,N'-methylene bisacrylamide (NMBA) and glutaraldehyde (Glu). Two series of IPNs gels were synthesized by applying different amounts of PEGMEA and gelatin in the initial feed. Sequential IPNs were prepared by polymerizing and cross-linking PEGMEA in the presence of gelatin using redox initiators (e.g., ammonium peroxydisulfate (APS) and N,N,N',N'-tetramethyl ethylenediamine (TEMED)), as well as NMBA as the cross-linking agent. Gelatin in firm gel was then cross-linked with 1% glutaraldehyde. The swelling kinetics, mechanical properties and drug-release behavior of these IPNs were analyzed. The surface properties were examined by scanning electron microscopy. The results indicated that the swelling ratio decreased with an increase in the content of both PEGMEA and gelatin in the IPNs. PEGMEA/gelatin-based full-IPNs had a significantly higher shear modulus (G) and cross-linking density (rho) when the content of PEGMEA was increased. The drug loading was very high due to the full-IPN structure. The drug-release velocity was mainly affected by the content of PEGMEA.

  11. Encapsulation of glucose oxidase within poly(ethylene glycol) methyl ether methacrylate microparticles for developing an amperometric glucose biosensor.

    PubMed

    Hervás Pérez, J P; López-Cabarcos, E; López-Ruiz, B

    2008-06-15

    Poly(ethylene glycol) methyl ether methacrylate (PEGMEM) microparticles were synthesized and glucose oxidase (GOx) was immobilized within the microparticles. An amperometric biosensor was fabricated using the microparticles with GOx as biological component. The enzyme immobilization method was optimized by investigating the influence of monomer concentration and cross-linker content used in the preparation of the microparticles in the response of the biosensor. The best analytical results were obtained with the microparticles prepared with 0.21 M PEGMEM and 0.74% cross-linking. Furthermore, we have investigated the influence on the biosensor behaviour of parameters such as working potential, pH, temperature and enzymatic load. In addition, analytical properties such as sensitivity, linear range, response time and detection limit were determined. The biosensor was used to determine glucose in human serum samples and to avoid common interferents present in human serum such as uric and ascorbic acids. A Nafion layer was deposited on the electrode surface with satisfactory results. The useful lifetime of the biosensor was at least 520 days.

  12. Exploration of CO2-Philicity of Poly(vinyl acetate-co-alkyl vinyl ether) through Molecular Modeling and Dissolution Behavior Measurement.

    PubMed

    Hu, Dongdong; Sun, Shaojun; Yuan, Pei-Qing; Zhao, Ling; Liu, Tao

    2015-09-24

    Hydrocarbon CO2-philes are of great interest for use in expanding CO2 applications as a green solvent. In this work, multiscale molecular modeling and dissolution behavior measurement were both applied to explore CO2-philicity of the poly(vinyl acetate) (PVAc)-based copolymer. Introduction of a favorable comonomer, i.e., vinyl ethyl ether (VEE), could significantly reduce the polymer-polymer interaction on the premise that the polymer-CO2 interaction was not weakened but enhanced. The ab initio calculated interaction of the model molecules with CO2 demonstrated that the ether group in VEE or VBE was the suitable CO2-philic segment. From the molecular dynamics (MD) simulations of polymer/CO2 systems, the interaction energy and Flory-Huggins parameter (χ12) of poly(VAc-alt-VEE)/CO2 supported that poly(VAc-alt-VEE) possessed better CO2-philicity than PVAc. The dissolution behaviors of the synthesized poly(VAc-co-alkyl vinyl ether) copolymers in CO2 showed the best CO2-phile had the VEE content of about 34 mol %. The MD simulations also indicated that the interaction of random poly(VAc-co-VEE) containing about 30 mol % VEE with CO2 was the strongest and the χ12 was the smallest in these polymer/CO2 systems. Not only could the VEE monomer reduce the polymer-polymer interaction, but it could also enhance the polymer-CO2 interaction with an optimized composition. Introducing a suitable comonomer with a certain composition might be a promising strategy to form the synergistic effect of polymer-polymer interaction and polymer-CO2 interaction for screening the hydrocarbon CO2-philes.

  13. Molecular Engineering of Liquid Crystalline Polymers by Living Polymerization. 8. Influence of Molecular Weight on the Phase Behavior pf Poly(Omega-((4-cyano-4’Biphenyl)oxy)alkyl Vinyl Ether)s with Ethyl, Propyl and Butyl Alkyl Groups

    DTIC Science & Technology

    1990-10-16

    diacetate l0 were synthesized as described previously. Methyl sulfide was refluxed over 9-borabicyclo[3,3, l ]nonane (crystalline, 98%, Aldrich) and then...LJ.I., poly(A-4) with different degrees of polynerization and narow molecular weight distribution was compared to that of L -1, U- and 6. and of 2.((4...vinyl ether I ( L ),, poy 3 [4-cyano-4’-biphenyl)oxy]propyl vinyl ether) &63) and poly (4-[4-cyano-4’- biphenyl)oxylbutyl vinyl ether) (6_-4). Their

  14. pH-Responsive Polyethylene Glycol Monomethyl Ether-ε-Polylysine-G-Poly (Lactic Acid)-Based Nanoparticles as Protein Delivery Systems.

    PubMed

    Liu, Huiqin; Li, Yijia; Yang, Rui; Gao, Xiujun; Ying, Guoguang

    2016-01-01

    The application of poly(lactic acid) for sustained protein delivery is restricted by the harsh pH inside carriers. In this study, we synthesized a pH-responsive comb-shaped block copolymer, polyethylene glycol monomethyl ether-ε-polylysine-g-poly (lactic acid) (PEP)to deliver protein (bovine serum albumin (BSA)). The PEP nanoparticles could automatically adjust the internal pH to a milder level, as shown by the quantitative ratio metric results. The circular dichroism spectra showed that proteins from the PEP nanoparticles were more stable than those from poly(lactic acid) nanoparticles. PEP nanoparticles could achieve sustained BSA release in both in vitro and in vivo experiments. Cytotoxicity results in HL-7702 cells suggested good cell compatibility of PEP carriers. Acute toxicity results showed that the PEP nanoparticles induced no toxic response in Kunming mice. Thus, PEP nanoparticles hold potential as efficient carriers for sustained protein release.

  15. pH-Responsive Polyethylene Glycol Monomethyl Ether-ε-Polylysine-G-Poly (Lactic Acid)-Based Nanoparticles as Protein Delivery Systems

    PubMed Central

    Liu, Huiqin; Li, Yijia; Yang, Rui; Gao, Xiujun; Ying, Guoguang

    2016-01-01

    The application of poly(lactic acid) for sustained protein delivery is restricted by the harsh pH inside carriers. In this study, we synthesized a pH-responsive comb-shaped block copolymer, polyethylene glycol monomethyl ether-ε-polylysine-g-poly (lactic acid) (PEP)to deliver protein (bovine serum albumin (BSA)). The PEP nanoparticles could automatically adjust the internal pH to a milder level, as shown by the quantitative ratio metric results. The circular dichroism spectra showed that proteins from the PEP nanoparticles were more stable than those from poly(lactic acid) nanoparticles. PEP nanoparticles could achieve sustained BSA release in both in vitro and in vivo experiments. Cytotoxicity results in HL-7702 cells suggested good cell compatibility of PEP carriers. Acute toxicity results showed that the PEP nanoparticles induced no toxic response in Kunming mice. Thus, PEP nanoparticles hold potential as efficient carriers for sustained protein release. PMID:27467072

  16. Phase Behavior of Poly(vinylidene fluoride)-graft-poly(diethylene glycol methyl ether methacrylate) in Alcohol-Water System: Coexistence of LCST and UCST.

    PubMed

    Kuila, Atanu; Maity, Nabasmita; Chatterjee, Dhruba P; Nandi, Arun K

    2016-03-10

    A thermoresponsive polymer poly(diethylene glycol methyl ether methacrylate) (PMeO2MA) is grafted from poly(vinylidene fluoride) (PVDF) backbone by using a combined ATRC and ATRP technique with a high conversion (69%) of the monomer to produce the graft copolymer (PD). It is highly soluble polymer and its solution property is studied by varying polarity in pure solvents (water, methanol, isopropanol) and also in mixed solvents (water-methanol and water-isopropanol) by measuring the hydrodynamic size (Z-average) of the particles by dynamic light scattering (DLS). The variation of Z-average size with temperature of the PD solution (0.2%, w/v) indicates a lower critical solution temperature (LCST)-type phase transition (T(PL)) in aqueous medium, an upper critical solution temperature (UCST)-type phase transition (T(PU)) in isopropanol medium, and no such phase transition for methanol solution. In the mixed solvent (water + isopropanol) at 0-20% (v/v) isopropanol the TPL increases, whereas the T(PU) decreases at 92-100% with isopropanol content. For the mixture 20-90% isopropanol, PD particles having larger sizes (400-750 nm) exhibit neither any break in Z-average size-temperature plot nor any cloudiness, indicating their dispersed swelled state in the medium. In the methanol + water mixture with methanol content of 0-30%, T(PL) increases, and at 40-60% both UCST- and LCST-type phase separations occur simultaneously, but at 70-90% methanol the swelled state of the particles (size 250-375 nm) is noticed. For 50 vol % methanol by varying polymer concentration (0.07-0.2% w/v) we have drawn a quasibinary phase diagram that indicates an approximate inverted hourglass phase diagram where a swelled state exists between two single phase boundary produced from LCST- and UCST-type phase transitions. An attempt is made to understand the phase separation process by temperature-dependent (1)H NMR spectroscopy along with transmission electron microscopy.

  17. Photochemical modification of poly(ether sulfone) ultrafiltration membranes by UV-assisted graft polymerization for the prevention of biofouling

    NASA Astrophysics Data System (ADS)

    Pieracci, John Paul

    Membranes are widely used by the biotechnology industry in the separation and recovery of proteins from biological solutions. Fouling of membrane surfaces by irreversible protein adsorption during ultrafiltration causes loss of membrane permeability and can reduce membrane selectivity and lead to significant product loss through denaturation. In this work, low fouling poly(ether sulfone) (PES) ultrafiltration membranes were produced by ultraviolet (UV) assisted graft polymerization of hydrophilic vinyl monomers using a newly developed photochemical dip modification technique. This technique was developed to make the UV modification process more easily adaptable to continuous membrane manufacturing processes. A method was also developed to measure and track the degree of polymer grafting on the membrane surface using attenuated total reflection Fourier transform infrared spectroscopy (FTIR/ATR). Grafting the hydrophilic monomer N-vinyl-2-pyrrolidinone (NVP) onto the membrane surface increased surface wettability and produced membranes with the high wettability of regenerated cellulose membranes. The enhanced surface wettability significantly decreased irreversible adsorptive fouling during the filtration of the protein bovine serum albumin (BSA). In order to maintain the rejection of BSA after modification, PES chain scission was tightly controlled by regulating the UV wavelength range and the light intensity used. The UV reactor system was operated with 300 nm UV lamps and a benzene filter used to remove high energy wavelengths below 275 nm that were determined to cause severe loss of BSA rejection due to pore enlargement from extensive chain scission. Dip modification caused membrane permeability to decrease due to the grafted chains blocking the membrane pores. The use of a chain transfer agent during modification followed by ethanol cleaning increased modified membrane permeability, but BSA rejection was severely decreased. The resultant membranes produced by

  18. Novel quaternized poly(arylene ether sulfone)/Nano-ZrO₂ composite anion exchange membranes for alkaline fuel cells.

    PubMed

    Li, Xiuhua; Yu, Yingfeng; Meng, Yuezhong

    2013-02-01

    A series of composite anion exchange membranes based on novel quaternized poly(arylene ether sulfone)/nanozirconia (QPAES/nano-ZrO₂) composites are prepared using a solution casting method. The QPAES/nano-ZrO₂ composite membranes are characterized by FTIR, X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray analysis (SEM/EDX). The ion exchange capacity (IEC), water uptake, swelling ratio, hydroxide ion conductivity, mechanical properties, thermal stability, and chemical stability of the composite membranes are measured to evaluate their applicability in fuel cells. The introduction of nano-ZrO₂ induces the crystallization of the matrix and enhances the IEC of the composite membranes. The modification with nano-ZrO₂ improves water uptake, dimension stability, hydroxide ion conductivity, mechanical properties, and thermal and chemical stabilities of the composite membranes. The QPAES/nano-ZrO₂ composite membranes show hydroxide ion conductivities over 25.7 mS cm⁻¹ at a temperature above 60 °C. Especially, the QPAES/nano-ZrO₂ composite membranes with the nano-ZrO₂ content above 7.5% display hydroxide ion conductivities over 41.4 mS cm⁻¹ at 80 °C. The E(a) values of the QPAES/nano-ZrO₂ composite membranes with the nano-ZrO₂ content above 5% are lower than 11.05 kJ mol⁻¹. The QPAES/7.5% nano-ZrO₂ composite membrane displays the lowest E(a) value and the best comprehensive properties and constitutes a good potential candidate for alkaline fuel cells.

  19. Design and formulation of nanoemulsions using 2-(poly(hexafluoropropylene oxide)) perfluoropropyl benzene in combination with linear perfluoro(polyethylene glycol dimethyl ether)

    PubMed Central

    Mountain, Gregory A.; Jelier, Benson J.; Bagia, Christina; Friesen, Chadron M.; Janjic, Jelena M.

    2014-01-01

    This is the first report where PFPAE aromatic conjugates and perfluoro(polyethylene glycol dimethyl ether) are combined and formulated as nanoemulsions with droplet size below 100 nm. A perfluoropolyalkylether (PFPAE) aromatic conjugate, 2-(poly(hexafluoropropylene oxide)) perfluoropropyl benzene, was used as fluorophilic-hydrophilic diblock (FLD) aimed at stabilizing perfluoro(polyethylene glycol dimethyl ether) nanoemulsions. Its effects on colloidal behaviors in triphasic (organic/fluorous/aqueous) nanoemulsions were studied. The addition of FLD construct to fluorous phase led to decrease in PFPAE nanoemulsion droplet size to as low as 85 nm. Prepared nanoemulsions showed high colloidal stability. Our results suggest that these materials represent viable novel approach to fluorous colloid systems design with potential for biomedical and synthetic applications. PMID:24976645

  20. Synthesis and characterization of poly(methoxyl ethylene glycol-caprolactone-co-methacrylic acid-co-poly(ethylene glycol) methyl ether methacrylate) pH-sensitive hydrogel for delivery of dexamethasone.

    PubMed

    Wang, Ke; Xu, Xu; Wang, YuJun; Yan, Xi; Guo, Gang; Huang, MeiJuan; Luo, Feng; Zhao, Xia; Wei, YuQuan; Qian, ZhiYong

    2010-04-15

    In this work, a novel pH-sensitive hydrogels based on macromonomer of methoxyl poly(ethylene glycol)-poly(caprolactone)-acryloyl chloride (MPEG-PCL-AC, PCE-AC), poly(ethylene glycol) methyl ether methacrylate (MPEGMA), and methacrylic acid (MAA) were successfully synthesized by heat-initiated free radical polymerization method. The obtained macromonomers and hydrogels were characterized by (1)H NMR and FT-IR, respectively. Morphology study, swelling behavior, in vitro drug release behavior, acute oral toxicity of hydrogels, and cytotoxicity of PCE-AC macromonomer were also investigated in this paper. Finally, the hydrogels demonstrated that the sharp change in different pH value, thus believing to be promising the suitability of the candidate for oral drug-delivery systems.

  1. 2,5-Thiophene-based liquid crystalline poly(amide)s, poly(arylene ether ketone)s, and poly(benzimidazole)s

    SciTech Connect

    Stompel, S.

    1993-01-01

    Poly(p-phenylene terephthalamide) (PPTA or Kevlar[sup TM]) adopts an extended-chain crystal habit in the solid state which derives from the chain parallelism in its liquid crystalline (LC) phase. The objective of this dissertation is to investigate how the deviation from core linearity which is achieved by replacing terephthalic acid, a linear monomer, with 2,5-thiophenedicarboxylic acid, a monomer with a [approximately]148[degrees] bend, affects liquid crystalline properties of aromatic polyamides. The mesogenic properties of the 2,5-thiophene are initially verified for newly synthesized low molar mass diamide model compounds where the characteristic texture of the smectic A phase is observed by polarized optical microscopy. Differential scanning calorimetry (DSC) studies shows that the observed mesophase for the thiophene-based diamide is much narrower and exists at lower temperatures than that observed for the corresponding p-phenylene diamide. Extensions to macromolecules show that if each terephthalamide unit in PPTA is replaced with a 2,5-thiophenylamide unit, high molecular weight polymer can be synthesized and, moreover, such 2,5-thiophene-based aromatic polyamide (PPThA) is stable and exhibits liquid crystalline phases in concentrated sulfuric acid solutions. Preliminary mechanical properties of coarse fibers spun from the liquid crystalline solutions and isotropic solutions in sulfuric acid are compared. PPThA lyotropic solutions are studied using deuterium NMR spectroscopy. LC solutions may be aligned in a magnetic field to yield a [open quotes]single liquid crystal[close quotes]-a macroscopically oriented phase. In such uniaxial solutions, the transition to isotropic state at elevated temperatures may be indirectly monitored by deuterium NMR; quadrupolar interactions of the probe molecule (deuterated sulfuric acid) reflects changes in the macromolecular ordering. Direct monitoring of polymer order is accomplished using deuterium labeled PPThA.

  2. Environmental effects of poly(phenylene ether) blends after long-term exposure to potable hot water

    NASA Astrophysics Data System (ADS)

    Maclean, Steven

    In recent years, engineering thermoplastic resins have been contemplated for use in a variety pressurized fluid handling components such as potable water delivery pipes, fitting and valves. In this research, rigid blends of glassy poly(phenylene ether) (PPE) polymer are studied to assess their suitability in long-term, potable, hot water environments. Three distinct PPE-based model compounds were prepared for this research: (i) a 50/50 blend of PPE and high impact polystyrene (HIPS); (ii) a 50/50 blend of PPE and HIPS with the inclusion of an anti-oxidant package and; (iii) a blend consisting of capped PPE, crystal polystyrene and styrene-ethyelene-butylene-styrene (SEBS) rubber. A fourth engineering thermoplastic, namely bisphenol-A polysulfone (PSU), was incorporated into the study as a benchmark material due to its proven reliability in hot water applications. Aging experiments were carried out for 8,000 hours in an 80°C water bath and an 80°C convection oven to characterize physical property retention and degradation mechanisms in each material. During water bath immersion, excessive, non-Fickian water diffusion occurred in both PPE/HIPS blends which led to water clustering and disc shaped microcavities on the order of 50 to 100 mum in diameter. These voids in the bulk caused appreciable losses in tensile elongation and fatigue resistance. The capped PPE/PS/SEBS blend, however, managed water uptake more effectively and its chemistry deterred water clustering. With further improvements to the formulation, such as larger rubber domains or an alternative impact modifier, the capped PPE blend may be able to offer physical property retention equal to that of PSU. With the exception of slight craze formation at sharp specimen edges during hot water immersion, the PSU material proved to be an exceptional material candidate throughout the entire experimentation. Surprisingly long-term hot water exposure did not cause gross chemical degradation in any of the materials

  3. Poly(vinyl methyl ether) hydrogels at temperatures below the freezing point of water-molecular interactions and states of water.

    PubMed

    Pastorczak, Marcin; Dominguez-Espinosa, Gustavo; Okrasa, Lidia; Pyda, Marek; Kozanecki, Marcin; Kadlubowski, Slawomir; Rosiak, Janusz M; Ulanski, Jacek

    2014-01-01

    Water interacting with a polymer reveals a number of properties very different to bulk water. These interactions lead to the redistribution of hydrogen bonds in water. It results in modification of thermodynamic properties of water and the molecular dynamics of water. That kind of water is particularly well observable at temperatures below the freezing point of water, when the bulk water crystallizes. In this work, we determine the amount of water bound to the polymer and of the so-called pre-melting water in poly(vinyl methyl ether) hydrogels with the use of Raman spectroscopy, dielectric spectroscopy, and calorimetry. This analysis allows us to compare various physical properties of the bulk and the pre-melting water. We also postulate the molecular mechanism responsible for the pre-melting of part of water in poly(vinyl methyl ether) hydrogels. We suggest that above -60 °C, the first segmental motions of the polymer chain are activated, which trigger the process of the pre-melting.

  4. Role of sulfonation in the stability, reactivity, and selectivity of poly(ether imide) used to develop ion exchange membranes: DFT study with application to fuel cells.

    PubMed

    López-Chávez, Ernesto; Peña-Castañeda, Yésica A; de la Portilla-Maldonado, L César; Guzmán-Pantoja, Javier; Martínez-Magadán, José Manuel; Oviedo-Roa, Raúl; de Landa Castillo-Alvarado, Fray; Cruz-Torres, Armando

    2014-07-01

    The design of polymer electrolyte membranes for fuel cells must satisfy two equally important fundamental principles: optimization of the reactivity and the selectivity in order to improve the ion transport properties of the membrane as well as its long-term stability in the hydrated state at high temperature (above 100 °C). A study utilizing density functional theory (DFT) to elucidate the effect of the degree of sulfonation on the chemical stability, reactivity, and selectivity of poly(ether imide) (PEI), which allows the ionic transport properties of the membrane to be predicted, is reported here. Sulfonated poly(ether imide) (SPEI) structures with (-SO3H) n (n = 1-6) groups were built and optimized in order to calculate the above properties as functions of the number of sulfonyl groups. A comparative study demonstrated that the SPEI with four sulfonyl groups in its backbone is the polymer with the properties best suited for use in fuel cells.

  5. Considerations of the Effects of Naphthalene Moieties on the Design of Proton-Conductive Poly(arylene ether ketone) Membranes for Direct Methanol Fuel Cells.

    PubMed

    Wang, Baolong; Hong, Lihua; Li, Yunfeng; Zhao, Liang; Wei, Yuxue; Zhao, Chengji; Na, Hui

    2016-09-14

    Novel sulfonated poly(arylene ether ketones) (SDN-PAEK-x), consisting of dual naphthalene and flexible sulfoalkyl groups, were prepared via polycondensation, demethylation, and sulfobutylation grafting reaction. Among them, SDN-PAEK-1.94 membrane with the highest ion exchange capacity (IEC = 2.46 mequiv·g(-1)) exhibited the highest proton conductivity, which was 0.147 S· cm(-1) at 25 °C and 0.271 S·cm(-1) at 80 °C, respectively. The introduction of dual naphthalene moieties is expected to achieve much enhanced properties compared to those of sulfonated poly(arylene ether ketones) (SNPAEK-x), consisting of single naphthalene and flexible sulfoalkyl groups. Compared with SNPAEK-1.60 with a similar IEC, SDN-PAEK-1.74 membrane showed higher proton conductivity, higher IEC normalized conductivity, and higher effective proton mobility, although it had lower analytical acid concentration. The SDN-PAEK-x membranes with IECs higher than 1.96 mequiv·g(-1) also exhibited higher proton conductivity than that of recast Nafion membrane. Furthermore, SDN-PAEK-1.94 displayed a better single cell performance with a maximum power density of 60 mW·cm(-2) at 80 °C. Considering its high proton conductivity, excellent single cell performance, good mechanical stabilities, low membrane swelling, and methanol permeability, SDN-PAEK-x membranes are promising candidates as alternative polymer electrolyte membranes to Nafion for direct methanol fuel cell applications.

  6. Multi-stimuli-responsive organometallic gels based on ferrocene-linked poly(aryl ether) dendrons: reversible redox switching and Pb2+-ion sensing.

    PubMed

    Lakshmi, Neelakandan Vidhya; Mandal, Dipendu; Ghosh, Sundargopal; Prasad, Edamana

    2014-07-14

    We describe the design, synthesis, and "stimuli-responsive" study of ferrocene-linked Fréchet-type [poly(aryl ether)]-dendron-based organometallic gels, in which the ferrocene moiety is attached to the dendron framework through an acyl hydrazone linkage. The low-molecular-weight gelators (LMWGs) form robust gels in both polar and non-polar solvent/solvent mixtures. The organometallic gels undergo stimuli-responsive behavior through 1) thermal, 2) chemical, and 3) electrochemical methods. Among them, conditions 1 and 3 lead to seamlessly reversible with repeated cycles of identical efficiency. Results indicate that the flexible nature of the poly(aryl ether) dendron framework plays a key role in retaining the reversible electrochemical behavior of ferrocene moiety in the LMWGs. Further, the organometallic gelators have exhibited unique selectivity towards Pb(2+) ions (detection limit ≈10(-8)  M). The metal ion-sensing results in a gel-sol phase transition associated with a color change visible to the naked eye. Most importantly, decomplexing the metal ion from the system leads to the regeneration of the initial gel morphology, indicating the restoring ability of the organometallic gel. The metal-ligand binding nature has been analyzed by using (1)H NMR spectroscopy, mass spectrometry, and DFT calculations.

  7. Synthesis and Properties of Poly(ether sulfone)s with Clustered Sulfonic Groups for PEMFC Applications under Various Relative Humidity.

    PubMed

    Lee, Shih-Wei; Chen, Jyh-Chien; Wu, Jin-An; Chen, Kuei-Hsien

    2017-03-22

    Novel sulfonated poly(ether sulfone) copolymers (S4PH-x-PSs) based on a new aromatic diol containing four phenyl substituents at the 2, 2', 6, and 6' positions of 4,4'-diphenyl ether were synthesized. Sulfonation was found to occur exclusively on the 4 position of phenyl substituents by NMR spectroscopy. The ion exchange capacity (IEC) values can be controlled by adjusting the mole percent (x in S4PH-x-PS) of the new diol. The fully hydrated sulfonated poly(ether sulfone) copolymers had good proton conductivity in the range 0.004-0.110 S/cm at room temperature. The surface morphology of S4PH-x-PSs and Nafion 212 was investigated by atomic force microscopy (tapping-mode) and related to the percolation limit and proton conductivity. Single H2/O2 fuel cell based on S4PH-40-PS loaded with 0.25 mg/cm(2) catalyst (Pt/C) exhibited a peak power density of 462.6 mW/cm(2), which was close to that of Nafion 212 (533.5 mW/cm(2)) at 80 °C with 80% RH. Furthermore, fuel cell performance of S4PH-35-PS with various relative humidity was investigated. It was confirmed from polarization curves that the fuel cell performance of S4PH-35-PS was not as high as that of Nafion 212 under fully hydrated state due to higher interfacial resistance between S4PH-35-PS and electrodes. While under low relative humidity (53% RH) at 80 °C, fuel cells based on S4PH-35-PS showed higher peak power density (234.9 mW/cm(2)) than that (214.0 mW/cm(2)) of Nafion 212.

  8. Mussel inspired polydopamine functionalized poly(ether ether ketone) tube for online solid-phase microextraction-high performance liquid chromatography and its application in analysis of protoberberine alkaloids in rat plasma.

    PubMed

    Zhang, Wenpeng; Chen, Zilin

    2013-02-22

    A novel and simple poly(ether ether ketone) (PEEK) tube-based solid-phase microextraction (SPME)-HPLC method was developed in this work. A mussel inspired polydopamine method was used to functionalize the chemically resistant surface of PEEK tube and a poly(acrylamide-ethylene glycol dimethacrylate) monolith was synthesized inside the PEEK tube and chemically bonded with its surface. The stability of the polydopamine layer was investigated and found to be well enduring to most of commonly used organic solvents and strong acidic conditions. The PEEK tube-based monolith was coupled with HPLC system through a six-port valve, and the performance of the online SPME-HPLC system was demonstrated by analyzing three protoberberine alkaloids in aqueous samples, namely jatrorrhizine (Jat), palmatine (Pal) and berberine (Ber). These analytes were well extracted and separated within 10 min, and enrichment factors of about 400 were obtained. The limit of detection of the proposed method was decreased to 0.01 ng/mL by using UV detection. Finally, the online SPME-HPLC method was applied for determining Jat, Pal and Ber in rat plasma samples. Reproducibility was obtained by evaluating the intra- and inter-day precisions with RSDs less than 6.1% and 8.5%, respectively, and recoveries of the analytes in spiked plasma samples ranged from 89.8% to 96.7%. The proposed method was also applied to determine the concentration of Jat, Pal and Ber in rat plasma after oral administration of Cortex Phellodendri Chinensis. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

    1992-01-01

    Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties.

  10. Novel quaternary ammonium microblock poly (p-phenylene-co-aryl ether ketone)s as anion exchange membranes for alkaline fuel cells

    NASA Astrophysics Data System (ADS)

    Dong, Xue; Xue, Boxin; Qian, Huidong; Zheng, Jifu; Li, Shenghai; Zhang, Suobo

    2017-02-01

    Using cation compounds as raw materials, three quaternized microblock poly(p-phenylene-co-aryl ether ketone)s (s-, m-, and l-QPP-co-PAEK) were synthesized using a nickel (0)-catalyzed coupling reaction. Hydrophilic and hydrophobic moieties were affixed using cationic quaternary ammonium (QA) groups attached to poly(p-phenylene) by a three-carbon interstitial spacer and nonionic dichloride monomers of various lengths, respectively. The morphology, water uptake, swelling ratio, mechanical properties, thermal stability, hydroxide conductivity and alkaline stability of these new membranes were investigated. Experimental results indicated that the membrane with the longest hydrophobic microblock exhibited high hydroxide conductivity (37.6 mS cm-1 at 80 °C) resulting from the aggregation of ionic clusters observed using TEM. The copolymers with longer hydrophobic nonionic segments exhibited improved alkaline stability, suggesting that the hydrophobic chain shields the QA groups and that the polymer chains pack in a manner that restricts rotation. Controlling the distribution of QA groups in poly(p-phenylene) moieties and tuning the block length of nonionic segments are demonstrated to be effective methods for improving the hydroxide conductivity and alkaline stability of anion exchange membranes.

  11. Drug-loading of poly(ethylene glycol methyl ether methacrylate) (PEGMEMA)-based micelles and mechanisms of uptake in colon carcinoma cells.

    PubMed

    Chang, Teddy; Gosain, Pallavi; Stenzel, Martina H; Lord, Megan S

    2016-08-01

    In this study polymeric micelles formed from poly(poly(ethylene glycol) methyl ether methacrylate)-block-poly(methyl methacrylate) (P(PEGMEMA75)-b-PMMA80) block copolymer of approximately 25nm in diameter were used to encapsulate the model drug, Nile Red, with a loading efficiency of 0.08wt% and a chemotherapeutic drug, doxorubicin (DOX), with an efficiency of 2.75wt%. The release of DOX from the micelles was sufficient to be cytotoxic to human colon carcinoma cells, WiDr, while Nile Red and the unloaded micelles were found not to be cytotoxic when exposed to the cells at polymer concentrations up to 200μg/mL. Nile Red loaded micelles were used to analyze uptake of the micelles into the cells which were rapidly internalized within minutes of exposure. The three major endocytotic pathways were involved in the internalization of micelles; however other passive mechanisms were also at play as the addition of inhibitors to all three pathways did not completely inhibit the uptake of these nanoparticles. These data demonstrate the potential of the P(PEGMEMA)75-b-PMMA80 block copolymer micelles to be rapidly internalized by carcinoma cells and deliver low doses of drugs intracellularly for controlled drug release.

  12. 40 CFR 721.7260 - Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymer of poly-ethylene-polyamine and... New Uses for Specific Chemical Substances § 721.7260 Polymer of poly-ethylene-polyamine and alkanediol... chemical substance identified generically as polymer of polyethylenepolyamine and alkanediol...

  13. 40 CFR 721.7260 - Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polymer of poly-ethylene-polyamine and... New Uses for Specific Chemical Substances § 721.7260 Polymer of poly-ethylene-polyamine and alkanediol... chemical substance identified generically as polymer of polyethylenepolyamine and alkanediol...

  14. 40 CFR 721.7260 - Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polymer of poly-ethylene-polyamine and... New Uses for Specific Chemical Substances § 721.7260 Polymer of poly-ethylene-polyamine and alkanediol... chemical substance identified generically as polymer of polyethylenepolyamine and alkanediol diglycidyl...

  15. 40 CFR 721.7260 - Polymer of poly-ethylene-polyamine and alkanediol di-gly-cidyl ether.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polymer of poly-ethylene-polyamine and... New Uses for Specific Chemical Substances § 721.7260 Polymer of poly-ethylene-polyamine and alkanediol... chemical substance identified generically as polymer of polyethylenepolyamine and alkanediol diglycidyl...

  16. Synthetic evaluation of disulphide-bonded sarafotoxin on a poly(oxy ether) grafted dendrimeric poly(alkyl amine) support for polymer assisted organic synthesis.

    PubMed

    Siyad, M A; Kumar, G S Vinod

    2013-08-07

    The present paper describes the synthesis, characterization and assessment of a novel class of insoluble polymeric polystyrene supports which combines polar poly(ethylene glycol)dimethacrylate as a cross-linker and poly(ethylene glycol) grafted poly(N,N-bisethylamine) as a dendritic template. Poly(N,N-bisethylamine) dendrimers were generated by a series of reactions such as Schiff base integration, acidolysis, diazotization and thionyl chloride treatment. The same successive sequences of reactions have been followed for second generation dendrimers also and subjected to PEGylation (PEG 600) to achieve the desirable physico-chemical properties. The applicability of the novel PEGylated dendrimer support was demonstrated by synthesizing linear as well as disulfide bonded peptides in high yields and purities.

  17. Poly(glycidyl ether)-Based Monolayers on Gold Surfaces: Control of Grafting Density and Chain Conformation by Grafting Procedure, Surface Anchor, and Molecular Weight.

    PubMed

    Heinen, Silke; Weinhart, Marie

    2017-03-07

    For a meaningful correlation of surface coatings with their respective biological response reproducible coating procedures, well-defined surface coatings, and thorough surface characterization with respect to layer thickness and grafting density are indispensable. The same applies to polymeric monolayer coatings which are intended to be used for, e.g., fundamental studies on the volume phase transition of surface end-tethered thermoresponsive polymer chains. Planar gold surfaces are frequently used as model substrates, since they allow a variety of straightforward surface characterization methods. Herein we present reproducible grafting-to procedures performed with thermoresponsive poly(glycidyl ether) copolymers composed of glycidyl methyl ether (GME) and ethyl glycidyl ether (EGE). The copolymers feature different molecular weights (2 kDa, 9 kDa, 24 kDa) and are equipped with varying sulfur-containing anchor groups in order to achieve adjustable grafting densities on gold surfaces and hence control the tethered polymers' chain conformation. We determined "wet" and "dry" thicknesses of these coatings by QCM-D and ellipsometry measurements and deduced anchor distances and degrees of chain overlap of the polymer chains assembled on gold. Grafting under cloud point conditions allowed for higher degrees of chain overlap compared to grafting from a good solvent like ethanol, independent of the used sulfur-containing anchor group for polymers with low (2 kDa) and medium (9 kDa) molecular weights. By contrast, the achieved grafting densities and thus chain overlaps of surface-tethered polymers with high (24 kDa) molecular weights were identical for both grafting methods. Monolayers prepared from an ethanolic solution of poly(glycidyl ether)s equipped with sterically demanding disulfide-containing anchors revealed the lowest degrees of chain overlap. The ratio of the radius of gyration to the anchor distance (2 Rg/l) of the latter coating was found to be lower than 1

  18. Use of the composite membrane of poly(ether-block-amide) and carbon nanotubes (CNTs) in a pervaporation system incorporated with fermentation for butanol production by Clostridium acetobutylicum.

    PubMed

    Yen, Hong-Wei; Chen, Zhi-Heng; Yang, I-Kuan

    2012-04-01

    Fermentation incorporated with pervaporation was regarded as an efficient way to relieve the feedback inhibition of butanol in acetone-butanol-ethanol (ABE) fermentation. The addition of CNTs (carbon nanotubes) to PEBA (poly(ether-block-amide)) could greatly enhance the removal flux of solvents (acetone, butanol and ethanol) in a model solution test. The butanol removing rate results in a 61% increase in the batch with PEBA+CNTs (5%) membrane compared with that of the batch with PEBA alone. Besides the increase of removal flux, the addition of CNTs enforces the mechanical strength of the pervaporation membrane, which leads to more resistance for a longer operational time. The combination of a 5-L fermenter with the pervaporation membrane of PEBA+CNTs (10%) indicates a 20% increase both in productivity and yield compared to using PEBA. In conclusion, the addition of CNTs to a PEBA pervaporation membrane has great potential when applied in the ABE fermentation industry.

  19. Atomic motions in poly(vinyl methyl ether): A combined study by quasielastic neutron scattering and molecular dynamics simulations in the light of the mode coupling theory.

    PubMed

    Capponi, S; Arbe, A; Alvarez, F; Colmenero, J; Frick, B; Embs, J P

    2009-11-28

    Quasielastic neutron scattering experiments (time-of-flight, neutron spin echo, and backscattering) on protonated poly(vinyl methyl ether) (PVME) have revealed the hydrogen dynamics above the glass-transition temperature. Fully atomistic molecular dynamics simulations properly validated with the neutron scattering results have allowed further characterization of the atomic motions accessing the correlation functions directly in real space. Deviations from Gaussian behavior are found in the high-momentum transfer range, which are compatible with the predictions of mode coupling theory (MCT). We have applied the MCT phenomenological version to the self-correlation functions of PVME atoms calculated from our simulation data, obtaining consistent results. The unusually large value found for the lambda-exponent parameter is close to that recently reported for polybutadiene and simple polymer models with intramolecular barriers.

  20. Immobilization of xylanase on poly (ethylene glycol) methyl ether 5000 and its self-extractive bioconversion for the production of xylo-oligosaccharides.

    PubMed

    Li, Xin; Shan, Zongxing; Song, Xiangyang; Ouyang, Jia; Xu, Yong; Yong, Qiang; Yu, Shiyuan

    2014-02-01

    Endo-β-1,4-xylanase derived from Trichoderma reesei was covalently immobilized on poly (ethylene glycol) methyl ether 5000 (mPEG5000), and the resulting immobilized enzyme had a residual activity of 72.4 % with 82.9 % of PEGylated amino groups. Compared with the free enzyme, the immobilized xylanase was stable at pH values in the range of 4.0-6.0 and temperatures in the range of 50-65 °C. A self-extractive bioconversion system composed of immobilized xylanase, mPEG5000, and sodium citrate was used to produce xylo-oligosaccharides and provided a better distribution of the xylo-oligosaccharides than the free enzyme. Furthermore, the immobilized xylanase could be effectively recovered in situ following the hydrolysis reaction.

  1. Generation of a Focused Poly(amino ether) Library: Polymer-mediated Transgene Delivery and Gold-Nanorod based Theranostic Systems

    PubMed Central

    Vu, Lucas; Ramos, James; Potta, Thrimoorthy; Rege, Kaushal

    2012-01-01

    A focused library of twenty-one cationic poly(amino ethers) was synthesized following ring-opening polymerization of two diglycidyl ethers by different oligoamines. The polymers were screened in parallel for plasmid DNA (pDNA) delivery, and transgene expression efficacies of individual polymers were compared to those of 25 kDa polyethylenimine (PEI), a current standard for polymer-mediated transgene delivery. Seven lead polymers that demonstrated higher transgene expression than PEI in pancreatic and prostate cancer cells lines were identified from the screen. All seven lead polymers showed highest transgene expression at a polymer:pDNA weight ratio of 5:1 in the MIA PaCa-2 pancreatic cancer cell line. Among the conditions studied, transgene expression efficacy correlated with minimal polymer cytotoxicity but not polyplex sizes. In addition, this study indicated that methylene spacing between amine centers in the monomers, amine content, and molecular weight of the polymers are all significant factors and should be considered when designing polymers for transgene delivery. A lead effective polymer was employed for coating gold nanorods, leading to theranostic nanoassemblies that possess combined transgene delivery and optical imaging capabilities, leading to potential theranostic systems. PMID:23382773

  2. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, J.V.

    1996-10-22

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of the above formula together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  3. Propenyl ether monomers for photopolymerization

    DOEpatents

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  4. Preparation and Characterization of poly(Azomethines) Containing Ether and Methylene Bridges: Photophysical, Electrochemical, Conductivity and Thermal Properties.

    PubMed

    Kaya, İsmet; Yılmaz, Tahsin

    2017-01-01

    In this paper, a series of polyazomethines (PAZs) were prepared using dihydroxy substituted Schiff bases and 1,4-diiodobenzene. Also, different group effect such as methylene carbon and etheric oxygen bridges on photophysical, electrochemical, conductivity and thermal properties were clarified. The new polymeric materials structures were confirmed by means of (1)H-NMR, FT-IR and UV-vis measurements. The molecular weight distributions of polymers were determined with gel permeation chromatography (GPC) measurements. Photophysical behaviors of polymers were explored by UV-vis absorption and fluorescence measurements. TGA-DTA and DSC techniques have been used for the thermal characterization of the PAZs. Thermal data and fluorescence measurements showed that etheric oxygen bridge containing polymers have a bit higher char and emission intensity than the methylene carbon bridge carrying polymers. According to TG analysis, Ton values of P-2MPDP, P-2-OPDP, P-4-MPDP and P-4-OPDP were found as 210, 250, 249 and 233 °C, respectively. The HOMO-LUMO energy levels, electrochemical (E' g ) and optical (E g ) band gaps were calculated from cyclic voltammetry (CV) and UV-vis measurements, respectively. The electrochemical (E g ') band gaps values of P-2MPDP, P-2-OPDP, P-4-MPDP and P-4-OPDP were calculated as 2.68, 2.32, 2.34 and 2.07, respectively. Additionally, four-point probe technique was used to measure solid state electrical conductivities of both doped and undoped states of the PAZs.

  5. Poly(arlyene ether sulfone) based semi-interpenetrating polymer network membranes containing cross-linked poly(vinyl phosphonic acid) chains for fuel cell applications at high temperature and low humidity conditions

    NASA Astrophysics Data System (ADS)

    Kim, Kihyun; Heo, Pilwon; Ko, Taeyun; Kim, Ki-hyun; Kim, Sung-Kon; Pak, Chanho; Lee, Jong-Chan

    2015-10-01

    Semi-interpenetrating polymer network (semi-IPN) membranes are prepared by in-situ casting and thermal-initiated radical polymerization of vinyl phosphonic acid (VPA) and bis(2-(methacryloyloxy)ethyl) phosphate (BMAEP) in N,N-dimethylacetamide solutions of sulfonated poly(arylene ether sulfone) (SPAES). The incorporation of VPA units into the SPAES membranes improves proton conductivity especially at high temperature and low humidity conditions. In addition the cross-linker, BMAEP, prevents the decrease of the mechanical and chemical stabilities by the aliphatic linear poly(vinyl phosphonic acid) chains in the semi-IPN membranes, and furthermore the phosphonic acid group in BMAEP can prevent the decrease of the proton conductivity by the formation of cross-linked structures. Therefore, the resulting semi-IPN membranes show high proton conductivities up to 15 mS cm-1 at 120 °C and 40% RH. The fuel cell performance (187 mW cm-2 at 120 °C and 40% RH) of membrane-electrode assembly (MEA) from the semi-IPN membrane is found to be superior to that (145 mW cm-2 at 120 °C and 40% RH) of MEA from the SPAES membrane. The durability test result at the operating conditions indicates that the semi-IPN membrane is electrochemically very stable maintaining the low hydrogen cross-over and high power densities.

  6. Thermo-responsive cell culture carriers based on poly(vinyl methyl ether)-the effect of biomolecular ligands to balance cell adhesion and stimulated detachment.

    PubMed

    Teichmann, Juliane; Nitschke, Mirko; Pette, Dagmar; Valtink, Monika; Gramm, Stefan; Härtel, Frauke V; Noll, Thomas; Funk, Richard H W; Engelmann, Katrin; Werner, Carsten

    2015-08-01

    Two established material systems for thermally stimulated detachment of adherent cells were combined in a cross-linked polymer blend to merge favorable properties. Through this approach poly(N-isopropylacrylamide) (PNiPAAm) with its superior switching characteristic was paired with a poly(vinyl methyl ether)-based composition that allows adjusting physico-chemical and biomolecular properties in a wide range. Beyond pure PNiPAAm, the proposed thermo-responsive coating provides thickness, stiffness and swelling behavior, as well as an apposite density of reactive sites for biomolecular functionalization, as effective tuning parameters to meet specific requirements of a particular cell type regarding initial adhesion and ease of detachment. To illustrate the strength of this approach, the novel cell culture carrier was applied to generate transplantable sheets of human corneal endothelial cells (HCEC). Sheets were grown, detached, and transferred onto planar targets. Cell morphology, viability and functionality were analyzed by immunocytochemistry and determination of transepithelial electrical resistance (TEER) before and after sheet detachment and transfer. HCEC layers showed regular morphology with appropriate TEER. Cells were positive for function-associated marker proteins ZO-1, Na(+)/K(+)-ATPase, and paxillin, and extracellular matrix proteins fibronectin, laminin and collagen type IV before and after transfer. Sheet detachment and transfer did not impair cell viability. Subsequently, a potential application in ophthalmology was demonstrated by transplantation onto de-endothelialized porcine corneas in vitro. The novel thermo-responsive cell culture carrier facilitates the generation and transfer of functional HCEC sheets. This paves the way to generate tissue engineered human corneal endothelium as an alternative transplant source for endothelial keratoplasty.

  7. Thermo-responsive cell culture carriers based on poly(vinyl methyl ether)—the effect of biomolecular ligands to balance cell adhesion and stimulated detachment

    NASA Astrophysics Data System (ADS)

    Teichmann, Juliane; Nitschke, Mirko; Pette, Dagmar; Valtink, Monika; Gramm, Stefan; Härtel, Frauke V.; Noll, Thomas; Funk, Richard H. W.; Engelmann, Katrin; Werner, Carsten

    2015-08-01

    Two established material systems for thermally stimulated detachment of adherent cells were combined in a cross-linked polymer blend to merge favorable properties. Through this approach poly(N-isopropylacrylamide) (PNiPAAm) with its superior switching characteristic was paired with a poly(vinyl methyl ether)-based composition that allows adjusting physico-chemical and biomolecular properties in a wide range. Beyond pure PNiPAAm, the proposed thermo-responsive coating provides thickness, stiffness and swelling behavior, as well as an apposite density of reactive sites for biomolecular functionalization, as effective tuning parameters to meet specific requirements of a particular cell type regarding initial adhesion and ease of detachment. To illustrate the strength of this approach, the novel cell culture carrier was applied to generate transplantable sheets of human corneal endothelial cells (HCEC). Sheets were grown, detached, and transferred onto planar targets. Cell morphology, viability and functionality were analyzed by immunocytochemistry and determination of transepithelial electrical resistance (TEER) before and after sheet detachment and transfer. HCEC layers showed regular morphology with appropriate TEER. Cells were positive for function-associated marker proteins ZO-1, Na+/K+-ATPase, and paxillin, and extracellular matrix proteins fibronectin, laminin and collagen type IV before and after transfer. Sheet detachment and transfer did not impair cell viability. Subsequently, a potential application in ophthalmology was demonstrated by transplantation onto de-endothelialized porcine corneas in vitro. The novel thermo-responsive cell culture carrier facilitates the generation and transfer of functional HCEC sheets. This paves the way to generate tissue engineered human corneal endothelium as an alternative transplant source for endothelial keratoplasty.

  8. Thermo-responsive cell culture carriers based on poly(vinyl methyl ether)—the effect of biomolecular ligands to balance cell adhesion and stimulated detachment

    PubMed Central

    Teichmann, Juliane; Nitschke, Mirko; Pette, Dagmar; Valtink, Monika; Gramm, Stefan; Härtel, Frauke V; Noll, Thomas; Funk, Richard H W; Engelmann, Katrin; Werner, Carsten

    2015-01-01

    Two established material systems for thermally stimulated detachment of adherent cells were combined in a cross-linked polymer blend to merge favorable properties. Through this approach poly(N-isopropylacrylamide) (PNiPAAm) with its superior switching characteristic was paired with a poly(vinyl methyl ether)-based composition that allows adjusting physico-chemical and biomolecular properties in a wide range. Beyond pure PNiPAAm, the proposed thermo-responsive coating provides thickness, stiffness and swelling behavior, as well as an apposite density of reactive sites for biomolecular functionalization, as effective tuning parameters to meet specific requirements of a particular cell type regarding initial adhesion and ease of detachment. To illustrate the strength of this approach, the novel cell culture carrier was applied to generate transplantable sheets of human corneal endothelial cells (HCEC). Sheets were grown, detached, and transferred onto planar targets. Cell morphology, viability and functionality were analyzed by immunocytochemistry and determination of transepithelial electrical resistance (TEER) before and after sheet detachment and transfer. HCEC layers showed regular morphology with appropriate TEER. Cells were positive for function-associated marker proteins ZO-1, Na+/K+-ATPase, and paxillin, and extracellular matrix proteins fibronectin, laminin and collagen type IV before and after transfer. Sheet detachment and transfer did not impair cell viability. Subsequently, a potential application in ophthalmology was demonstrated by transplantation onto de-endothelialized porcine corneas in vitro. The novel thermo-responsive cell culture carrier facilitates the generation and transfer of functional HCEC sheets. This paves the way to generate tissue engineered human corneal endothelium as an alternative transplant source for endothelial keratoplasty. PMID:27877823

  9. Toxic metal ion separation by cellulose acetate/sulfonated poly(ether imide) blend membranes: effect of polymer composition and additive.

    PubMed

    Nagendran, A; Vijayalakshmi, A; Arockiasamy, D Lawrence; Shobana, K H; Mohan, D

    2008-07-15

    Toxic heavy metal ion removal from industrial effluents are gaining increased visibility owing to environmental concern and saving precious materials. In this work, an attempt has been made to remove the valuable metal ions using modified ultrafiltration (UF) blend membranes based on cellulose acetate (CA) and sulfonated poly(ether imide) (SPEI) were prepared in the presence and absence of additive, poly(ethylene glycol) 600 (PEG600) in various compositions. Prepared membranes were characterized in terms of pure water flux (PWF), water content and membrane hydraulic resistance. High flux UF membranes were obtained in the range of 15-25 wt% SPEI and 2.5-10 wt% PEG600 in the polymer blend. The molecular weight cut-off (MWCO) of the blend membranes were determined using protein separation studies found to vary from 20 to greater than 69 kDa. Surface morphology of the blend membranes were analysed with scanning electron microscopy. Studies were carried out to find the rejection and permeate flux of metal ions such as Cu(II), Ni(II), Zn(II) and Cd(II) using polyethyleneimine as the chelating ligand. On increasing the composition of SPEI and PEG600, the rejection of metal ions is decreasing while the permeate flux has an increasing trend. These effects are due to the increased pore formation in the CA/SPEI blend membranes because of the hydrophilic SPEI and polymeric additive PEG600. In general, it was found that CA/SPEI blend membranes displayed higher permeate flux and lower rejection compared to pure CA membranes. The extent of separation of metal ions depends on the affinity of metal ions to polyethyleneimine to form macromolecular complexes and the stability of the formed complexes.

  10. pH-sensitive micelles self-assembled from multi-arm star triblock co-polymers poly(ε-caprolactone)-b-poly(2-(diethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) for controlled anticancer drug delivery.

    PubMed

    Yang, You Qiang; Zhao, Bin; Li, Zhen Dong; Lin, Wen Jing; Zhang, Can Yang; Guo, Xin Dong; Wang, Ju Fang; Zhang, Li Juan

    2013-08-01

    A series of amphiphilic 4- and 6-armed star triblock co-polymers poly(ε-caprolactone)-b-poly(2-(diethylamino)ethyl methacrylate)-b-poly(poly(ethylene glycol) methyl ether methacrylate) (4/6AS-PCL-b-PDEAEMA-b-PPEGMA) were developed by a combination of ring opening polymerization and continuous activators regenerated by electron transfer atom transfer radical polymerization. The critical micelle concentration values of the star co-polymers in aqueous solution were extremely low (2.2-4.0mgl(-1)), depending on the architecture of the co-polymers. The self-assembled blank and doxorubicin (DOX)-loaded three layer micelles were spherical in shape with an average size of 60-220nm determined by scanning electron microscopy and dynamic light scattering. The in vitro release behavior of DOX from the three layer micelles exhibited pH-dependent properties. The DOX release rate was significantly accelerated by decreasing the pH from 7.4 to 5.0, due to swelling of the micelles at lower pH values caused by the protonation of tertiary amine groups in DEAEMA in the middle layer of the micelles. The in vitro cytotoxicity of DOX-loaded micelles to HepG2 cells suggested that the 4/6AS-PCL-b-PDEAEMA-b-PPEGMA micelles could provide equivalent or even enhanced anticancer activity and bioavailability of DOX and thus a lower dosage is sufficient for the same therapeutic efficacy. The results demonstrate that the pH-sensitive multilayer micelles could have great potential application in delivering hydrophobic anticancer drugs for improved cancer therapy.

  11. Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Hergenrother, Paul M.; Bass, Robert G.

    1991-01-01

    New imide/arylene ether copolymers prepared by reacting anhydride-terminated poly(amic acids) with amine-terminated poly(arylene ethers) in polar aprotic solvents. Each resulting copolymer may have one glass-transition temperature or two, depending on chemical structure and/or compatibility of block units. Most of copolymers form tough, solvent-resistant films with high tensile properties. Films cast from solution tough and flexible, and exhibit useful thermal and mechanical properties. Potentially useful as moldings, adhesives, or composite matrices. Because of flexible arylene ether blocks, these copolymers easier to process than polyimides.

  12. 40 CFR 721.3488 - Poly(oxy-1,2-ethanediyl), alpha substituted-omega-hydroxy-, C16-20 alkyl ethers.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... substituted-omega-hydroxy-, C16-20 alkyl ethers. 721.3488 Section 721.3488 Protection of Environment... substituted-omega-hydroxy-, C16-20 alkyl ethers. (a) Chemical substance and significant new uses subject to...-omega-hydroxy-, C16-20 alkyl ethers (PMN P-87-323) is subject to reporting under this section for...

  13. 40 CFR 721.3488 - Poly(oxy-1,2-ethanediyl), alpha substituted-omega-hydroxy-, C16-20 alkyl ethers.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... substituted-omega-hydroxy-, C16-20 alkyl ethers. 721.3488 Section 721.3488 Protection of Environment... substituted-omega-hydroxy-, C16-20 alkyl ethers. (a) Chemical substance and significant new uses subject to...-omega-hydroxy-, C16-20 alkyl ethers (PMN P-87-323) is subject to reporting under this section for...

  14. 40 CFR 721.3488 - Poly(oxy-1,2-ethanediyl), alpha substituted-omega-hydroxy-, C16-20 alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... substituted-omega-hydroxy-, C16-20 alkyl ethers. 721.3488 Section 721.3488 Protection of Environment... substituted-omega-hydroxy-, C16-20 alkyl ethers. (a) Chemical substance and significant new uses subject to...-omega-hydroxy-, C16-20 alkyl ethers (PMN P-87-323) is subject to reporting under this section for...

  15. 40 CFR 721.3488 - Poly(oxy-1,2-ethanediyl), alpha substituted-omega-hydroxy-, C16-20 alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... substituted-omega-hydroxy-, C16-20 alkyl ethers. 721.3488 Section 721.3488 Protection of Environment... substituted-omega-hydroxy-, C16-20 alkyl ethers. (a) Chemical substance and significant new uses subject to...-omega-hydroxy-, C16-20 alkyl ethers (PMN P-87-323) is subject to reporting under this section for...

  16. 40 CFR 721.3488 - Poly(oxy-1,2-ethanediyl), alpha substituted-omega-hydroxy-, C16-20 alkyl ethers.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... substituted-omega-hydroxy-, C16-20 alkyl ethers. 721.3488 Section 721.3488 Protection of Environment... substituted-omega-hydroxy-, C16-20 alkyl ethers. (a) Chemical substance and significant new uses subject to...-omega-hydroxy-, C16-20 alkyl ethers (PMN P-87-323) is subject to reporting under this section for...

  17. Use of poly(ether-block-amide) in pervaporation coupling with a fermentor to enhance butanol production in the cultivation of Clostridium acetobutylicum.

    PubMed

    Yen, Hong-Wei; Lin, Shang-Fu; Yang, I-Kuan

    2012-03-01

    The toxicity of the end-products of acetone-butanol-ethanol (ABE) process, mainly butanol, is recognized as the major problem contributing to the low productivity of butanol. The pervaporation technique was regarded as one of the ways to efficiently remove organic components. The results of pervaporation performance of poly(ether-block-amide) (PEBA) and polydimethylsiloxane (PDMS) membrane in a model solution indicated that PEBA membrane owned a higher butanol permeation flux of 9.975 gm(-2)h(-1) as opposed to 3.911 gm(-2)h(-1) using a PDMS membrane. Moreover, a higher temperature would result in a higher permeation flux, but has a lower separation factor (α) obtained, while using PEBA membrane. The batch fermentor operation connected to the pervaporation with PEBA membrane created 43% and 34% of increase in the butanol productivity and in the yield as compared to that of the simple batch. The fed-batch fermentation mode by glucose feeding combined with PEBA pervaporation lasting for 24h could achieve 39% increase of butanol productivity as compared to a simple batch. Conclusively, the pervaporation with PEBA membrane coupling with fermentor was presumed to be capable of enhancing butanol production in ABE fermentation, which might have the potential applied in the commercialized ABE fermentation process.

  18. Solvent resistant chitosan/poly(ether-block-amide) composite membranes for pervaporation of n-methyl-2-pyrrolidone/water mixtures.

    PubMed

    Prasad, N Shiva; Moulik, Siddhartha; Bohra, Subha; Rani, K Yamuna; Sridhar, S

    2016-01-20

    A novel composite barrier comprising of hydrophilic and solvent resistant chitosan (CS) membrane on porous solvent resistant poly(ether-block-amide) (PEBA-2533) substrate was synthesized for pervaporation (PV) based dehydration of the polar aprotic n-methyl-2-pyrolidone (NMP) green solvent. The composite barrier was crosslinked with tetraethyl orthosilicate (TEOS) to control swelling and enhance selectivity. Operating parameters such as feed water concentration, permeate pressure and membrane thickness were varied to assess membrane flux and selectivity. A two-dimensional finite element method (FEM) model was developed to predict the concentration profile within the membrane through computational fluid dynamics (CFD). On the basis of complete mixing experiments, a numerical simulation was performed to predict membrane area requirement and exit streams' compositions for commercial pervaporation units operated in plug flow mode. Both unmodified chitosan and tetraethyl orthosilicate crosslinked composite membranes successfully separated feed mixture containing 4.6 wt% water by exhibiting water fluxes of 0.024 and 0.019 kg/m(2)h, whereas the corresponding selectivities were found to be as high as 182 and 225, respectively.

  19. Self-healing pH-sensitive poly[(methyl vinyl ether)-alt-(maleic acid)]-based supramolecular hydrogels formed by inclusion complexation between cyclodextrin and adamantane.

    PubMed

    Ma, Xiaoe; Zhou, Naizhen; Zhang, Tianzhu; Hu, Wanjun; Gu, Ning

    2017-04-01

    Self-healing materials are of interest for drug delivery, cell and gene therapy, tissue engineering, and other biomedical applications. In this work, on the base of biocompatible polymer poly(methyl vinyl ether-alt-maleic acid) (P(MVE-alt-MA)), host polymer β-cyclodextrin-grafted P(MVE-alt-MA) (P(MVE-alt-MA)-g-β-CD) and guest polymer adamantane-grafted P(MVE-alt-MA) (P(MVE-alt-MA)-g-Ad) were first prepared. Then through taking advantage of the traditional host-guest interaction of β-cyclodextrin and adamantane, a novel self-healing pH-sensitive physical P(MVE-alt-MA)-g-β-CD/P(MVE-alt-MA)-g-Ad supramolecular hydrogels were obtained after simply mixing the aqueous solution of host polymer and guest polymer. This kind of supramolecular hydrogels not only possess pH-sensitivity, but also possess the ability to repair themselves after being damaged. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Poly(phthalazine ether sulfone ketone) as novel stationary phase for stir bar sorptive extraction of organochlorine compounds and organophosphorus pesticides.

    PubMed

    Guan, Wenna; Wang, Yanjuan; Xu, Feng; Guan, Yafeng

    2008-01-04

    A novel poly(phthalazine ether sulfone ketone) (PPESK) film prepared by immersion precipitation technique was coated on stir bars for sorptive extraction. Scanning electron micrographs showed that the coating has a denser porous surface (about 1 microm in thickness) with a sponge-like sublayer, and the thickness of the coating was 250 microm. The PPESK coated stir bar has high thermostability (290 degrees C) and long lifetime (50 times). The extraction properties of this stir bar were evaluated for the extraction of both polar and semi-polar analytes, including organochlorine compounds and organophosphorus pesticides. The PPESK stir bar was proved to show higher affinity towards polar compounds than that of PDMS coated stir bar and higher sample load compared with corresponding PPESK fiber. It was applied to the determination of organochlorine compounds in seawater samples and organophosphorus pesticides in juices by gas chromatographic analysis. The effect of sample matrix was evaluated at optimized condition of extraction temperature, extraction time and salt concentration. Limits of detection were in the range of 0.05-2.53 ng L(-1) for organochlorine compounds in seawater samples using electron capture detector (ECD), with precisions of less than 11% RSD. Limits of detection for organophosphorus pesticides were in the range of 0.17-2.25 ng L(-1) and 2.47-10.3 ng L(-1) in grape and peach juice, respectively, using thermionic specified detector (TSD), with precisions of less than 12% RSD and 20% RSD, respectively.

  1. [Analysis of phenolic compounds in aqueous samples by gas chromatography coupled with headspace solid-phase microextraction using poly (phthalazine ether sulfone ketone) coated fiber].

    PubMed

    Yao, Guiyan; Guan, Wenna; Xu, Feng; Wang, Hua; Guan, Yafeng

    2008-09-01

    The direct trace analysis of phenolic compounds in aqueous samples was performed by headspace solid-phase microextraction/gas chromatography (HS-SPME/GC). A laboratory made poly (phthalazine ether sulfone ketone) (PPESK, 30 microm) coated fiber was used to extract the phenols from aqueous samples. The parameters affecting the extraction efficiency, such as extraction temperature and time, pH value, and salt concentration, were optimized. The low pH value and high salt concentration can increase the extraction efficiency of phenols. The limits of detection (LODs) were from 0.003 to 0.041 microg/L, which were within the range of EPA Method 604. The relative standard deviations (RSDs) were less than 16%. Compared with commercial polyacrylate (PA) fiber (85 microm), the PPESK fiber shows high affinity toward phenolic compounds, and therefore, high absolute recoveries. The phenols were detected with the recoveries of 100.5%-111.8% for a tap water sample and 94.8%-117.3% for a seawater sample at the spiked level of 20 microg/L.

  2. Effects of Block Length and Membrane Processing Conditions on the Morphology and Properties of Perfluorosulfonated Poly(arylene ether sulfone) Multiblock Copolymer Membranes for PEMFC.

    PubMed

    Assumma, Luca; Nguyen, Huu-Dat; Iojoiu, Cristina; Lyonnard, Sandrine; Mercier, Régis; Espuche, Eliane

    2015-07-01

    Perfluorosulfonated poly(arylene ether sulfone) multiblock copolymers have been shown to be promising as proton exchange membranes. The commonly used approach for preparation of the membrane is solvent casting; the properties of the resulting membranes are very dependent on the membrane processing conditions. In this paper, we study the effects of block length, selectivity of the solvent, and thermal treatment on the membrane properties such as morphology, water uptake, and ionic conductivity. DiMethylSulfOxide (DMSO), and DiMethylAcetamide (DMAc) were selected as casting solvents based on the Flory-Huggins parameter calculated by inversion gas chromatography (IGC). It was found that the solvent selectivity has a mild impact on the mean size of the ionic domains and the expansion upon swelling, while it dramatically affects the supramolecular ordering of the blocks. The membranes cast from DMSO exhibit more interconnected ionic clusters yielding higher conductivities and water uptake as compared to membranes cast from DMAc. A 10-fold increase in proton conductivity was achieved after thermal annealing of membranes at 150 °C, and the ionomers with longer block lengths show conductivities similar to Nafion at 80 °C and low relative humidity (30%).

  3. Nafion-assisted cross-linking of sulfonated poly(arylene ether ketone) bearing carboxylic acid groups and their composite membranes for fuel cells

    NASA Astrophysics Data System (ADS)

    Lin, Haidan; Zhao, Chengji; Na, Hui

    In this study, a new type of cross-linked composite membrane is prepared and considered for its potential applications in direct methanol fuel cell. Nafion and sulfonated poly(arylene ether ketone) bearing carboxylic acid groups (SPAEK-C) are blended and subsequently cross-linked by a Friedel-Craft reaction using the carboxylic acid groups in the SPAEK-C to achieve lower methanol permeability. The perfluoroalkyl sulfonic acid groups of Nafion act as a benign solid catalyst, which assist the cross-linking of SPAEK-C. The physical and chemical characterizations of the cross-linked composite membranes are performed by varying the contents of SPAEK-C. The c-Nafion-15% membrane exhibits appropriate water uptake (10.49-25.22%), low methanol permeability (2.57 × 10 -7 cm 2 s -1), and high proton conductivity (0.179 S cm -1 at 80 °C). DSC and FTIR analyze suggest the cross-linking reaction. These results show that the self-cross-linking of SPAEK-C in the Nafion membrane can effectively reduce methanol permeability while maintaining high proton conductivity.

  4. Imidazolium-Functionalized Poly(arylene ether sulfone) Anion-Exchange Membranes Densely Grafted with Flexible Side Chains for Fuel Cells.

    PubMed

    Guo, Dong; Lai, Ao Nan; Lin, Chen Xiao; Zhang, Qiu Gen; Zhu, Ai Mei; Liu, Qing Lin

    2016-09-28

    With the intention of optimizing the performance of anion-exchange membranes (AEMs), a set of imidazolium-functionalized poly(arylene ether sulfone)s with densely distributed long flexible aliphatic side chains were synthesized. The membranes made from the as-synthesized polymers are robust, transparent, and endowed with microphase segregation capability. The ionic exchange capacity (IEC), hydroxide conductivity, water uptake, thermal stability, and alkaline resistance of the AEMs were evaluated in detail for fuel cell applications. Morphological observation with the use of atomic force microscopy and small-angle X-ray scattering reveals that the combination of high-local-density-type and side-chain-type architectures induces distinguished nanophase separation in the AEMs. The as-prepared membranes have advantages in effective water management and ionic conductivity over traditional main-chain polymers. Typically, the conductivity and IEC were in the ranges of 57.3-112.5 mS cm(-1) and 1.35-1.84 mequiv g(-1) at 80 °C, respectively. Furthermore, the membranes exhibit good thermal and alkaline stability and achieve a peak power density of 114.5 mW cm(-2) at a current density of 250.1 mA cm(-2). Therefore, the present polymers containing clustered flexible pendent aliphatic imidazolium promise to be attractive AEM materials for fuel cells.

  5. Self-assembly and gelation of poly(aryl ether) dendrons containing hydrazide units: factors controlling the formation of helical structures.

    PubMed

    Malakar, Partha; Prasad, Edamana

    2015-03-23

    Self-assembly of AB2 and AB3 type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self-assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J-type aggregation, ii) the hydrogen-bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self-assemble to form dimer structures through hydrogen-bonding and further assembly of the hydrogen-bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self-assembly in the system was driven by hydrogen-bonding and π-π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self-assembly follows a nucleation-elongation model to form helical structures, rather than the isodesmic model.

  6. Note: Thermal conductivity measurement of individual poly(ether ketone)/carbon nanotube fibers using a steady-state dc thermal bridge method.

    PubMed

    Moon, Jaeyun; Weaver, Keith; Feng, Bo; Chae, Han Gi; Kumar, Satish; Baek, Jong-Beom; Peterson, G P

    2012-01-01

    Customized engineered fibers are currently being used extensively in the aerospace and automobile industries due to the ability to "design in" specific engineering characteristics. Understanding the thermal conductivity of these new fibers is critical for thermal management and design optimization. In the current investigation, a steady-state dc thermal bridge method (DCTBM) is developed to measure the thermal conductivity of individual poly(ether ketone) (PEK)/carbon nanotube (CNT) fibers. For non-conductive fibers, a thin platinum layer was deposited on the test articles to serve as the heater and temperature sensor. The effect of the platinum layer on the thermal conductivity is presented and discussed. DCTBM is first validated using gold and platinum wires (25 μm in diameter) over a temperature ranging from room temperature to 400 K with ±11% uncertainty, and then applied to PEK/CNT fibers with diverse CNT loadings. At a 28 wt. % CNT loading, the thermal conductivity of fibers at 390 K is over 27 Wm(-1)K(-1), which is comparable to some engineering alloys.

  7. Macromolecular cross-linked polybenzimidazole based on bromomethylated poly (aryl ether ketone) with enhanced stability for high temperature fuel cell applications

    NASA Astrophysics Data System (ADS)

    Wang, Shuang; Zhao, Chengji; Ma, Wenjia; Zhang, Na; Liu, Zhongguo; Zhang, Gang; Na, Hui

    2013-12-01

    A series of macromolecular cross-linked polybenzimidazole (PBI) membranes have been successfully prepared for the high temperature proton exchange membrane fuel cell (HT-PEMFC) applications. Bromomethylated poly (aryl ether ketone) (BrPAEK) is synthesized and used as a macromolecular cross-linker, the cross-linking reaction can be accomplished at 160 °C using an easy facial heating treatment. The resulting cross-linked membranes CBrPBI-X (X is the weight fraction of the cross-linker) display excellent mechanical strength. After phosphoric acid (PA) doping, the mechanical strength and proton conductivity of the PA/CBrPBI-X membranes are both enhanced comparing with the pristine PA/PBI. Considering the tradeoff of the mechanical strength and proton conductivity, 10 wt% BrPAEK is demonstrated to be an optimum content in the matrix. For instance, the proton conductivity of PA/CBrPBI-10 is 0.038 S cm-1 at 200 °C, which is higher than that of pristine PA/PBI with the proton conductivity of 0.029 S cm-1 at the same temperature. Other properties of the cross-linked membranes are also investigated in detail, including the oxidative stability, solubility and thermal stability. All the results indicate that the PA/CBrPBI-10 membrane has the potential application in HT-PEMFCs.

  8. Nanoscale confinement effects on the relaxation dynamics in networks of diglycidyl ether of bisphenol-A and low-molecular-weight poly(ethylene oxide).

    PubMed

    Kalogeras, Ioannis M; Stathopoulos, Andreas; Vassilikou-Dova, Aglaia; Brostow, Witold

    2007-03-22

    Thermoplastic poly(ethylene oxide) (PEO) (Mw(PEO) approximately 4000) has been used to prepare thermosetting nanocomposites incorporating diglycidyl ether of bisphenol A (DGEBA) epoxy oligomer. Blends with various PEO/DGEBA weight ratios were cured using stoichiometric portions of 4,4'-diaminodiphenylmethane. The resulting semi-interpenetrating polymer networks were studied by several techniques. Nanoscale confinement effects, thermal (glass transition, melting and crystallization temperatures) and structural features of our materials are similar to those for networks with much higher Mw(PEO) and different curing agents; however, the polyether crystallization onset occurs in our case at a lower PEO concentration; shorter PEO chains organize themselves more easily into crystalline domains. Very low estimates of the k parameter of the Gordon-Taylor equation, used to fit the compositional dependences of the dielectric and calorimetric glass transition temperatures, and a strong plasticization of the motion of the glyceryl segments (beta-relaxation) in the epoxy resin were observed. These illustrate an intensified weakening in the strength of the intermolecular interactions in the modified networks, as compared to the high strength of the self-association of hydroxyls in the neat resin. The significance of hydrogen-bonding interactions between the components for obtaining structurally homogeneous thermoset-i-thermoplastic networks is discussed.

  9. Photoinduced Iron-Based Water-Induced Phase Separable Catalysis (WPSC) ICAR ATRP of Poly(ethylene glycol) Methyl Ether Methacrylate.

    PubMed

    Wu, Jian; Zhang, Bingjie; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2017-06-01

    Iron-mediated atom transfer radical polymerization (ATRP) has gained extensive attention because of the superiority of iron catalysts, such as low toxicity, abundant reserves, and good biocompatibility. Herein, a practical iron catalyst recycling system, photoinduced iron-based water-induced phase separable catalysis ATRP with initiators for continuous activator regeneration, at room temperature is developed for the first time. In this polymerization system, the polymerization is conducted in homogenous solvents consisting of p-xylene and ethanol, using commercially available 5,10,15,20-tetraphenyl-21H,23H-porphine iron(III) chloride as the iron catalyst, ethyl 2-bromophenylacetate as the ATRP initiator, 2,4,6-trimethylbenzoyl diphenylphosphine oxide as the photoinitiator, and poly(ethylene glycol) methyl ether methacrylate as the model hydrophilic monomer. After polymerization, a certain amount of water is added to induce the phase separation so that the catalyst can be separated and recycled in p-xylene phase with very low residual metal complexes (<12 ppm) in the resultant polymers even after six times recycle experiments. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Remarkable reduction of irreversible fouling and improvement of the permeation properties of poly(ether sulfone) ultrafiltration membranes by blending with pluronic F127.

    PubMed

    Wang, Yan-qiang; Wang, Ting; Su, Yan-lei; Peng, Fu-bing; Wu, Hong; Jiang, Zhong-yi

    2005-12-06

    Hydrophilic modification of ultrafiltration membranes was achieved through blending of Pluronic F127 with poly(ether sulfone) (PES). The chemical composition and morphology changes of the membrane surface were confirmed by water contact angle, X-ray photoelectron spectroscopy, scanning electron microscopy, and protein adsorption measurements. The decreased static water contact angle with an increase in the Pluronic F127 content indicated an increase of surface hydrophilicity. XPS analysis revealed enrichment of PEO segments of Pluronic F127 at the membrane surface. The apparent protein adsorption amount decreased significantly from 56.2 to 0 microg/cm(2) when the Pluronic F127 content varied from 0% to 10.5%, which indicated that the blend membrane had an excellent ability to resist protein adsorption. The ultrafiltration experiments revealed that the Pluronic F127 content had little influence on the protein rejection ratio and pure water flux. Most importantly, at a high Pluronic F127 content membrane fouling, especially irreversible fouling, has been remarkably reduced. The flux recoveries of blend membranes reached as high as 90% after periodic cleaning in three cycles.

  11. Chemical modification of wheat protein-based natural polymers: grafting and cross-linking reactions with poly(ethylene oxide) diglycidyl ether and ethyl diamine.

    PubMed

    Kurniawan, Lusiana; Qiao, Greg G; Zhang, Xiaoqing

    2007-09-01

    Mobile poly(ethylene oxide) diglycidyl ether (PEODGE) segments were chemically grafted onto a soluble wheat protein (WP), and different network structures were formed via coupling reactions with ethyl diamine (EDA) in different PEODGE/EDA (PE) ratios. When the PE ratio was 1:1, linear PEs were the predominant segments grafted onto WP chains and the whole WP-PEODGE-EDA (WPE) system was still soluble with an increased molecular weight. Reducing the amount of EDA in the systems produced insoluble cross-linked WPE networks. The broad distribution of network structures and chain mobility resulted in a broad glass transition for the WPE materials. However, the glass transition started at lower temperatures, and the materials became flexible at room temperature. The PE segments were present in all rigid, intermediate, and mobile phases in WPE networks, while the proportion of mobile WP chains was increased as a result of the plasticization effect from the mobile PE segments. The mobility of the most mobile component lipid was also restricted to some extent when forming the cross-linked WPE networks. The study demonstrated that the formation of different network structures with PE segments could significantly improve the flexibility of WP materials, vary the solubility, and modify the mechanical performance of WP-based natural polymer materials.

  12. Aluminum-phthalocyanine chloride associated to poly(methyl vinyl ether-co-maleic anhydride) nanoparticles as a new third-generation photosensitizer for anticancer photodynamic therapy.

    PubMed

    Muehlmann, Luis Alexandre; Ma, Beatriz Chiyin; Longo, João Paulo Figueiró; Almeida Santos, Maria de Fátima Menezes; Azevedo, Ricardo Bentes

    2014-01-01

    Photodynamic therapy is generally considered to be safer than conventional anticancer therapies, and it is effective against different kinds of cancer. However, its clinical application has been significantly limited by the hydrophobicity of photosensitizers. In this work, a system composed of the hydrophobic photosensitizer aluminum-phthalocyanine chloride (AlPc) associated with water dispersible poly(methyl vinyl ether-co-maleic anhydride) nanoparticles is described. AlPc was associated with nanoparticles produced by a method of solvent displacement. This system was analyzed for its physicochemical characteristics, and for its photodynamic activity in vitro in cancerous (murine mammary carcinoma cell lineage 4T1, and human mammary adenocarcinoma cells MCF-7) and noncancerous (murine fibroblast cell lineage NIH/3T3, and human mammary epithelial cell lineage MCF-10A) cell lines. Cell viability and the elicited mechanisms of cell death were evaluated after the application of photodynamic therapy. This system showed improved photophysical and photochemical properties in aqueous media in comparison to the free photosensitizer, and it was effective against cancerous cells in vitro.

  13. Luteinizing hormone-releasing hormone targeted poly(methyl vinyl ether maleic acid) nanoparticles for doxorubicin delivery to MCF-7 breast cancer cells.

    PubMed

    Varshosaz, Jaleh; Jahanian-Najafabadi, Ali; Ghazzavi, Jila

    2016-08-01

    The purpose of this study was to design a targeted anti-cancer drug delivery system for breast cancer. Therefore, doxorubicin (DOX) loaded poly(methyl vinyl ether maleic acid) nanoparticles (NPs) were prepared by ionic cross-linking method using Zn(2+) ions. To optimise the effect of DOX/polymer ratio, Zn/polymer ratio, and stirrer rate a full factorial design was used and their effects on particle size, zeta potential, loading efficiency (LE, %), and release efficiency in 72 h (RE72, %) were studied. Targeted NPs were prepared by chemical coating of tiptorelin/polyallylamin conjugate on the surface of NPs by using 1-ethyl-3-(3-dimethylaminopropyl) carboiimid HCl as cross-linking agent. Conjugation efficiency was measured by Bradford assay. Conjugated triptorelin and targeted NPs were studied by Fourier-transform infrared spectroscopy (FTIR). The cytotoxicity of DOX loaded in targeted NPs and non-targeted ones were studied on MCF-7 cells which overexpress luteinizing hormone-releasing hormone (LHRH) receptors and SKOV3 cells as negative LHRH receptors using Thiazolyl blue tetrazolium bromide assay. The best results obtained from NPs prepared by DOX/polymer ratio of 5%, Zn/polymer ratio of 50%, and stirrer rate of 960 rpm. FTIR spectrum confirmed successful conjugation of triptorelin to NPs. The conjugation efficiency was about 70%. The targeted NPs showed significantly less IC50 for MCF-7 cells compared to free DOX and non-targeted NPs.

  14. High Dielectric Constants of Composites of Fiber-Like Copper Phthalocyanine-Coated Graphene Oxide Embedded in Poly(arylene Ether Nitriles)

    NASA Astrophysics Data System (ADS)

    Li, Jingwei; Pu, Zejun; Wang, Zicheng; Long, Ya; Jia, Kun; Liu, Xiaobo

    2015-07-01

    The surfaces of graphene oxide (GO) sheets were coated with fiber-like copper phthalocyanine (CuPc) by use of a solvothermal process. The product, GO@ CuPc, was used as a filler in high-performance poly(arylene ether nitrile) (PEN) composites. Films of the composites had high thermal stability, and glass-transition temperatures in the range 170-182°C. Thermogravimetric analysis revealed their initial decomposition temperatures were in the range 470-483°C. Scanning electron microscopy showed that dispersion of GO@ CuPc in PEN was much better than that of unmodified GO; this can be attributed to relatively strong interaction between GO@CuPc and the PEN matrix. All the composite films were highly flexible and had enhanced mechanical properties. Tensile strengths of the composites were as high as 89 MPa in the presence of 1 wt.% GO@CuPc, an increase of 20% compared with pure PEN film. Dielectric constants of the composite films were as high as 52 at 100 Hz when the GO@CuPc content was 5%. Because of these excellent mechanical and dielectric properties, PEN/GO@CuPc composites have much potential for use as film capacitors.

  15. Aluminum–phthalocyanine chloride associated to poly(methyl vinyl ether-co-maleic anhydride) nanoparticles as a new third-generation photosensitizer for anticancer photodynamic therapy

    PubMed Central

    Muehlmann, Luis Alexandre; Ma, Beatriz Chiyin; Longo, João Paulo Figueiró; Almeida Santos, Maria de Fátima Menezes; Azevedo, Ricardo Bentes

    2014-01-01

    Photodynamic therapy is generally considered to be safer than conventional anticancer therapies, and it is effective against different kinds of cancer. However, its clinical application has been significantly limited by the hydrophobicity of photosensitizers. In this work, a system composed of the hydrophobic photosensitizer aluminum–phthalocyanine chloride (AlPc) associated with water dispersible poly(methyl vinyl ether-co-maleic anhydride) nanoparticles is described. AlPc was associated with nanoparticles produced by a method of solvent displacement. This system was analyzed for its physicochemical characteristics, and for its photodynamic activity in vitro in cancerous (murine mammary carcinoma cell lineage 4T1, and human mammary adenocarcinoma cells MCF-7) and noncancerous (murine fibroblast cell lineage NIH/3T3, and human mammary epithelial cell lineage MCF-10A) cell lines. Cell viability and the elicited mechanisms of cell death were evaluated after the application of photodynamic therapy. This system showed improved photophysical and photochemical properties in aqueous media in comparison to the free photosensitizer, and it was effective against cancerous cells in vitro. PMID:24634582

  16. Preparation and characterization of mucoadhesive nanoparticles of poly (methyl vinyl ether-co-maleic anhydride) containing glycyrrhizic acid intended for vaginal administration.

    PubMed

    Aguilar-Rosas, Irene; Alcalá-Alcalá, Sergio; Llera-Rojas, Viridiana; Ganem-Rondero, Adriana

    2015-01-01

    Traditional vaginal preparations reside in the vaginal cavity for relatively a short period of time, requiring multiple doses in order to attain the desired therapeutic effect. Therefore, mucoadhesive systems appear to be appropriate to prolong the residence time in the vaginal cavity. In the current study, mucoadhesive nanoparticles based on poly(methyl vinyl ether-co-maleic anhydride) (PVM/MA) intended for vaginal delivery of glycyrrhizic acid (GA) (a drug with well-known antiviral properties) were prepared and characterized. Nanoparticles were generated by a solvent displacement method. Incorporation of GA was performed during nanoprecipitation, followed by adsorption of drug once nanoparticles were formed. The prepared nanoparticles were characterized in terms of size, Z-potential, morphology, drug loading, interaction of GA with PVM/MA (by differential scanning calorimetry) and the in vitro interaction of nanoparticles with pig mucin (at two pH values, 3.6 and 5; with and without GA adsorbed). The preparation method led to nanoparticles of a mean diameter of 198.5 ± 24.3 nm, zeta potential of -44.8 ± 2.8 mV and drug loading of 15.07 ± 0.86 µg/mg polymer. The highest mucin interaction resulted at pH 3.6 for nanoparticles without GA adsorbed. The data obtained suggest the promise of using mucoadhesive nanoparticles of PVM/MA for intravaginal delivery of GA.

  17. Effect of fluorene groups on the properties of multiblock poly(arylene ether sulfone)s-based anion-exchange membranes.

    PubMed

    Xu, Pei Yu; Zhou, Ke; Han, Guang Lu; Zhang, Qiu Gen; Zhu, Ai Mei; Liu, Qing Lin

    2014-05-14

    Two kinds of novel multiblock poly(arylene ether sulfone)s were synthesized via block copolycondensation of telechelic oligomers as a starting material for the preparation of anion-exchange membranes (AEMs). The as-synthesized copolymers have extremely similar main chains. The difference is that the benzylmethyl groups for one are located on the fluorene-sulfone segments and they are located on the isopropylidene-sulfone segments for the other. The benzylmethyl moieties served as precursors to cationic sites and were brominated using N-bromosuccinimide (NBS) and then quaternized with N,N,N',N'-tetramethyl-1,6-diaminohexane (TMHDA). Controlled bromination and quaternization at specific positions of the benzylmethy-containing fluorene-sulfone segments and isopropylidene-sulfone segments can be achieved. 1H NMR spectroscopy, Fourier transform infrared spectroscopy, and gel permeation chromatography were used to characterize the as-synthesized copolymers. Distinct microphase separation in the as-prepared AEMs was observed using small-angle X-ray scattering and transmission electron microscopy. The AEM containing fluorene-sulfone segments (IEC=1.89 meq·g(-1)) showed higher ionic conductivity and methanol permeability than that containing isopropylidene-sulfone segments (IEC=2.03 meq·g(-1)). Moreover, the former showed better alkaline stability than the latter.

  18. Phase behavior in blends of ethylene oxide-propylene oxide copolymer and poly(ether sulfone) studied by modulated-temperature DSC and NMR relaxometry.

    PubMed

    Van Lokeren, Luk; Gotzen, Nicolaas-Alexander; Pieters, Ronny; Van Assche, Guy; Biesemans, Monique; Willem, Rudolph; Van Mele, Bruno

    2009-01-01

    The state diagram of a blend consisting of a copolymer containing ethylene oxide and propylene oxide, P(EO-ran-PO), and poly(ether sulfone), PES, is constructed by using modulated-temperature differential scanning calorimetry (MTDSC), T(2) NMR relaxometry, and light scattering. The apparent heat capacity signal in MTDSC is used for the characterization of polymer miscibility and morphology development. T(2) NMR relaxometry is used to detect the onset of phase separation, which is in good agreement with the onset of phase separation in the apparent heat capacity from MTDSC and the cloud-point temperature as determined from light scattering. The coexistence curve can be constructed from T(2) values at various temperatures by using a few blends with well-chosen compositions. These T(2) values also allow the detection of the boundary between the demixing zones with and without interference of partial vitrification and are in good agreement with stepwise quasi-isothermal MTDSC heat capacity measurements. Important interphases are detected in the heterogeneous P(EO-ran-PO)/PES blends.

  19. A new poly(phthalazine ether sulfone ketone)-coated fiber for solid-phase microextraction to determine nitroaromatic explosives in aqueous samples.

    PubMed

    Guan, Wenna; Xu, Feng; Liu, Wenmin; Zhao, Jinghong; Guan, Yafeng

    2007-04-13

    A novel polar solid-phase microextraction (SPME) fiber coated with poly(phthalazine ether sulfone ketone) (PPESK) was prepared by immersion precipitation technique. The microstructure of the coating exhibits a sponge-like sublayer supporting a dense cracking shaped top layer (about 1 microm in thickness). This coating shows long lifetime (up to 100 times) and is stable at desorption temperature up to 290 degrees C due to the rigid aromatic rings in chemical structure. We evaluated the extraction-desorption properties of the PPESK fiber for nitroaromatic explosives in aqueous samples. The parameters affecting the extraction were optimized, including extraction temperature and time, salt addition, desorption temperature and time. Limits of detection (LOD), precisions and linear dynamic range for the analysis of explosives by SPME-GC/TSD or ECD were evaluated. Limits of detection of the new fiber was three orders of magnitude lower than those with carbowax/divinylbenzene (CW/DVB), and the relative standard deviation (RSD) of single fiber and fiber-to-fiber were less than 9.3 and 10.4%, respectively. The results demonstrated that the PPESK coating exhibited high extraction efficiency for nitroaromatic compounds due to the pi-pi interaction, dipole-dipole interactions and interactions by polar functional groups. The method was applied to the analysis of nitroaromatic explosives in real aqueous samples including seawater and groundwater samples, with relative recoveries better than 90.7%.

  20. Organic-inorganic crosslinked and hybrid membranes derived from sulfonated poly(arylene ether sulfone)/silica via sol-gel process

    NASA Astrophysics Data System (ADS)

    Feng, Shaoguang; Shang, Yuming; Wang, Yingzi; Xie, Xiaofeng; Mathur, V. K.; Xu, Jingming

    A series of covalently crosslinkable organic-inorganic hybrid membranes have been prepared from sulfonated poly(arylene ether sulfone) (SPAES) with pendant propenyl moiety and various amounts of vinyl substituted silica via sol-gel process which are then thermally crosslinked in the presence of benzoyl peroxide (BPO) initiator. The obtained membranes are characterized in terms of oxidative stability, thermal property, ion exchange capacity (IEC), water uptake, swelling ratio in methanol aqueous solution, proton conductivity, and methanol permeability coefficient. The results indicate that the oxidative stability and thermal stability of the hybrid membranes are improved. Moreover, introduction of silica reduces the water uptake and methanol swelling of membranes. The swelling ratio of membranes in 2 mol L -1 methanol aqueous solution at 80 °C slowly decreases from 26 to 19% with the increase of SiO 2 content from 0 to 12 wt.%. Furthermore, with the increase in silica content, the methanol permeability coefficient of the hybrid membranes decreases at first and then increases. When the silica content reaches 8 wt.%, the methanol permeability coefficient is at the minimum of 6.02 × 10 -7 cm 2 s -1, a 2.64-fold decrease compared with that of the pristine SPAES membrane. Moreover, the proton conductivity is found to be at about 95% of that of pristine polymer at that silica content.

  1. Effects of temperature, packaging and electron beam irradiation processing conditions on the property behaviour of Poly (ether-block-amide) blends.

    PubMed

    Murray, Kieran A; Kennedy, James E; McEvoy, Brian; Vrain, Olivier; Ryan, Damien; Cowman, Richard; Higginbotham, Clement L

    2014-06-01

    The radiation stability of Poly (ether-block-amide) (PEBA) blended with a multifunctional phenolic antioxidant and a hindered amide light stabiliser was examined under various temperatures, packaging and electron beam processing conditions. FTIR revealed that there were slight alterations to the PEBA before irradiation; however, these became more pronounced following irradiation. The effect of varying the temperature, packaging and processing conditions on the resultant PEBA properties was apparent. For example, rheology demonstrated that the structural properties could be enhanced by manipulating the aforementioned criteria. Mechanical testing exhibited less radiation resistance when the PEBA samples were vacuum packed and exposed to irradiation. MFI and AFM confirmed that the melting strength and surface topography could be reduced/increased depending on the conditions employed. From this study it was concluded that virgin PEBA submerged in dry ice with non-vacuum packaging during the irradiation process, provided excellent radiation resistance (20.9% improvement) in contrast to the traditional method. Copyright © 2014. Published by Elsevier B.V.

  2. Pore size and concentration effect of mesoporous silica nanoparticles on the coefficient of thermal expansion and optical transparency of poly(ether sulfone) films.

    PubMed

    Vo, Nhat Tri; Patra, Astam K; Kim, Dukjoon

    2017-01-18

    Mesoporous silica nanoparticles (MSNs) with uniform size (<50 nm) yet with different pore diameters were synthesized, and used as fillers in poly(ether sulfone) (PES) films in order to decrease their coefficient of thermal expansion (CTE) without sacrificing optical transparency. Here, both CTE and optical transparency of the MSN/PES nanocomposite films gradually decreased with increasing MSN concentration. The PES films containing MSNs with larger pores showed the best performance in CTE and optical transparency. While the CTE decreased by 32.3% with increasing MSN content up to 0.5 wt%, the optical transparency decreased by only less than 6.9% because of the small and uniform particle size of less than 50 nm, which minimizes light scattering. This pore size effect is more clearly observed via an annealing process, which enables the polymer chains to slowly move and fill in the free volume in the pores of the MSN, and thus restricts the thermal motion. The effect of the silica nanoparticles was investigated not only on the thermal stability but also on the mechanical stability. We expect the MSNs synthesized in this study to be used as a promising filler to enhance the thermal and mechanical stability of the PES substrate without sacrificing its optical transparency.

  3. Note: Thermal conductivity measurement of individual poly(ether ketone)/carbon nanotube fibers using a steady-state dc thermal bridge method

    NASA Astrophysics Data System (ADS)

    Moon, Jaeyun; Weaver, Keith; Feng, Bo; Gi Chae, Han; Kumar, Satish; Baek, Jong-Beom; Peterson, G. P.

    2012-01-01

    Customized engineered fibers are currently being used extensively in the aerospace and automobile industries due to the ability to "design in" specific engineering characteristics. Understanding the thermal conductivity of these new fibers is critical for thermal management and design optimization. In the current investigation, a steady-state dc thermal bridge method (DCTBM) is developed to measure the thermal conductivity of individual poly(ether ketone) (PEK)/carbon nanotube (CNT) fibers. For non-conductive fibers, a thin platinum layer was deposited on the test articles to serve as the heater and temperature sensor. The effect of the platinum layer on the thermal conductivity is presented and discussed. DCTBM is first validated using gold and platinum wires (25 μm in diameter) over a temperature ranging from room temperature to 400 K with ±11% uncertainty, and then applied to PEK/CNT fibers with diverse CNT loadings. At a 28 wt. % CNT loading, the thermal conductivity of fibers at 390 K is over 27 Wm-1K-1, which is comparable to some engineering alloys.

  4. Thin Poly(Di(Ethylene Glycol)Methyl Ether Methacrylate) Homopolymer Brushes Allow Controlled Adsorption and Desorption of PaTu 8988t Cells.

    PubMed

    Voß, Yvonne; Wassel, Ekram; Jiang, Siyu; Song, Qimeng; Druzhinin, Sergey I; Schönherr, Holger

    2016-10-20

    Poly(di(ethylene glycol)methyl ether methacrylate) (PDEGMA) brushes, which are known to suppress protein adsorption and prevent cell attachment, are reported here to possess interesting and tunable thermoresponsive behavior, if the brush thickness is reduced or the grafting density is altered. PDEGMA brushes with a dry ellipsometric thickness of 5 ± 1 nm can be switched from cell adherent behavior at 37 °C to cell nonadherent at 25 °C. This behavior coincides with the temperature-dependent irreversible adsorption of fibronectin from phosphate saline buffer and proteins present in the cell culture medium, as unveiled by surface plasmon resonance measurements. Unlike for tissue culture polystyrene reference surfaces, swelling of the PDEGMA chains below the lower critical solution temperature results in the absence of paxillin and actin containing cellular filaments responsible for cell attachment. These tunable properties of very thin homopolymer PDEGMA brushes render this system interesting as an alternative thermoresponsive layer for continuous cell culture or enzyme-free cell culture systems.

  5. 40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. 721.10556 Section 721.10556 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers (PMN P-06-450; CAS...

  6. 40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. 721.10558 Section 721.10558 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS...

  7. 40 CFR 721.10558 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. 721.10558 Section 721.10558 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-16-alkyl ethers (PMN P-06-452; CAS...

  8. 40 CFR 721.10556 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. 721.10556 Section 721.10556 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C12-15-alkyl ethers (PMN P-06-450; CAS...

  9. 40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. 721.10557 Section 721.10557 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers (PMN P-06-451; CAS...

  10. 40 CFR 721.10557 - Poly(oxy-1,2-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. 721.10557 Section 721.10557 Protection of...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers. (a) Chemical substance...-ethanediyl), .alpha.- (2-methyl-2-propen-1-yl) -.omega.-hydroxy-,C10-16-alkyl ethers (PMN P-06-451; CAS...

  11. Adverse eff ects of polymeric nanoparticle poly(ethylene glycol)- block-polylactide methyl ether (PEG-b-PLA) on steroid hormone secretion by porcine granulosa cells.

    PubMed

    Scsukova, Sona; Bujnakova, Mlynarcikova A; Kiss, A; Rollerova, E

    2017-04-25

    Development of nanoparticles (NPs) for biomedical applications, including medical imaging and drug delivery, is currently undergoing a dramatic expansion. Diverse effects of different type NPs relating to mammalian reproductive tissues have been demonstrated. Th e objective of this study was to explore the in vitro effects of polymeric nanoparticle poly(ethylene glycol)-blockpolylactide methyl ether (PEG-b-PLA NPs) on functional state and viability of ovarian granulosa cells (GCs), which play an important role in maintaining ovarian function and female fertility. The GCs isolated from porcine ovarian follicles were incubated with the different concentrations of PEG-b-PLA NPs (PEG average Mn=350 g/mol and PLA average Mn=1000 g/mol; 0.2-100 μg/ml) or poly(ethylene glycol) with an average molecular weight of 300 (PEG-300; 0.2- 40 mg/ml) in the presence or absence of stimulators, follicle-stimulating hormone (FSH; 1 μg/ml), androstenedione (100 nM), forskolin (10 μM) or 8Br-cAMP (100 μM), for different time periods (24, 48, 72 h). At the end of the incubation, progesterone and estradiol levels produced by GCs were measured in the culture media by radioimmunoassay. Th e viability of GCs was determined by the method using a colorimetric assay with MTT. Treatment of GCs with PEG-b-PLA NPs induced a significant decrease in basal as well as FSH-stimulated progesterone secretion above the concentration of 20 and 4 μg/ml, respectively. Moreover, PEG-b-PLA NPs reduced forskolin-stimulated, but not cAMP-stimulated progesterone production by GCs. A dose-dependent inhibition of androstenedione-stimulated estradiol release by GCs was found by the action of PEG-b-PLA NPs. Incubation of GCs with PEG-300 significantly inhibited basal as well as FSH-stimulated progesterone secretion above the concentration of 40 mg/ml. PEG-b-PLA NPs and PEG-300 significantly reduced the viability of GCs at the highest tested concentrations (100 μg/ml and 40 mg/ml, respectively). The obtained

  12. Effect of extracts of poly(ether imide) microparticles on cytotoxicity, ROS generation and proinflammatory effects on human monocytic (THP-1) cells.

    PubMed

    Kumar, Reddi K; Basu, Sayantani; Lemke, Horst-Dieter; Jankowski, Joachim; Kratz, Karl; Lendlein, Andreas; Tetali, Sarada D

    2016-01-01

    Current haemodialysis techniques are not capable to remove efficiently low molecular weight hydrophobic uremic toxins from the blood of patients suffering from chronic renal failure. With respect to the hydrophobic characteristics and the high level of protein binding of these uremic toxins, hydrophobic adsorber materials might be an alternative to remove these substances from the plasma of the chronic kidney disease (CKD) patients. Here nanoporous microparticles prepared from poly(ether imide) (PEI) with an average diameter of 90 ± 30 μm and a porosity around 88 ± 2% prepared by a spraying/coagulation process are considered as candidate adsorber materials. A prerequisite for the clinical application of such particles is their biocompatibility, which can be examined i.e. indirectly in cell culture experiments with the particles' extracts. In this work we studied the effects of aqueous extracts of PEI microparticles on the viability of THP-1 cells, a human leukemia monocytic cell line, as well as their macrophage differentiation, reactive oxygen species (ROS) generation and inflammation.A high cell viability of around 99 ± 18% and 99 ± 5% was observed when THP-1 cells were cultured in the presence of aqueous extracts of the PEI microparticles in medium A and medium B respectively. The obtained microscopic data suggested that PEI particle extracts have no significant effect on cell death, oxidative stress or differentiation to macrophages. It was further found that the investigated proinflammatory markers in THP-1 cells were not up-regulated. These results are promising with regard to the biocompatibility of PEI microparticles and in a next step the hemocompatibility of the microparticles will be examined.

  13. Dynamic in vitro hemocompatibility testing of poly(ether imide) membranes functionalized with linear, methylated oligoglycerol and oligo(ethylene glycol).

    PubMed

    Braune, Steffen; von Ruesten-Lange, Maik; Mrowietz, Christof; Lützow, Karola; Roch, Toralf; Neffe, Axel T; Lendlein, Andreas; Jung, Friedrich

    2013-01-01

    Linear, side-chain methylated oligoglycerols (OGMe) were recently reported as potential surface passivating molecules for improving the protein resistance of cardiovascular application relevant poly(ether imide) (PEI) membranes. A previously reported in vitro screening under static test conditions allowed an end-point evaluation of the adhesion and activation of adherent thrombocytes performed on the material surfaces and revealed similar levels of thrombogenicity on PEI membranes, functionalized with OGMe and oligo(ethylene glycol) (OEG) of similar molecular weight (Mn = 1,300 g·mol-1 - 1,800 g·mol-1). In the present study, we investigated the hemocompatibility of these materials in a dynamic closed loop system, in order to study time-dependent thrombocyte material interactions also of the circulating thrombocytes by mimicking in vivo relevant flow conditions in a dynamic test system with multiple material contacts. Activation and aggregation of circulating thrombocytes as well as complement activation and plasmatic coagulation were evaluated after 40 circulations of thrombocyte rich plasma in the closed loop system. The results of the dynamic tests revealed no differences between the OGMe and OEG functionalized PEI membranes. Furthermore, no differences were observed between the latter and a PEI membrane treated under the conditions of functionalization at pH 11 (PEI-pH11) without an oligoether being present. Blood plasma protein adsorption, as well as activation, and adherence of circulating thrombocytes occurred in a comparable, but minor manner on all investigated PEI membranes. From this we conclude that the OGMe and OEG surface functionalization did not lead to an improvement of the already good hemocompatibility of the PEI-pH11 membrane.

  14. Effects of gamma ray and electron beam irradiation on the mechanical, thermal, structural and physicochemical properties of poly (ether-block-amide) thermoplastic elastomers.

    PubMed

    Murray, Kieran A; Kennedy, James E; McEvoy, Brian; Vrain, Olivier; Ryan, Damien; Cowman, Richard; Higginbotham, Clement L

    2013-01-01

    Both gamma ray and electron beam irradiation are widely used as a means of medical device sterilisation. However, it is known that the radiation produced by both processes can lead to undesirable changes within biomedical polymers. The main objective of this research was to conduct a comparative study on the two key radiosterilisation methods (gamma ray and electron beam) in order to identify the more detrimental process in terms of the mechanical, structural, chemical and thermal properties of a common biomedical grade polymer. Poly (ether-block-amide) (PEBA) was prepared by injection moulding ASTM testing specimens and these were exposed to an extensive range of irradiation doses (5-200 kGy) in an air atmosphere. The effect of varying the irradiation dose concentration on the resultant PEBA properties was apparent. For instance, the tensile strength, percentage elongation at break and shore D hardness can be increased/decreased by controlling the aforementioned criteria. In addition, it was observed that the stiffness of the material increased with incremental irradiation doses as anticipated. Melt flow index demonstrated a dramatic increase in the melting strength of the material indicating a sharp increase in molecular weight. Conversely, modulated differential scanning calorimetry established that there were no significant alterations to the thermal transitions. Noteworthy trends were observed for the dynamic frequency sweeps of the material, where the crosslink density increased according to an increase in electron beam irradiation dose. Trans-vinylene unsaturations and the carbonyl group concentration increased with an increment in irradiation dose for both processes when observed by FTIR. The relationship between the irradiation dose rate, mechanical properties and the subsequent surface properties of PEBA material is further elucidated throughout this paper. This study revealed that the gamma irradiation process produced more adverse effects in the PEBA

  15. Unexpected behavior of ultra-thin films of blends of polystyrene/poly(vinyl methyl ether) studied by specific heat spectroscopy.

    PubMed

    Madkour, Sherif; Szymoniak, Paulina; Schick, Christoph; Schönhals, Andreas

    2017-05-28

    Specific heat spectroscopy (SHS) employing AC nanochip calorimetry was used to investigate the glassy dynamics of ultra-thin films (thicknesses: 10 nm-340 nm) of a polymer blend, which is miscible in the bulk. In detail, a Poly(vinyl methyl ether) (PVME)/Polystyrene (PS) blend with the composition of 25/75 wt. % was studied. The film thickness was controlled by ellipsometry while the film topography was checked by atomic force microscopy. The results are discussed in the framework of the balance between an adsorbed and a free surface layer on the glassy dynamics. By a self-assembling process, a layer with a reduced mobility is irreversibly adsorbed at the polymer/substrate interface. This layer is discussed employing two different scenarios. In the first approach, it is assumed that a PS-rich layer is adsorbed at the substrate. Whereas in the second approach, a PVME-rich layer is suggested to be formed at the SiO2 substrate. Further, due to the lower surface tension of PVME, with respect to air, a nanometer thick PVME-rich surface layer, with higher molecular mobility, is formed at the polymer/air interface. By measuring the glassy dynamics of the thin films of PVME/PS in dependence on the film thickness, it was shown that down to 30 nm thicknesses, the dynamic Tg of the whole film was strongly influenced by the adsorbed layer yielding a systematic increase in the dynamic Tg with decreasing the film thickness. However, at a thickness of ca. 30 nm, the influence of the mobile surface layer becomes more pronounced. This results in a systematic decrease in Tg with the further decrease of the film thickness, below 30 nm. These results were discussed with respect to thin films of PVME/PS blend with a composition of 50/50 wt. % as well as literature results.

  16. Unveiling the Dynamics of Self-Assembled Layers of Thin Films of Poly(vinyl methyl ether) (PVME) by Nanosized Relaxation Spectroscopy.

    PubMed

    Madkour, Sherif; Szymoniak, Paulina; Heidari, Mojdeh; von Klitzing, Regine; Schönhals, Andreas

    2017-03-01

    A combination of nanosized dielectric relaxation (BDS) and thermal spectroscopy (SHS) was utilized to characterize the dynamics of thin films of poly(vinyl methyl ether) (PVME) (thicknesses: 7-160 nm). For the BDS measurements, a recently designed nanostructured electrode system is employed. A thin film is spin-coated on an ultraflat highly conductive silicon wafer serving as the bottom electrode. As top electrode, a highly conductive wafer with nonconducting nanostructured SiO2 nanospacers with heights of 35 or 70 nm is assembled on the bottom electrode. This procedure results in thin supported films with a free polymer/air interface. The BDS measurements show two relaxation processes, which are analyzed unambiguously for thicknesses smaller than 50 nm. The relaxation rates of both processes have different temperature dependencies. One process coincides in its position and temperature dependence with the glassy dynamics of bulk PVME and is ascribed to the dynamic glass transition of a bulk-like layer in the middle of the film. The relaxation rates were found to be thickness independent as confirmed by SHS. Unexpectedly, the relaxation rates of the second process obey an Arrhenius-like temperature dependence. This process was not observed by SHS and was related to the constrained fluctuations in a layer, which is irreversibly adsorbed at the substrate with a heterogeneous structure. Its molecular fluctuations undergo a confinement effect resulting in the localization of the segmental dynamics. To our knowledge, this is the first report on the molecular dynamics of an adsorbed layer in thin films.

  17. Influence of N-phthaloyl chitosan on poly (ether imide) ultrafiltration membranes and its application in biomolecules and toxic heavy metal ion separation and their antifouling properties

    NASA Astrophysics Data System (ADS)

    Kanagaraj, P.; Nagendran, A.; Rana, D.; Matsuura, T.; Neelakandan, S.; Karthikkumar, T.; Muthumeenal, A.

    2015-02-01

    N-phthaloyl chitosan (NPHCs), which could be dissolved in various organic solvents, is synthesized for the modification of poly (ether imide) (PEI) ultrafiltration membrane. Blend membrane with 2 wt% NPHCs exhibited higher pure water flux (112.2 l m-2 h-1), higher water content (63.4%) and lower hydraulic resistance (3 kPa/l m-2 h-1). The top surface morphology of the control PEI membrane changed from a dense surface to visible pores with the increase in NPHCs concentration. The surface roughness of PEI membranes increased with an increase in NPHCs concentration in the casting solution. Application studies were carried out to find the rejection and permeate flux of proteins such as bovine serum albumin (BSA), egg albumin (EA), pepsin and trypsin and toxic heavy metal ions such as Cr(III), Zn(II), Cd(II) and Pb(II). The result shows that the flux and separation performances are dependent upon the content of NPHCs. Furthermore, the blend membranes were subjected to the determination of pore statistics and MWCO. It was found that the blending of NPHCs into the PEI membrane had a visible effect upon MWCO and pore size. The significant effect of hydrophilicity of NPHCs on the fouling of PEI/NPHCs blend membranes by BSA was also discussed. It was found that the blend membranes with 2 wt% NPHCs content had a higher FRR (88.6%), higher reversible fouling (23.7%) and lower irreversible fouling (11.4%) which explained their improved antifouling properties. Thus, the modified chitosan proved to play an important role in the improvement of UF membrane performance.

  18. Unexpected behavior of ultra-thin films of blends of polystyrene/poly(vinyl methyl ether) studied by specific heat spectroscopy

    NASA Astrophysics Data System (ADS)

    Madkour, Sherif; Szymoniak, Paulina; Schick, Christoph; Schönhals, Andreas

    2017-05-01

    Specific heat spectroscopy (SHS) employing AC nanochip calorimetry was used to investigate the glassy dynamics of ultra-thin films (thicknesses: 10 nm-340 nm) of a polymer blend, which is miscible in the bulk. In detail, a Poly(vinyl methyl ether) (PVME)/Polystyrene (PS) blend with the composition of 25/75 wt. % was studied. The film thickness was controlled by ellipsometry while the film topography was checked by atomic force microscopy. The results are discussed in the framework of the balance between an adsorbed and a free surface layer on the glassy dynamics. By a self-assembling process, a layer with a reduced mobility is irreversibly adsorbed at the polymer/substrate interface. This layer is discussed employing two different scenarios. In the first approach, it is assumed that a PS-rich layer is adsorbed at the substrate. Whereas in the second approach, a PVME-rich layer is suggested to be formed at the SiO2 substrate. Further, due to the lower surface tension of PVME, with respect to air, a nanometer thick PVME-rich surface layer, with higher molecular mobility, is formed at the polymer/air interface. By measuring the glassy dynamics of the thin films of PVME/PS in dependence on the film thickness, it was shown that down to 30 nm thicknesses, the dynamic Tg of the whole film was strongly influenced by the adsorbed layer yielding a systematic increase in the dynamic Tg with decreasing the film thickness. However, at a thickness of ca. 30 nm, the influence of the mobile surface layer becomes more pronounced. This results in a systematic decrease in Tg with the further decrease of the film thickness, below 30 nm. These results were discussed with respect to thin films of PVME/PS blend with a composition of 50/50 wt. % as well as literature results.

  19. Ionic-liquid-mediated poly(dimethylsiloxane)- grafted carbon nanotube fiber prepared by the sol-gel technique for the head space solid-phase microextraction of methyl tert-butyl ether using GC.

    PubMed

    Vatani, Hossein; Yazdi, Ali Sarafraz

    2014-01-01

    A headspace solid-phase microextraction method was developed for the preconcentration and extraction of methyl tert-butyl ether. An ionic-liquid-mediated multiwalled carbon nanotube-poly(dimethylsiloxane) hybrid coating, which was prepared by covalent functionalization of multiwalled carbon nanotubes with hydroxyl-terminated poly(dimethylsiloxane) using the sol-gel technique, was used as solid-phase microextraction adsorbent. This innovative fiber exhibited a highly porous surface structure, high thermal stability (at least 320°C) and long lifespan (over 210 uses). Potential factors affecting the extraction efficiency were optimized. Under the optimum conditions, the method LOD (S/N = 3) was 0.007 ng/mL and the LOQ (S/N = 10) was 0.03 ng/mL. The calibration curve was linear in the range of 0.03-200 ng/mL. The RSDs for one fiber (repeatability, n = 5) at three different concentrations (0.05, 1, and 150 ng/mL) were 5.1, 4.2, and 4.6% and for the fibers obtained from different batches (reproducibility, n = 3) were 6.5, 5.9, and 6.3%, respectively. The developed method was successfully applied to the determination of methyl tert-butyl ether in different real water samples on three consecutive days. The relative recoveries for the spiked samples with 0.05, 1, and 150 ng/mL were between 94-104%.

  20. Biodegradation of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly{(2-hydroxyethyl methacrylate)-co-[poly(ethylene glycol) methyl ether methacrylate]} hydrogels containing peptide-based cross-linking agents.

    PubMed

    Casadio, Ylenia S; Brown, David H; Chirila, Traian V; Kraatz, Heinz-Bernhard; Baker, Murray V

    2010-11-08

    PHEMA-peptide and P[HEMA-co-(MeO-PEGMA)]-peptide conjugate hydrogels [where PHEMA = poly(2-hydroxyethyl methacrylate; PEGMA = poly(ethylene glycol) methacrylate] were readily prepared via photoinitiated free-radical polymerization in water. The PHEMA-peptide hydrogels were opaque and had a heterogeneous morphology of interconnected polymer droplets, characteristic of polymers that separate from the aqueous phase during the polymerization experiment. The P[HEMA-co-(MeO-PEGMA)]-peptide conjugates were transparent gels with a homogeneous morphology when formed in water, but when formed in aqueous NaCl solutions the P[HEMA-co-(MeO-PEGMA)]-peptide conjugates were also opaque and exhibited the heterogeneous morphology of interconnected polymer droplets. When incubated in solutions containing activated papain, P[HEMA-co-(MeO-PEGMA)]-peptide conjugates underwent degradation that was characterized by macroscopic changes to sample shape and size, sample weight, and microscopic structure. PHEMA-peptide conjugates did not undergo any significant degradation when incubated with papain, although ninhydrin-staining experiments suggested that some peptide cross-linker groups were cleaved during the incubation. The difference in degradation behavior of PHEMA-peptide and P[HEMA-co-(MeO-PEGMA)]-peptide conjugates is attributed to differences in aqueous solubility of PHEMA and P[HEMA-co-(MeO-PEGMA)].

  1. 40 CFR 721.7700 - Poly(oxy-1,2-ethanediyl), α-hydro-ω-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1). 721.7700 Section 721.7700...-propanediol (3:1). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical...-(hydroxymethyl)-1,3-propanediol (3:1) (PMN P-88-2188) is subject to reporting under this section for...

  2. 40 CFR 721.7700 - Poly(oxy-1,2-ethanediyl), α-hydro-ω-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-(oxiranylmethoxy)-, ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (3:1). 721.7700 Section 721.7700...-propanediol (3:1). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical...-(hydroxymethyl)-1,3-propanediol (3:1) (PMN P-88-2188) is subject to reporting under this section for...

  3. Phase transformations in aqueous low molar mass poly(vinyl methyl ether) solutions: theoretical prediction and experimental validation of the peculiar solvent melting line, bimodal LCST, and (adjacent) UCST miscibility gaps.

    PubMed

    Van Durme, Kurt; Van Assche, Guy; Nies, Erik; Van Mele, Bruno

    2007-02-15

    Supported by theoretical predictions based on the Wertheim Lattice Thermodynamic Perturbation Theory, modulated temperature differential scanning calorimetry (MTDSC) was used to further the knowledge of the phase behavior of aqueous poly(vinyl methyl ether) (PVME) solutions. Using a narrowly dispersed low molar mass PVME, we determined the following phase boundaries: (i) a bimodal lower critical solution temperature (LCST) miscibility gap at physiological temperature (around 37 degrees C), (ii) an upper critical solution temperature (UCST) two-phase area at sub-zero temperatures and high polymer concentration, and (iii) the melting line of the solvent across the entire concentration range, showing a peculiar stepwise decrease with composition. The location of the glass transition region and its influence on the crystallization/melting behavior of the solvent is discussed.

  4. Crystalline imide/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor); Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor)

    1995-01-01

    Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

  5. Development of a poly(ether urethane) system for the controlled release of two novel anti-biofilm agents based on gallium or zinc and its efficacy to prevent bacterial biofilm formation.

    PubMed

    Ma, Hongyan; Darmawan, Erica T; Zhang, Min; Zhang, Lei; Bryers, James D

    2013-12-28

    Traditional antibiotic therapy to control medical device-based infections typically fails to clear biofilm infections and may even promote the evolution of antibiotic resistant species. We report here the development of two novel antibiofilm agents; gallium (Ga) or zinc (Zn) complexed with protoporphyrin IX (PP) or mesoprotoporphyrin IX (MP) that are both highly effective in negating suspended bacterial growth and biofilm formation. These chelated gallium or zinc complexes act as iron siderophore analogs, supplanting the natural iron uptake of most bacteria. Poly (ether urethane) (PEU; Biospan®) polymer films were fabricated for the controlled sustained release of the Ga- or Zn-complexes, using an incorporated pore-forming agent, poly(ethylene glycol) (PEG). An optimum formulation containing 8% PEG (MW=1450) in the PEU polymer effectively sustained drug release for at least 3months. All drug-loaded PEU films exhibited in vitro ≥ 90% reduction of Gram-positive (Staphylococcus epidermidis) and Gram-negative (Pseudomonas aeruginosa) bacteria in both suspended and biofilm culture versus the negative control PEU films releasing nothing. Cytotoxicity and endotoxin evaluation demonstrated no adverse responses to the Ga- or Zn-complex releasing PEU films. Finally, in vivo studies further substantiate the anti-biofilm efficacy of the PEU films releasing Ga- or Zn- complexes. © 2013.

  6. Development of a poly (ether urethane) system for the controlled release of two novel anti-biofilm agents based on gallium or zinc and its efficacy to prevent bacterial biofilm formation

    PubMed Central

    Ma, Hongyan; Darmawan, Erica T.; Zhang, Min; Zhange, Lei; Bryers, James D.

    2013-01-01

    Traditional antibiotic therapy to control medical device-based infections typically fails to clear biofilm infections and may even promote the evolution of antibiotic resistant species. We report here the development of two novel antibiofilm agents; gallium (Ga) or zinc (Zn) complexed with protoporphyrin IX (PP) or mesoprotoporphyrin IX (MP) that are both highly effective in negating suspended bacterial growth and biofilm formation. These chelated gallium or zinc complexes act as iron siderophore analogs, surplanting the natural iron uptake of most bacteria. Poly (ether urethane) (PEU; Biospan®) polymer films were fabricated for the controlled sustained release of the Ga- or Zn-complexes, using an incorporated pore-forming agent, poly (ethylene glycol) (PEG). An optimum formulation containing 8% PEG (MW=1450) in the PEU polymer effectively sustained drug release for at least 3 months. All drug-loaded PEU films exhibited in vitro ≥ 90% reduction of Gram-positive (Staphylococcus epidermidis) and Gram-negative (Pseudomonas aeruginosa) bacteria in both suspended and biofilm culture versus the negative control PEU films releasing nothing. Cytotoxicity and endotoxin evaluation demonstrated no adverse responses to the Ga- or Zn-complex releasing PEU films. Finally, in vivo studies further substantiate the anti-biofilm efficacy of the PEU films releasing Ga- or Zn- complexes. PMID:24140747

  7. Nonabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Nonabromodiphenyl ether ; CASRN 63936 - 56 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  8. Pentabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Pentabromodiphenyl ether ; CASRN 32534 - 81 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

  9. Octabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Octabromodiphenyl ether ; CASRN 32536 - 52 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  10. Tribromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Tribromodiphenyl ether ; CASRN 49690 - 94 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarci

  11. Hexabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Hexabromodiphenyl ether ; CASRN 36483 - 60 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  12. Ethyl ether

    Integrated Risk Information System (IRIS)

    Ethyl ether ; CASRN 60 - 29 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  13. Tetrabromodiphenyl ether

    Integrated Risk Information System (IRIS)

    Tetrabromodiphenyl ether ; CASRN 40088 - 47 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

  14. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOEpatents

    Crivello, J.V.

    1996-01-23

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} (V) wherein n is an integer from one to six and A is selected from cyclic ethers, polyether, and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  15. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOEpatents

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  16. Evidence of chemical reactions between di- and poly-glycidyl ether resins and tannins isolated from Pinus radiata D. Don bark.

    PubMed

    Soto, Roy; Freer, Juanita; Baeza, Jaime

    2005-01-01

    This work evaluates the feasibility of reacting tannins isolated from Pinus radiata D. Don bark with epoxide resins of the diglycidyl and polyglycidyl ether type. To this end, gel times of aqueous tannin dispersions (40% w/w) with every one of nine selected resins (5% w/w), at previously established pH values (initial equal to 3.3, 4, 7 and 10), have been determined. Products of these reactions were analyzed by FT-IR spectroscopy, and the results were compared with those obtained from tannin-p-formaldehyde and (+)-catechin-p-formaldehyde systems, at the same pH values. Their mechanical properties were evaluated, by dynamic mechanical analysis, at two pH values (3.3 and 10). In general, it was concluded that tannin-epoxide resin systems behave similarly to tannin-paraformaldehyde systems, especially at basic pH values.

  17. Ion Exchange and Antibiofouling Properties of Poly(ether sulfone) Membranes Prepared by the Surface Immobilization of Brønsted Acidic Ionic Liquids via Double-Click Reactions.

    PubMed

    Yi, Zhuan; Liu, Cui-Jing; Zhu, Li-Ping; Xu, You-Yi

    2015-07-28

    Brønsted acidic ionic liquids (BAILs) are unique ionic liquids that display chemical structures similar to zwitterions, and they were typically used as solvents and catalysts. In this work, an imidazole-based BAIL monolayer was fabricated onto poly(ether sulfone) (PES) membranes via surface clicking reactions, and the multifunctionality, including ion exchange and biofouling resistance to proteins and bacteria, was demonstrated, which was believed to be one of few works in which BAIL had been considered to be a novel fouling resistance layer for porous membranes. The successful immobilization of the BAILs onto a membrane surface was confirmed by X-ray photoelectron spectroscopy analysis, contact angle measurement, and ζ potential determination. The results from Raman spectroscopy showed that, as a decisive step prior to zwitterion, the BAIL was deprotonated in aqueous solution, and biofouling resistance to proteins and bacteria was found. However, BAIL displayed ion exchange ability at lower pH, and surface hydrophilicity/hydrophobicity of membranes could be tuned on purpose. Our results have demonstrated that the BAIL grafted onto membranes will not only act as an antibiofouling barrier like zwitterions but also provide a platform for surface chemical tailoring by ion exchange, the property of which will become especially important in acidic solutions where the fouling resistance performances of zwitterions are greatly weakened.

  18. Phase behavior of the mixtures of poly(oxyethylene) (10) stearyl ether (Brij-76), 1-butanol, isooctane, and mixed polar solvents II. Water and ethylene glycol (EG) or tetraethylene glycol (TEG).

    PubMed

    Nandy, Debdurlav; Mitra, Rajib K; Paul, Bidyut K

    2007-06-01

    The phase diagrams of the pseudo-quaternary systems poly(oxyethylene) (10) stearyl ether (Brij-76)/1-butanol/isooctane/water (with equal amounts of oil and water in the presence of two nonaqueous polar solvents (NPS), ethylene glycol (EG), and tetraethylene glycol (TEG)), have been constructed at 30 degrees C. Regular fish-tail diagrams were obtained up to psi (weight fraction of EG or TEG in the mixture of polar solvents) equal to 0.5, confirming the establishment of hydrophile-lipophile balance (HLB) of the systems. The maximum solubilization capacity passed through a minimum at psi=0.2. No HLB was obtained at higher psi. The usual fish-tail diagrams were also obtained in temperature-induced phase mapping at fixed W(1) (weight fraction of 1-butanol in total amphiphile). Solubilization capacity and HLB temperature (T(HLB)) decreased with increasing psi at a fixed W(1), the effect being more pronounced for TEG than EG. A correlation between HLB temperature (T(HLB)) and HLB number (N(HLB)) of mixed amphiphiles (Brij-76+Bu) in pseudo-quaternary systems (in the presence of water and partial substitution of water with both NPS) has been established. The novelty of the work with respect to possible applications has been discussed.

  19. System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers.

    PubMed

    Moultos, Othonas A; Zhang, Yong; Tsimpanogiannis, Ioannis N; Economou, Ioannis G; Maginn, Edward J

    2016-08-21

    Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

  20. System-size corrections for self-diffusion coefficients calculated from molecular dynamics simulations: The case of CO2, n-alkanes, and poly(ethylene glycol) dimethyl ethers

    NASA Astrophysics Data System (ADS)

    Moultos, Othonas A.; Zhang, Yong; Tsimpanogiannis, Ioannis N.; Economou, Ioannis G.; Maginn, Edward J.

    2016-08-01

    Molecular dynamics simulations were carried out to study the self-diffusion coefficients of CO2, methane, propane, n-hexane, n-hexadecane, and various poly(ethylene glycol) dimethyl ethers (glymes in short, CH3O-(CH2CH2O)n-CH3 with n = 1, 2, 3, and 4, labeled as G1, G2, G3, and G4, respectively) at different conditions. Various system sizes were examined. The widely used Yeh and Hummer [J. Phys. Chem. B 108, 15873 (2004)] correction for the prediction of diffusion coefficient at the thermodynamic limit was applied and shown to be accurate in all cases compared to extrapolated values at infinite system size. The magnitude of correction, in all cases examined, is significant, with the smallest systems examined giving for some cases a self-diffusion coefficient approximately 15% lower than the infinite system-size extrapolated value. The results suggest that finite size corrections to computed self-diffusivities must be used in order to obtain accurate results.

  1. Delayed adverse effects of neonatal exposure to polymeric nanoparticle poly(ethylene glycol)-block-polylactide methyl ether on hypothalamic-pituitary-ovarian axis development and function in Wistar rats.

    PubMed

    Rollerova, Eva; Jurcovicova, Jana; Mlynarcikova, Alzbeta; Sadlonova, Irina; Bilanicova, Dagmar; Wsolova, Ladislava; Kiss, Alexander; Kovriznych, Jevgenij; Kronek, Juraj; Ciampor, Fedor; Vavra, Ivo; Scsukova, Sona

    2015-11-01

    We studied delayed effects of neonatal exposure to polymeric nanoparticle poly(ethylene glycol)-block-polylactide methyl ether (PEG-b-PLA) on the endpoints related to pubertal development and reproductive function in female Wistar rats from postnatal day 4 (PND4) to PND 176. Female pups were injected intraperitoneally, daily, from PND4 to PND7 with PEG-b-PLA (20 or 40mg/kg b.w.). Both doses of PEG-b-PLA accelerated the onset of vaginal opening compared with the control group. In the low-dose PEG-b-PLA-treated group, a significantly reduced number of regular estrous cycles, increased pituitary weight due to hyperemia, vascular dilatation and congestion, altered course of hypothalamic gonadotropin-releasing hormone-stimulated luteinizing hormone secretion, and increased progesterone serum levels were observed. The obtained data indicate that neonatal exposure to PEG-b-PLA might affect the development and function of hypothalamic-pituitary-ovarian axis (HPO), and thereby alter functions of the reproductive system in adult female rats. Our study indicates a possible neuroendocrine disrupting effect of PEG-b-PLA nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    SciTech Connect

    McGrath, James E.; Baird, Donald G.

    2010-06-03

    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and

  3. Functional polyester materials with tunable degradability: Investigations into the use of reductive amination, ketoxime ether, and hydrazone linkages for functionalization, covalent stabilization and crosslinking of poly(epsilon-caprolactone) materials

    NASA Astrophysics Data System (ADS)

    van Horn, Brooke Angela

    Aliphatic polyesters represent one class of degradable, polymeric materials that is receiving significant attention in the search for, and design of, biocompatible and bioresorbable synthetic substances. Functional and crosslinked polyesters, having potential biomedical value, are the target of many avenues of current research. This dissertation work expands the utility of a specific aliphatic polyester, poly(epsilon-caprolactone-co-2-oxepane-1,5-dione) (P(CL-co-OPD)), which contains backbone ketone units that can be reacted with various functional, nucleophilic agents. Results presented in this dissertation convey both the successes had and the challenges encountered in the employment of different "iminyl" chemistries for the synthesis of functional and crosslinked materials. Specifically, the ketone-functionalized polyester was investigated as a general substrate designed to undergo solution-state intramolecular crosslinking and functionalization upon reductive amination with 1,6-hexanediamine and hexylamine, respectively, in the presence of NaCNBH3. Through detailed analysis of the products from these reactions, and simpler systems including small molecule model compounds, the polymeric gamma-keto ester functionality was determined to be incompatible with the reductive amination chemistry, resulting in chain cleavage via intramolecular lactam formation. Subsequent investigation of ketoxime ether formation using synthetic model hydroxylamines, 1-aminooxydodecane and 1,6-bis(aminooxy)hexane, in solution and in the presence of an acid catalyst, resulted in the targeted graft and crosslinked particulate/gel materials, respectively. With the significant interest in the development of synthetic polymer materials of increasing degrees of complexity, attention has been focused on the efficient and high-yielding conversion of polyesters into multi-functional materials. Facile conjugation of aminooxy- and sulfonyl hydrazide model ligands with P(CL-co-OPD) were also

  4. Crown ethers in graphene

    DOE PAGES

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; ...

    2014-11-13

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basicmore » structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.« less

  5. Crown ethers in graphene

    SciTech Connect

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I.; Gallego, Nidia C.; Pantelides, Sokrates T.; Pennycook, Stephen J.; Moyer, Bruce A.; Chisholm, Matthew F.

    2014-11-13

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.

  6. Crown ethers in graphene.

    PubMed

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I; Gallego, Nidia C; Pantelides, Sokrates T; Pennycook, Stephen J; Moyer, Bruce A; Chisholm, Matthew F

    2014-11-13

    Crown ethers are at their most basic level rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted attention for their ability to selectively incorporate various atoms or molecules within the cavity formed by the ring. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity. Here we present atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar. First-principles calculations show that the close similarity of the structures should also extend to their selectivity towards specific metal cations. Crown ethers in graphene offer a simple environment that can be systematically tested and modelled. Thus, we expect that our finding will introduce a new wave of investigations and applications of chemically functionalized graphene.

  7. Molecular Dynamics Study of Self-Assembly of Aqueous Solutions of Poly[9,9-bis(4-Sulfonylbutoxyphenylphenyl) Fluorene-2,7-diyl-2,2’-Bithiophene] (PBS-PF2T) in the Presence of Pentaethylene Glycol Monododecyl Ether (C12E5)

    PubMed Central

    Stewart, Beverly; Burrows, Hugh Douglas

    2016-01-01

    Results are presented using molecular dynamics (MD) of the self-assembly of the conjugated polyelectrolyte poly[9,9-bis(4-sulfonylbutoxyphenylphenyl) fluorene-2,7-diyl-2,2’-bithiophene] (PBS-PF2T) with 680 mM pentaethylene glycol monododecyl ether (C12E5) in water. Simulations are used to examine the interaction between PBS-PF2T and C12E5 and suggest a break-up of PBS-PF2T aggregates in solution. These systems are dominated by the formation of cylindrical phases at temperatures between 0 °C and 20 °C and also between 45 °C and 90 °C. More diffuse phases are seen to occur between 20 °C and 45 °C and also above 90 °C. Simulations are related to previous computational and experimental studies on PBS-PF2T aggregation in the presence of tetraethylene glycol monododecyl ether (C12E4) in bulk and thin films. PMID:28773506

  8. Catalytic oxidation of dimethyl ether

    SciTech Connect

    Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

    2016-05-10

    A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

  9. Poly(arylene)-based anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Bae, Chulsung

    2015-06-09

    Poly(arylene) electrolytes including copolymers lacking ether groups in the polymer may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  10. Cationic Polymerization of Vinyl Ethers Controlled by Visible Light.

    PubMed

    Kottisch, Veronika; Michaudel, Quentin; Fors, Brett P

    2016-12-07

    Photoinitiated cationic polymerizations are widely used in industrial processes; however, gaining photocontrol over chain growth would expand the utility of these methods and facilitate the design of novel complex architectures. We report herein a cationic polymerization regulated by visible light. This polymerization proceeds under mild conditions: a combination of a metal-free photocatalyst, a chain-transfer agent, and light irradiation enables the synthesis of various poly(vinyl ether)s with good control over molecular weight and dispersity as well as excellent chain-end fidelity. Significantly, photoreversible cation formation in this system enables efficient control over polymer chain growth with light.

  11. Triethylene glycol monoethyl ether

    Integrated Risk Information System (IRIS)

    Triethylene glycol monoethyl ether ; CASRN 112 - 50 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  12. Triethylene glycol monobutyl ether

    Integrated Risk Information System (IRIS)

    Triethylene glycol monobutyl ether ; CASRN 143 - 22 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  13. p-Bromodiphenyl ether

    Integrated Risk Information System (IRIS)

    p - Bromodiphenyl ether ; CASRN 101 - 55 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcin

  14. Propylene glycol monoethyl ether

    Integrated Risk Information System (IRIS)

    Propylene glycol monoethyl ether ; CASRN 52125 - 53 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  15. Chloromethyl methyl ether (CMME)

    Integrated Risk Information System (IRIS)

    Chloromethyl methyl ether ( CMME ) ; CASRN 107 - 30 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  16. Glycol Ethers As Groundwater Contaminants

    NASA Astrophysics Data System (ADS)

    Ross, Benjamin; Johannson, Gunnar; Foster, Gregory D.; Eckel, William P.

    1992-01-01

    Ether derivatives of dihydroxy alcohols, which are formed from ethylene or propylene, comprise an important group of groundwater contaminants known as glycol ethers. Compounds in this group are used as solvents, cleaning agents, and emulsifiers in many chemical products and manufacturing operations. Glycol ethers have been associated with a variety of toxic effects, and some compounds in the group are relatively potent teratogens. The limited information available suggests that glycol ethers are contaminants in groundwater, especially in anaerobic plumes emanating from disposal of mixed industrial and household waste. Most methods used to analyze groundwater samples cannot adequately detect μg/? (ppb) concentrations of glycol ethers, and the existing methods perform worst for the most widely used and toxic species. A new method capable of analyzing μg/? concentrations of glycol ethers was recently developed, and its use is recommended for groundwater samples where glycol ethers are likely to be present.

  17. Aliphatic polycarbonates based on carbon dioxide, furfuryl glycidyl ether, and glycidyl methyl ether: reversible functionalization and cross-linking.

    PubMed

    Hilf, Jeannette; Scharfenberg, Markus; Poon, Jeffrey; Moers, Christian; Frey, Holger

    2015-01-01

    Well-defined poly((furfuryl glycidyl ether)-co-(glycidyl methyl ether) carbonate) (P((FGE-co-GME)C)) copolymers with varying furfuryl glycidyl ether (FGE) content in the range of 26% to 100% are prepared directly from CO2 and the respective epoxides in a solvent-free synthesis. All materials are characterized by size-exclusion chromatography (SEC), (1)H NMR spectroscopy, and differential scanning calorimetry (DSC). The furfuryl-functional samples exhibit monomodal molecular weight distributions with Mw/Mn in the range of 1.16 to 1.43 and molecular weights (Mn) between 2300 and 4300 g mol(-1). Thermal properties reflect the amorphous structure of the polymers. Both post-functionalization and cross-linking are performed via Diels-Alder chemistry using maleimide derivatives, leading to reversible network formation. This transformation is shown to be thermally reversible at 110 °C.

  18. Marchantin M trimethyl ether.

    PubMed

    Mombrú, A W; Suescun, L; Pandolfi, E; Seoane, G; López, G; Mariezcurrena, R

    2000-11-01

    The title macrocycle, C(31)H(30)O(5), is comprised of two bibenzyl ether moieties linked cyclically by spacers which each consist of two-carbon alkyl chains. The observed conformation of the macrocycle may be partly stabilized by intramolecular C-H.O close contacts. The packing appears to be directed by van der Waals forces. This work explains the occurrence of a signal found in the (1)H NMR spectra of both marchantinquinone and marchantin M trimethyl ether at delta = 5. 49 and 5.56 p.p.m., respectively. The shift in the position of the expected peak can be explained by the proximity of an H atom belonging to one of the aromatic rings to another ring in the same molecule.

  19. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems.

    PubMed

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar

    2015-10-07

    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed.

  20. Allene ether Nazarov cyclization.

    PubMed

    Tius, Marcus A

    2014-05-07

    The ease of synthesis and the exceptional reactivity of alkoxyallenes has led to their use in a large number of highly diverse applications. This Report describes their use in various versions of the allene ether Nazarov cyclization. Following a brief introduction to the Nazarov cyclization (Section 1), the oxidative cyclization of vinyl alkoxyallenes is discussed first (Section 2). Nazarov cyclizations of α-alkoxyallenyl vinyl ketones and of α-alkoxyallenyl vinyl tertiary carbinols are covered (Section 3). The discovery and the subsequent rational design of acetals that serve as chiral auxiliaries on the allene in highly enantioselective Nazarov cyclizations is explained (Section 4). Interrupted Nazarov cyclizations of alkoxyallenes that are generated in situ from the isomerization of propargyl ethers on solid supports are discussed, including the evolution of a highly diastereoselective, chiral auxiliary controlled version of the reaction. Some applications of the methodology to natural products total synthesis have been included so as to provide the reader with benchmarks with which to judge the utility of the methodology.

  1. Stable, hydroxyl functional polycarbonates with glycerol side chains synthesized from CO(2) and isopropylidene(glyceryl glycidyl ether).

    PubMed

    Geschwind, Jeannette; Frey, Holger

    2013-01-25

    A series of functional polycarbonates, poly((isopropylidene glyceryl glycidyl ether)-co-(glycidyl methyl ether) carbonate) (P((IGG-co-GME) C)) random copolymers with different fractions of 1,2-isopropylidene glyceryl glycidyl ether (IGG) units, is synthesized. After acidic hydrolysis of the acetal protecting groups, a new type of functional polycarbonate prepared directly from CO(2) and glycerol is obtained, namely poly((glyceryl glycerol)-co-(glycidyl methyl ether) carbonate) (P((GG-co-GME) C)). All hydroxyl functional samples exhibit monomodal molecular weight distributions with PDIs between 2.5 and 3.3 and M(n) between 12 000 and 25 000 g mol(-1) . Thermal properties reflect the amorphous structure of the polymers. The materials are stable in bulk and solution. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Polyarylene Ethers with Improved Properties

    NASA Technical Reports Server (NTRS)

    Hergenrother, P. M. (Inventor); Jensen, B. J. (Inventor); Havens, S. J. (Inventor)

    1986-01-01

    This invention relates to novel polyarylene ethers which possess the combination of high strength, toughness, and high use temperature with ease of extrusion and formation into complex objects. These polyarylene ethers are suitable for use in adhesives, coatings, films, membranes, and composite matrices. The polyarylene ethers of this invention are the polycondensation products from the reaction of either 1,3-bis (4-chloro or fluorobenzoyl) benzene with any one of the following bisphenolic compounds: bis (3-hydroxyphenyl) methane; bis (4-hydroxyphenyl) methane; 1,1-dimethyl-bis (4-hydroxyphenyl)methane, or 9,9-bis (4-hydroxyphenyl) fluorene. Random and block copolymers are also comprehended.

  3. Self-Controlled Synthesis of Hyperbranched Poly(etherketone)s from A2 + B3 Approach in Poly(phosphoric acid)

    DTIC Science & Technology

    2009-01-01

    polymerization condition was indeed strong enough to effi- ciently facilitate polycondensation via ‘‘direct’’ Friedel - Crafts reaction without gelation...Keywords: Friedel - Crafts acylation; high performance polymer; hyperbranched polymer; poly(ether-ketone)s; poly(phosphoric acid) INTRODUCTION Dendritic...Hence, the applied polymerization condition was indeed strong enough to efficiently facilitate polycondensation via ??direct?? Friedel - Crafts reaction

  4. Synthesis and Characterization of bis(Tetrahydrofurfuryl) Ether

    PubMed Central

    Stenger‐Smith, John D.; Baldwin, Lawrence; Chafin, Andrew

    2016-01-01

    Abstract Despite the availability of a large number of alkyl tetrahydrofurfuryl ethers that have a wide range of applications, pure bis(tetrahydrofurfuryl) ether (BTHFE) has not been previously synthesized. Here, we report the synthesis of BTHFE (consisting of the RR, SS, and meso stereoisomers) at greater than 99 % purity from tetrahydrofurfuryl alcohol, using (tetrahydrofuran‐2‐yl)methyl methanesulfonate as an intermediate. Additionally, we demonstrate that BTHFE can be used as a non‐volatile solvent in poly(3,4‐propylenedioxythiophene)‐based supercapacitors. Supercapacitor devices employing solutions of the ionic liquid 1‐ethyl‐3‐methyl‐imidizolium bis(trifluoromethylsulfonyl)imide in BTHFE display similar performances to those prepared by using the neat ionic liquid as an electrolyte, although solution‐based devices exhibit a somewhat higher resistance. PMID:27547636

  5. Tailoring chemical and physical properties of fibrous scaffolds from block copolyesters containing ether and thio-ether linkages for skeletal differentiation of human mesenchymal stromal cells.

    PubMed

    Chen, Honglin; Gigli, Matteo; Gualandi, Chiara; Truckenmüller, Roman; van Blitterswijk, Clemens; Lotti, Nadia; Munari, Andrea; Focarete, Maria Letizia; Moroni, Lorenzo

    2016-01-01

    Bioactive scaffolds for tissue engineering call for demands on new materials which can enhance traditional biocompatibility requirements previously considered for clinical implantation. The current commercially available thermoplastic materials, such as poly(lactic acid) (PLA), poly(glycolic acid) (PGA), poly(ε-caprolactone) (PCL) and their copolymers, have been used to fabricate scaffolds for regenerative medicine. However, these polymers have limitations including lacking of broadly tuning mechanical and degradable properties, and activation of specific cell-scaffold interactions, which limit their further application in tissue engineering. In the present study, electrospun scaffolds were successfully fabricated from a new class of block poly(butylene succinate)-based (PBS-based) copolyesters containing either butylene thiodiglycolate (BTDG) or butylene diglycolate (BDG) sequences. The polyesters displayed tunable mechanical properties and hydrolysis rate depending on the molecular architecture and on the kind of heteroatom introduced along the polymer backbone. To investigate their potential for skeletal regeneration, human mesenchymal stromal cells (hMSCs) were cultured on the scaffolds in basic, osteogenic and chondrogenic media. Our results demonstrated that PBS-based copolyesters containing thio-ether linkages (i.e. BTDG segments) were more favorable for chondrogenesis of hMSCs than those containing ether linkages (i.e. BDG sequences). In contrast, PBS-based copolyesters containing ether linkages showed enhanced mineralization. Therefore, these new functional scaffolds might hold potential for osteochondral tissue engineering applications.

  6. Pressure and temperature dependence of excess enthalpies of methanol + tetraethylene glycol dimethyl ether and methanol + polyethylene glycol dimethyl ether 250

    SciTech Connect

    Lopez, E.R.; Coxam, J.Y.; Fernandez, J.; Grolier, J.P.E.

    1999-12-01

    The excess molar enthalpies at 323.15 K, 373.15 K, and 423.15 K, at 8 MPa, are reported for the binary mixtures methanol + tetraethylene glycol dimethyl ether (TEGDME) and methanol + poly(ethylene glycol) dimethyl ether 250 (PEGDME 250). Excess molar enthalpies were determined with a Setaram C-80 calorimeter equipped with a flow mixing cell. For both systems, the excess enthalpies are positive over the whole composition range, increasing with temperature. The H{sup E}(x) curves are slightly asymmetrical, and their maxima are skewed toward the methanol-rich region. The excess enthalpies slightly change with the pressure, the sign of this change being composition-dependent. In the case of mixtures with TEGDME, the experimental H{sup E} values have been compared with those predicted with the Gmehling et al. version of UNIFAC (Dortmund) and the Nitta-Chao and DISQUAC group contribution models.

  7. Space, Time, Ether, and Kant

    NASA Astrophysics Data System (ADS)

    Wong, Wing-Chun Godwin

    This dissertation focused on Kant's conception of physical matter in the Opus postumum. In this work, Kant postulates the existence of an ether which fills the whole of space and time with its moving forces. Kant's arguments for the existence of an ether in the so-called Ubergang have been acutely criticized by commentators. Guyer, for instance, thinks that Kant pushes the technique of transcendental deduction too far in trying to deduce the empirical ether. In defense of Kant, I held that it is not the actual existence of the empirical ether, but the concept of the ether as a space-time filler that is subject to a transcendental deduction. I suggested that Kant is doing three things in the Ubergang: First, he deduces the pure concept of a space-time filler as a conceptual hybrid of the transcendental object and permanent substance to replace the category of substance in the Critique. Then he tries to prove the existence of such a space-time filler as a reworking of the First Analogy. Finally, he takes into consideration the empirical determinations of the ether by adding the concept of moving forces to the space -time filler. In reconstructing Kant's proofs, I pointed out that Kant is absolutely committed to the impossibility of action-at-a-distance. If we add this new principle of no-action-at-a-distance to the Third Analogy, the existence of a space-time filler follows. I argued with textual evidence that Kant's conception of ether satisfies the basic structure of a field: (1) the ether is a material continuum; (2) a physical quantity is definable on each point in the continuum; and (3) the ether provides a medium to support the continuous transmission of action. The thrust of Kant's conception of ether is to provide a holistic ontology for the transition to physics, which can best be understood from a field-theoretical point of view. This is the main thesis I attempted to establish in this dissertation.

  8. Uniaxial Stretching of Poly(keto-ether-imide) Films

    NASA Technical Reports Server (NTRS)

    Hinkley, Jeffrey A.; Dezern, James F.; Feuz, L.; Klinedinst, D.

    1999-01-01

    Fully-cured aromatic polyimides were prepared from various combinations of five dianhydrides and six diamines. When heated progressively under constant load, most of the films elongated rapidly near their glass transition temperatures. In about half of the nineteen materials, the strain was self-limiting - a possible indication of strain-induced crystallinity. The presence of crystallinity was established unambiguously for one material.

  9. 13C Solution NMR Spectra of Poly(ether)urethanes

    DTIC Science & Technology

    2002-11-01

    MDIO CH2 2019 14 DRDC Atlantic TM 2002-146 1 6 2 .9 8 1 5 4 .6 7 1 5 4 .5 8 1 3 8 .4 0 1 3 6 .6 2 1 2 9 .7 8 1...OCH2CH2 MDIO CH2CH2HN NH O C C O1 2 3 4 5 6 21 22 O CH2 OHCH2CH2O CH2CH2HN NH O C C O1 2 3 4 5 6 23 24 18 DRDC Atlantic TM 2002-146 1 6 2...DRDC Atlantic TM 2002-146 23 of the carbons arising from the diethylene glycol portion of DREA7. Comparison of the chemical environments

  10. Characterization of Poly(ether)urethanes - High Resolution Thermogravimetric Analysis

    DTIC Science & Technology

    2004-02-01

    temperature is held constant until the rate of weight loss falls below a predetermined rate. Heating is then resumed until the rate of weight loss...TGA) is a technique where the weight loss of a sample is monitored at constant temperature or as temperature is scanned. It is known that plastic...thermogravimétrique (ATG) est une technique qui permet de suivre la perte de poids d’un échantillon à une température constante ou en fonction d’une variation de

  11. Preparation of ordered and crosslinked films from liquid crystalline vinyl ether monomers

    SciTech Connect

    Andersson, H.; Sahlen, F.; Gedde, U.W.; Hult, A.

    1993-12-31

    Highly ordered densely crosslinked liquid crystalline poly(vinyl ether) films have been prepared by in-situ photopolymerization of oriented bifunctional mesogenic vinyl ether monomers. Orientation was achieved either by a simple surface treatment, using an unidirectionally rubbed polyimide film or by a magnetic field. Polymerization from various monomer phases resulted in LC polymer network films with different molecular organizations. The films were analyzed with small-angle X-ray scattering, polarized light microscopy and infrared-dichroism measurements. It was shown that films with nematic, smectic A and smectic B structures were obtained, the latter having a very high degree of orientation.

  12. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a...

  13. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Ether hook. 868.5420 Section 868.5420 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES ANESTHESIOLOGY DEVICES Therapeutic Devices § 868.5420 Ether hook. (a) Identification. An ether hook is a device...

  14. Propylene glycol monomethyl ether (PGME)

    Integrated Risk Information System (IRIS)

    Propylene glycol monomethyl ether ( PGME ) ; CASRN 107 - 98 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

  15. Desoxyhemigossypol-6-methyl-ether

    USDA-ARS?s Scientific Manuscript database

    Desoxyhemigossypol-6-methyl ether is an antimicrobial compound produced by the cotton plant in response to attack by pathogens. For the first time, we now report the crystal structure of this compound. This may prove useful in studies on the interaction of the compound with pathogenic fungal cells...

  16. Lacinilene C 7-methyl ether

    USDA-ARS?s Scientific Manuscript database

    Lacinilene C 7-methyl ether is an antimicrobial compound produced by the cotton plant in response to attack by pathogens. For the first time, we now report the crystal structure of this compound. This may prove useful in studies on the interaction of the compound with pathogenic fungal cells....

  17. p,p\\'-Dibromodiphenyl ether

    Integrated Risk Information System (IRIS)

    p , p ' - Dibromodiphenyl ether ; CASRN 2050 - 47 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for

  18. Bis(chloroethyl)ether (BCEE)

    Integrated Risk Information System (IRIS)

    Bis ( chloroethyl ) ether ( BCEE ) ; CASRN 111 - 44 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments fo

  19. Bis(chloromethyl)ether (BCME)

    Integrated Risk Information System (IRIS)

    Bis ( chloromethyl ) ether ( BCME ) ; CASRN 542 - 88 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

  20. PVDF-HFP/ether-modified polysiloxane membranes obtained via airbrush spraying as active separators for application in lithium ion batteries.

    PubMed

    Seidel, S M; Jeschke, S; Vettikuzha, P; Wiemhöfer, H-D

    2015-08-04

    Improved hybrid polymer electrolyte membranes are introduced based on ether-modified polysiloxanes and poly(vinylidene fluoride-co-hexafluoropropylene) yielding a safe separator membrane, which is able to be sprayed directly onto lithium ion battery active materials, with an active role for enhanced ion transport.

  1. Organocatalyzed synthesis of fluorinated poly(aryl thioethers).

    PubMed

    Park, Nathaniel H; Gomes, Gabriel Dos Passos; Fevre, Mareva; Jones, Gavin O; Alabugin, Igor V; Hedrick, James L

    2017-08-01

    The preparation of high-performance fluorinated poly(aryl thioethers) has received little attention compared to the corresponding poly(aryl ethers), despite the excellent physical properties displayed by many polysulfides. Herein, we report a highly efficient route to fluorinated poly(aryl thioethers) via an organocatalyzed nucleophilic aromatic substitution of silyl-protected dithiols. This approach requires low catalyst loadings, proceeds rapidly at room temperature, and is effective for many different perfluorinated or highly activated aryl monomers. Computational investigations of the reaction mechanism reveal an unexpected, concerted SNAr mechanism, with the organocatalyst playing a critical, dual-activation role in facilitating the process. Not only does this remarkable reactivity enable rapid access to fluorinated poly(aryl thioethers), but also opens new avenues for the processing, fabrication, and functionalization of fluorinated materials with easy removal of the volatile catalyst and TMSF byproducts.Fluorinated poly(aryl thioethers), unlike their poly(aryl ethers) counterparts, have received little attention despite excellent physical properties displayed by many polysulfides. Here the authors show a highly efficient route to fluorinated poly(aryl thioethers) via an organocatalyzed nucleophilic aromatic substitution of silyl-protected dithiols.

  2. Protein-resistant polymer coatings based on surface-adsorbed poly(aminoethyl methacrylate)/poly(ethylene glycol) copolymers.

    PubMed

    Ionov, Leonid; Synytska, Alla; Kaul, Elisabeth; Diez, Stefan

    2010-01-11

    We report on the protein-resistant properties of glass substrates coated with novel copolymers of 2-aminoethyl methacrylate hydrochloride and poly(ethylene glycol) methyl ether methacrylate (AEM-PEG). In comparison to currently available protein-blocking polymer systems, such as poly-l-lysine-poly(ethylene glycol), silane-based poly(ethylene glycol), and poly(ethylene glycol) brushes prepared by surface-initiated polymerization, the proposed AEM-PEG offers the combined advantages of low cost, simplicity of use, and applicability in aqueous solutions. We demonstrate the capability of AEM-PEG to block the surface binding of globular proteins (tubulin), their assemblies (microtubules), and functional motor proteins (kinesin-1). Moreover, we demonstrate the applicability of AEM-PEG for surface patterning of proteins in microfluidic devices.

  3. Measuring exposures to glycol ethers.

    PubMed

    Clapp, D E; Zaebst, D D; Herrick, R F

    1984-08-01

    In 1981, NIOSH began investigating the potential reproductive health effects resulting from exposures to a class of organic solvents known generically as glycol ethers (GE). This research was begun as a result of the NIOSH criteria document development program which revealed little data available on the health effects of glycol ether exposure. Toxicologic research was begun by NIOSH and other researchers which suggested substantial reproductive effects in animals. These animal data motivated a study of human exposures in the occupational setting. In 1981 and 1982 NIOSH conducted several walk-through surveys which included preliminary measurements of exposures in a variety of industries including painting trades, coal mining, production blending and distribution facilities, aircraft fueling, and communications equipment repair facilities. The human exposure data from these surveys is summarized in this paper with most results well below 1 parts per million (ppm) and only a few values approaching 10 ppm. Blood samples were collected at one site resulting in GE concentrations below the limit of detection. Exposures to airborne glycol ethers, in the industries investigated during the collection of this data, revealed several problems in reliably sampling GE at low concentrations. It became apparent, from the data and observations of work practices, that air monitoring alone provided an inadequate index of GE exposure. Further field studies of exposure to GE are anticipated, pending location of additional groups of exposed workers and development of more reliable methods for characterizing exposure, especially biological monitoring.

  4. Molecular Engineering of Liquid Crystalline Polymers by Living Polymerization. 10. Influence of Molecular Weight on the Phase Transitions of Poly(Omega-((4-Cyano-4’-Biphenyl)oxy)alkyl Vinyl Ethers)s with Nonyl and Decanyl Alkyl Groups

    DTIC Science & Technology

    1990-10-16

    Report No. 41 NAMAE OF PERFOMN4iNG OIRGANLZAI0N 60 OF~iCE SYMBOL 76 NAME OF MONITORING ORGANIZATION ase Western Reserve Univ. 4Btak N L ADRESS (Oty...PL/NO’NG/SPONSOMRNG 8b OfFCE SYMBOL 9 PROCUJREMENT INSTRUJMENT IOENTIFiC-ATiON NJMBEgt ,ftGANLZATION 0f sp9J’catJe) L ADORE S(Cfry. Stire..ria ZIP...polymerization of 9.-[(4-cyano-4’-biphenyl)oxylnonyI vinyl ether ( L -9) and 10-[(4- cyano-4’-bipnenyl)oxy]decanyl vinyl ether (6-10) are described. The

  5. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  6. Aza crown ether compounds as anion receptors

    DOEpatents

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  7. Crystalline Imide/Arylene Ether Copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Hergenrother, Paul M.; Bass, Robert G.

    1991-01-01

    Series of imide/arylene ether block copolymers prepared by using arylene ether blocks to impart low melt viscosity, and imide blocks to provide high strength and other desirable mechanical properties. Work represents extension of LAR-14159 on imide/arylene ether copolymers in form of films, moldings, adhesives, and composite matrices. Copolymers potentially useful in variety of high-temperature aerospace and microelectronic applications.

  8. Polyphenylene ethers with imide linking groups

    NASA Technical Reports Server (NTRS)

    St.clair, T. L.; Burks, H. D. (Inventor)

    1984-01-01

    Novel polyphenylene ethers with imide linking units are disclosed. These polymers incorporate the solvent and thermal resistance of polyimides and the processability of polyphenylene ethers. Improved physical properties over those of the prior art are obtained by incorporating meta linked ethers and/or polyphenylene oxides into the polymer backbone. A novel process for making polymers of this type is also disclosed. The process is unique in that the expected need of high process temperatures and/or special atmospheres are eliminated.

  9. Is the ether group hydrophilic or hydrophobic?

    PubMed

    Menger, Fredric M; Chlebowski, Mary E

    2005-03-29

    A series of six surfactants, each with two ether oxygens within otherwise all-hydrocarbon chains, were synthesized and examined for their colloidal properties. Since an ether oxygen is sterically and conformationally similar to the methylene group it has replaced, the ether effect on micellization should stem mainly from solvation of the oxygen and, possibly, disrupted hydrophobicity of its adjacent carbons. It was found that critical aggregation values among the surfactants differ only modestly despite the total length of the ether-separated carbon segments ranging from 12 to 18. Shorter ether surfactants with only 12 or 14 total carbons appear to form small, loose aggregates owing, presumably, to a mild hydrophilicity of the ether groups. A surfactant with 18 chain carbons has a greater tendency to associate hydrophobically, but this is counterbalanced by a relatively water-free environment encountered by the ether groups within a more conventional micelle interior. The result is a leveling effect in which the critical aggregation concentration (cac) loses it sensitivity to chain length. Above their cac's, none of the ether surfactants is a good solubilizer of tetramethysilane or mesitylene. This is not necessarily a predictable finding since it was conceivable that the presence of interior ether groups might actually enhance solubilization (much as ether is a better solvent than hexane). Foamability and solid adsorption studies also indicate that the ethers impair surface activity. In response to the question posed in the paper's title, two ether groups are not sufficiently hydrophilic to prevent aggregation, but they do manage to alter the micelles' morphology and properties considerably.

  10. Novel Thermooxidatively Stable Poly(ether-imide-benzoxazole) and Poly (ester-imide-benzoxazole)

    DTIC Science & Technology

    1994-07-15

    INTRODUCTION Wholly aromatic polyimldes (PI), polybenzoxazoles (PBO) and polyesters (PES, Scheme 1) all have high thermal stabilities, and find use In high...strength, high modulus fibers and engineering resins.1*2A4 Drawbacks of these systems are their insolubility and intractability, which cause difficulties...method for the production of PBO films and fibers ." Insolubility is circumvented in polyesters through polycondensations under melt conditions

  11. LaRC-ITPI/arylene ether copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.; Working, Dennis C.

    1991-01-01

    As part of an effort to develop high performance structural resins for aerospace applications, work has continued on block copolymers containing imide and arylene ether segments. The arylene ether block used in this study contains a bulky fluorene group in the polymer backbone while the imide block contains an arylene ketone segment similar to that in the arylene ether block and has been named LaRC-ITPI. A series of imide/arylene ether block and segmented copolymers were prepared and characterized. Films were prepared from these copolymers and mechanical properties were measured.

  12. Two crown-ether-coordinated caesium halogen salts.

    PubMed

    Well, Natalija van; Klein, Christian; Ritter, Franz; Assmus, Wolf; Krellner, Cornelius; Bolte, Michael

    2014-05-01

    The crystal structures of two crown-ether-coordinated caesium halogen salt hydrates, namely di-μ-bromido-bis[aqua(1,4,7,10,13,16-hexaoxacyclooctadecane)caesium(I)] dihydrate, [Cs2Br2(C12H24O6)2(H2O)2]·2H2O, (I), and poly[[diaquadi-μ-chlorido-μ-(1,4,7,10,13,16-hexaoxacyclooctadecane)dicaesium(I)] dihydrate], {[Cs2Cl2(C12H24O6)(H2O)2]·2H2O}n, (II), are reported. In (I), all atoms are located on general positions. In (II), the Cs(+) cation is located on a mirror plane perpendicular to the a axis, the chloride anion is located on a mirror plane perpendicular to the c axis and the crown-ether ring is located around a special position with site symmetry 2/m, with two opposite O atoms exactly on the mirror plane perpendicular to the a axis; of one water molecule, only the O atom is located on a mirror plane perpendicular on the a axis, while the other water molecule is completely located on a mirror plane perpendicular to the c axis. Whereas in (I), hydrogen bonds between bromide ligands and water molecules lead to one-dimensional chains running along the b axis, in (II) two-dimensional sheets of water molecules and chloride ligands are formed which combine with the polymeric caesium-crown polymer to give a three-dimensional network. Although both compounds have a similar composition, i.e. a Cs(+) cation with a halogen, an 18-crown-6 ether and a water ligand, the crystal structures are rather different. On the other hand, it is remarkable that (I) is isomorphous with the already published iodide compound.

  13. Conformational Study of Dibenzyl Ether

    NASA Astrophysics Data System (ADS)

    Hernandez-Castillo, Alicia O.; Abeysekera, Chamara; Hewett, Daniel M.; Zwier, Timothy S.

    2017-06-01

    Understanding the initial stages of polycyclic aromatic hydrocarbon (PAH) aggregation, the onset of soot formation, is an important goal on the pathway to cleaner combustion processes. PAHs with short alkyl chains, present in fuel-rich combustion environments, can undergo reactions that will chemically link aromatic rings together. One such example of a linked diaryl compound is dibenzyl ether, C_{6}H_{5}-CH_{2}-O-CH_{2}-C_{6}H_{5}. The -CH_{2}-O-CH_{2}- linkage has a length and flexibility well-suited to forming a π-stacked conformation between the two phenyl rings. In this talk, we will explore the single-conformation spectroscopy of dibenzyl ether under jet-cooled conditions in the gas phase. Laser-induced fluorescence, chirped pulse Fourier transform microwave (8-18 GHz region), and single-conformation infrared spectroscopy in the alkyl CH stretch region were all carried out on the molecule, thereby interrogating its full array of electronic, vibrational and rotational degrees of freedom. This work is the first step in a broader study to determine the extent of π-stacking in linked aryl compounds as a function of linkage and PAH size.

  14. Purification of aqueous cellulose ethers

    SciTech Connect

    Bartscherer, K.A.; de Pablo, J.J.; Bonnin, M.C.; Prausnitz, J.M.

    1990-07-01

    Manufacture of cellulose ethers usually involves high amounts of salt by-products. For application of the product, salt must be removed. In this work, we have studied the injection of high-pressure CO{sub 2} into an aqueous polymer-salt solution; we find that upon addition of isopropanol in addition to CO{sub 2}, the solution separates into two phases. One phase is rich in polymer and water, and the other phase contains mostly isopropanol, water and CO{sub 2}. The salt distributes between the two phases, thereby offering interesting possibilities for development of a new purification process for water-soluble polymers. This work presents experimental phase-equilibrium data for hydroxyethyl cellulose and sodium carboxymethyl cellulose with sodium acetate and potassium sulfate, respectively, in the region 40{degree}C and 30 to 80 bar. Based on these data, we suggest a process for the manufacture and purification of water-soluble cellulose ethers. 15 refs., 14 figs., 9 tabs.

  15. Bacterial Utilization of Ether Glycols

    PubMed Central

    Fincher, Edward L.; Payne, W. J.

    1962-01-01

    A soil bacterium capable of using oligo- and polyethylene glycols and ether alcohols as sole sources of carbon for aerobic growth was isolated. The effects of substituent groups added to the ether bonds on the acceptability of the compounds as substrates were studied. Mechanisms for the incorporation of two-carbon compounds were demonstrated by the observation that acetate, glyoxylate, ethylene glycol, and a number of the tricarboxylic acid cycle intermediates served as growth substrates in minimal media. The rate of oxidation of the short-chained ethylene glycols by adapted resting cells varied directly with increasing numbers of two-carbon units in the chains from one to four. The amount of oxygen consumed per carbon atom of oligo- and polyethylene glycols was 100% of theoretical, but only 67% of theoretical for ethylene glycol. Resting cells oxidized oligo- and polyethylene glycols with 2 to 600 two-carbon units in the chains. Longer chained polyethylene glycols (up to 6,000) were oxidized at a very slow rate by these cells. Dehydrogenation of triethylene glycol by adapted cells was observed, coupling the reaction with methylene blue reduction. PMID:13945208

  16. 27 CFR 21.108 - Ethyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Ethyl ether. 21.108 Section 21.108 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT....108 Ethyl ether. (a) Odor. Characteristic odor. (b) Specific gravity at 15.56 °/15.56 °C. Not...

  17. Polymeric Electrolyte Containing 12-Crown-4 Ether

    NASA Technical Reports Server (NTRS)

    Nagasubramanian, Ganesa; Distefano, Salvador

    1992-01-01

    Experiments show incorporation of 12-crown-4 ether into solid electrolytes based on polyethylene oxide enhances their electrochemical properties. More specifically, 12-crown-4 ether increases Faradaic efficiency for Li+ ions in low-power secondary Li cells and enables operation of these cells at lower temperatures with higher efficiencies.

  18. An expedient synthesis of linden ether.

    PubMed

    Serra, Stefano; Cominetti, Alessandra A

    2014-03-01

    We here describe a comprehensive study on the preparation of the intensive flavor 3,9-epoxy-p-mentha-1,4(8)-diene (1). Key steps of the presented synthesis are the selective addition of MeLi to the keto-ester 7, the regioselective cyclization of the obtained triol to give the ethers 4 and 8 and the selective dehydration of ether 4 through the use of POCI3 and pyridine. It is worth noting that the presented synthesis represents the first expedient and reliable entry to ether 1. Being present in linden honey, 1 is also known as linden ether and it has been regarded as a potential marker for the authentication of the linden honey origin. Therefore, ether 1 can be used as a useful reference standard for the analysis of the natural flavors, as we demonstrated by means of its identification in a sample ofunifloral linden honey.

  19. Process for preparing solvent resistant, thermoplastic aromatic poly(imidesulfone)

    NASA Technical Reports Server (NTRS)

    St.clair, T. L.; Yamaki, D. A. (Inventor)

    1984-01-01

    A process for preparing a thermoplastic poly(midesulfone) is disclosed. This resulting material has thermoplastic properties which are generally associated with polysulfones but not polyimides, and solvent resistant which is generally associated with polyimides but not polysulfones. This system is processable in the 250 to 350 C range for molding, adhesive and laminating applications. This unique thermoplastic poly(imidesulfone) is obtained by incorporating an aromatic sulfone moiety into the backbone of an aromatic linear polyimide by dissolving a quantity of a 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) in a solution of 3,3'-diaminodiphenylsulfone and bis(2-methoxyethyl)ether, precipitating the reactant product in water, filtering and drying the recovered poly(amide-acid sulfone) and converting it to the poly(imidesulfone) by heating.

  20. 40 CFR 721.10284 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10284 Poly , .alpha.-sulfo-.omega.-hydroxy-, C14-15-branched and linear alkyl ethers, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly ,...

  1. 40 CFR 721.10283 - Poly[oxy(methyl-1,2-ethanediyl)], .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10283 Poly , .alpha.-sulfo-.omega.-hydroxy-, C12-13-branched and linear alkyl ethers, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as poly ,...

  2. 21 CFR 73.3121 - Poly(hydroxyethyl methacrylate)-dye copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... sulfate group (or groups) or chlorine substituent of the dye is replaced by an ether linkage to poly.... No. 17095-24-8); (2) Reactive Blue 21 [copper, (29H,31H-phthalocyaninato(2-)-N 29,N 30,N 31,N 32...

  3. A transferable force field to predict phase equilibria and surface tension of ethers and glycol ethers.

    PubMed

    Ferrando, Nicolas; Lachet, Véronique; Pérez-Pellitero, Javier; Mackie, Allan D; Malfreyt, Patrice; Boutin, Anne

    2011-09-15

    We propose a new transferable force field to simulate phase equilibrium and interfacial properties of systems involving ethers and glycol ethers. On the basis of the anisotropic united-atom force field, only one new group is introduced: the ether oxygen atom. The optimized Lennard-Jones (LJ) parameters of this atom are identical whatever the molecule simulated (linear ether, branched ether, cyclic ether, aromatic ether, diether, or glycol ether). Accurate predictions are achieved for pure compound saturated properties, critical properties, and surface tensions of the liquid-vapor interface, as well as for pressure-composition binary mixture diagrams. Multifunctional molecules (1,2-dimethoxyethane, 2-methoxyethanol, diethylene glycol) have also been studied using a recently proposed methodology for the calculation of the intramolecular electrostatic energy avoiding the use of additional empirical parameters. This new force field appears transferable for a wide variety of molecules and properties. It is furthermore worth noticing that binary mixtures have been simulated without introducing empirical binary parameters, highlighting also the transferability to mixtures. Hence, this new force field gives future opportunities to simulate complex systems of industrial interest involving molecules with ether functions.

  4. Sulphonated polyether ether ketone diaphragms used in commercial scale alkaline water electrolysis

    NASA Astrophysics Data System (ADS)

    Otero, Jesus; Sese, Javier; Michaus, Igor; Santa Maria, Maria; Guelbenzu, Eugenio; Irusta, Silvia; Carrilero, Isabel; Arruebo, Manuel

    2014-02-01

    Sulphonated poly-ether-ether-ketone porous diaphragms were prepared by immersion precipitation using chemically induced phase separation to obtain a tight diaphragm skin layer and underneath finger-like bulk morphology. Different variables including sulphonation degree, diaphragm thickness, precipitation temperature and the presence of an inorganic filler were analyzed in order to evaluate the performance of the resulting diaphragms in water alkaline electrolysis using a bipolar electrolyzer and a commercial scale (50 kW) electrolyzer stack. Their performance was compared with a commercially available diaphragm in terms of cell voltage and oxygen purity (HTO) under normal operation conditions (10 bar, 80 °C) and under transient operation with up to 80 shutdown cycles (a total of 20 days in operation). Long term stability and operation reliability were assured for the SPEEK diaphragms showing lower cell voltage and HTO than the ones obtained with the commercial Zirfon® HTP 500 diaphragm.

  5. Polybrominated Diphenyl Ethers (PBDEs) Action Plan

    EPA Pesticide Factsheets

    Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants in a number of applications. EPA is concerned that some of the component congeners are persistent, bioaccumulative and toxic.

  6. Triethylene Glycol Monomethyl Ether; Final Test Rule

    EPA Pesticide Factsheets

    EPA is issuing a final test rule under section 4 of the Toxic Substances Control Act (TSCA) requiring manufacturers and processors of triethylene glycol monomethyl ether (TGME, CAS No. 112-35-6) to perform developmental neurotoxicity tasting.

  7. Thermodynamic analysis of alkali metal complex formation of polymer-bonded crown ether.

    PubMed

    Bey, Alexandra; Dreyer, Oliver; Abetz, Volker

    2017-06-21

    The complex formation of two crown ethers with colored alkali metal salts was investigated by UV/Vis spectroscopy. Complexation was accomplished with free benzo-15-crown-5 (B15C5) and 15-crown-5 bonded to a diblock copolymer (Poly15C5). The diblock copolymer was synthesized by two controlled polymerization techniques and copper(i)-catalyzed azide-alkyne cycloaddition. Depending on the inserted cation, 1 : 1- or 1 : 2-complexes are formed. A significant difference of the stability constants was determined by concentration dependence solvent extraction with sodium or potassium salt. For Poly15C5 the stability constants increase for both salts compared to the stability constants of B15C5, which suggests a more effective complexation. Evaluation of the thermodynamics (ΔH, ΔS, ΔG) of cation complexation was achieved by temperature dependence phase extraction on the basis of established thermodynamic equations. Remarkably, in all cases the entropic gain seems to be the major propulsion facilitating the complexation between alkali metal salts and crown ethers. Indeed, by using Poly15C5 a more pronounced dependency of enthalpy and entropy on the complex formation is calculated.

  8. Crosslinkage of collagen by polyglycidyl ethers.

    PubMed

    Tang, Z; Yue, Y

    1995-01-01

    Calcification is the principal cause of failure of glutaraldehyde treated bioprosthetic heart valves. This article reports the crosslinkage of several polyglycidyl ethers. Calcification of yak pericardium with polyglycidyl ethers was significantly decreased compared with that crosslinked with glutaraldehyde. The process of calcification of crosslinked yak pericardium was studied using 21 day subdermal implants in rats. The uptake of calcium with ethane diglycidyl ether was reduced (0.57 +/- 0.19 vs 4.28 +/- 1.62 micrograms/mg) over that with glutaraldehyde. Four polyglycidyl ethers were developed and compared. The best compound for raising the shrinkage temperature was the shortest chain compound without steric hindrance. In the polyglycidyl ether process, a suitable amount of alcohol was necessary to promote crosslinking; the catalyst, 2, 4, 6 -tris (dimethyl aminomethyl) phenol (TDAMP) and salicylic acid, were not favorable for long-term treatment of tissues because of the unnecessarily deep dyeing of the tissue, in addition to raising the shrinkage temperature. Unlike glutaraldehyde treatment, which reacts with lysine, polyglycidyl ether treated tissues maintained flexibility of the pericardial tissue, while binding amino acids such as lysine, methionine, tyrosine, aspartic acid and glutamic acid. The authors conclude that the ethane diglycidyl ether process combined with formaldehyde would further raise the shrinkage temperature from 78 degrees C to 87.5 degrees C and sustain it above 80 degrees C. Reverse treatment was not as effective. Compared with glutaraldehyde, polyglycidyl ether treatment renders tissue more flexible, increases the thermal stability of collagen, and decreases the incidence of calcification in vivo.

  9. Anaerobic biodegradation of ether compounds by ether bond-cleaving bacteria and methanogenic consortia

    SciTech Connect

    Dwyer, D.F.

    1989-01-01

    Ether compounds are manufactured for use in nonionic detergents, plastics, pesticides and other products and occur as toxic organic compounds, the most famous being tetrachlorodibenzo-p-dioxin. Ether compounds were considered recalcitrant to anaerobic biodegradation due to the lack of an appropriate oxidant for ether bond-cleavage in reducing environments. Many of these compounds reside in anaerobic environments or are exposed to anaerobic waste treatment processes. Thus, it is of interest to identify: (i) whether ether compounds are anaerobically biodegradable, (ii) the anaerobic microorganisms able to degrade these compounds, and (iii) the mechanism(s) of anaerobic ether bond-cleavage. The ether bonds of polyethylene glycol (PEG; HO-(CH{sub 2}CH{sub 2}-O-){sub n}H), phenyl ether ((C{sub 6}H{sub 5}){sub 2}O), and dibenzo-p-dioxin ((C{sub 6}H{sub 4}){sub 2}O{sub 2}) were shown to be degraded in methanogenic consortia enriched with these compounds and polyethoxylate (nonionic) surfactants as substrates. Two anaerobic microorganisms which used PEGs as sole substrates were isolated and characterized. Desulfovibrio desulfuricans strain DG2 degraded the monomer ethylene glycol and oligomers up to tetraethylene glycol (HO-(CH{sub 2}CH{sub 2}-O-){sub 4}H) in length. Bacteroides sp. strain PG1 degraded diethylene glycol and all other polymer lengths of PEG. PEGs were degraded by Bacteroides sp. strain PG1 via an external depolymerization which was either a hydrolytic or a reductive cleavage of the ether bond. The ether bond of diaryl ethers was apparently cleaved by a reductive mechanism which produced benzene and phenol as products from phenyl ether degradation and benzene and, by indirect analysis, catechol from dibenzo-dioxin.

  10. Polyaryl ethers and related polysiloxane copolymer molecular coatings preparation and radiation degrdation

    NASA Technical Reports Server (NTRS)

    Mcgrath, J. E.; Hedrick, J. L.; Webster, D. C.; Johnson, B. C.; Mohanty, D. K.; Yilgor, I.

    1983-01-01

    Poly(arylene ether sulfones) comprise a class of materials known as engineering thermoplastics which have a variety of important applications. These polymers are tough, rigid materials with good mechanical properties over a wide temperature range, and they are processed by conventional methods into products typically having excellent hydrolytic, thermal, oxidative and dimensional stability. Wholly aromatic random copolymers of hydroquinone and biphenol with 4.4 prime dichlorodiphenyl sulfone were synthesized via mechanical nucleophilic displacement. Their structures were characterized and mechanical behavior studied. These tough, ductile copolymers show excellent radiation resistance to electron beam treatment and retain much of the mechanical properties up to at least 700 Mrads under argon.

  11. Conformations and Barriers to Methyl Group Internal Rotation in Two Asymmetric Ethers: Propyl Methyl Ether and Butyl Methyl Ether

    NASA Astrophysics Data System (ADS)

    Long, B. E.; Dechirico, F.; Cooke, S. A.

    2012-06-01

    The conformational preferences of the O-C-C-C unit are important in many biological systems with the unit generally preferring a gauche configuration compared to an anti configuration. Butyl methyl ether and propyl methyl ether provide very simple systems for this phenomenom to manifest. Pure rotational spectra of the title molecules have been recorded using chirped pulse Fourier transform microwave spectroscopy (CP-FTMW). In the case of butyl methyl ether, only one conformer has been observed. This conformer has torsional angles of COCC = 180°, OCCC = 62° and CCCC = 180° (anti-gauche-anti) and rotational constants of A = 10259.4591(33) MHz, B = 1445.6470(13) MHz, and C = 1356.2944(14) MHz. The rotational spectrum was doubled and has been analyzed to produce an effective barrier to methyl group internal rotation of 780(35) cm-1. A prior rotational spectroscopic study on propyl methyl ether had focused only on the high energy anti-anti conformer. We have analyzed spectra from the lowest energy anti-gauche conformer and the spectroscopic constants will be presented. A summary of the differences in conformational energies and methyl group internal rotation barriers for the class of aliphatic asymmetric ethers will be presented. K. N. Houk, J. E. Eksterowicz, Y.-D. Wu, C. D. Fuglesang, D. B. Mitchell. J. Am. Chem. Soc. 115 (4170), 1993. Hiroshi Kato, Jun Nakagawa, Michiro Hayashi. J. Mol. Spectrosc. 80 (272), 1980.

  12. Stereocontrolled Cyanohydrin Ether Synthesis through Chiral Brønsted Acid-Mediated Vinyl Ether Hydrocyanation

    PubMed Central

    Lu, Chunliang; Su, Xiaoge; Floreancig, Paul E.

    2013-01-01

    Vinyl ethers can be protonated to generate oxocarbenium ions that react with Me3SiCN to form cyanohydrin alkyl ethers. Reactions that form racemic products proceed efficiently upon converting the vinyl ether to an α-chloro ether prior to cyanide addition in a pathway that proceeds through Brønsted acid-mediated chloride ionization. Enantiomerically enriched products can be accessed by directly protonating the vinyl ether with a chiral Brønsted acid to form a chiral ion pair. Me3SiCN acts as the nucleophile and PhOH serves as a stoichiometric proton source in a rare example of an asymmetric bimolecular nucleophilic addition reaction into an oxocarbenium ion. Computational studies provide a model for the interaction between the catalyst and the oxocarbenium ion. PMID:23968162

  13. Thermodynamic equilibrium calculations of dimethyl ether steam reforming and dimethyl ether hydrolysis

    NASA Astrophysics Data System (ADS)

    Semelsberger, Troy A.; Borup, Rodney L.

    The production of a hydrogen-rich fuel-cell feed by dimethyl ether (DME) steam reforming was investigated using calculations of thermodynamic equilibrium as a function of steam-to-carbon ratio (0.00-4.00), temperature (100-600 °C), pressure (1-5 atm), and product species. Species considered were acetone, acetylene, carbon dioxide, carbon monoxide, dimethyl ether, ethane, ethanol, ethylene, formaldehyde, formic acid, hydrogen, isopropanol, methane, methanol, methyl-ethyl ether, n-propanol and water. Thermodynamic equilibrium calculations of DME steam reforming indicate complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide at temperatures greater than 200 °C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure ( P = 1 atm). Increasing the operating pressure shifts the equilibrium toward the reactants; increasing the pressure from 1 to 5 atm decreases the conversion of dimethyl ether from 99.5 to 76.2%. The trend of thermodynamically stable products in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol-formaldehyde, formic acid, and acetylene were not observed. Based on the equilibrium calculations, the optimal processing conditions for dimethyl ether steam reforming occur at a steam-to-carbon ratio of 1.50, a pressure of 1 atm, and a temperature of 200 °C. These thermodynamic equilibrium calculations show dimethyl ether processed with steam will produce hydrogen-rich fuel-cell feeds—with hydrogen concentrations exceeding 70%. The conversion of dimethyl ether via hydrolysis (considering methanol as the only product) is limited by thermodynamic equilibrium. Equilibrium conversion increases with temperature and steam-to-carbon ratio. A maximum dimethyl ether conversion of 62% is achieved at a steam-to-carbon ratio of 5.00 and a processing temperature of 600 °C.

  14. Ether and the atmospheric chemistry data assimilation

    NASA Astrophysics Data System (ADS)

    Ricaud, P.; Phulpin, T.; Girod, F.; Boonne, C.

    The French atmospheric chemistry data base Ether has been developed and funded by the French Space Agency (CNES) and the Institut National des Sciences de l'Univers (INSU/CNRS) for about 6 years. The role of Ether is to assist French atmospheric researchers, European scientists, as long as they are involved in co-operation agreements with French scientists, to locate, access and interpret atmospheric data. This centre gathers data from satellite, balloon campaigns linked to satellite validation, aircraft and model results for stratospheric and tropospheric purposes and from different levels of production (raw data, physical data, interpolated or assimilated data). All Ether data are available on-line through a World Web interface (http://ether.ipsl.jussieu.fr). Software and added-value services are provided to assist in the manipulation of the data or to generate higher levels standard data products. Extensive information is also provided on the data collection procedures, formats, contact names and references to scientific papers. In addition to data support activities, a major goal of Ether is to promote the creation of different expertise networks on varying atmospheric chemistry topics. The first working group has been created on data assimilation. It consists in gathering expertises in different themes (satellites, assimilation techniques, modelling, real-time processing) in order to optimally develop a tool able to answer different scientific questions relative to the evolution of the Earth atmosphere in terms of chemistry and dynamics. Based on the PALM tool able to interconnect different codes, it will be able to process different satellite data using two atmospheric models and assimilation schemes within the French Ether data base. Ether will focus on the handling and on the development of added-value services of data for which the French community is directly or indirectly involved. For these projects Ether will provide all the data needed, and will

  15. Wholly Aromatic Ether-Imides as n-Type Semiconductors

    NASA Technical Reports Server (NTRS)

    Weiser, Erik; St. Clair, Terry L.; Dingemans, Theo J.; Samulski, Edward T.; Irene, Gene

    2006-01-01

    Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able

  16. Atmospheric degradation of 2-chloroethyl vinyl ether, allyl ether and allyl ethyl ether: Kinetics with OH radicals and UV photochemistry.

    PubMed

    Antiñolo, M; Ocaña, A J; Aranguren, J P; Lane, S I; Albaladejo, J; Jiménez, E

    2017-08-01

    Unsaturated ethers are oxygenated volatile organic compounds (OVOCs) emitted by anthropogenic sources. Potential removal processes in the troposphere are initiated by hydroxyl (OH) radicals and photochemistry. In this work, we report for the first time the rate coefficients of the gas-phase reaction with OH radicals (kOH) of 2-chloroethyl vinyl ether (2ClEVE), allyl ether (AE), and allyl ethyl ether (AEE) as a function of temperature in the 263-358 K range, measured by the pulsed laser photolysis-laser induced fluorescence technique. No pressure dependence of kOH was observed in the 50-500 Torr range in He as bath gas, while a slightly negative T-dependence was observed. The temperature dependent expressions for the rate coefficients determined in this work are: The estimated atmospheric lifetimes (τOH) assuming kOH at 288 K were 3, 2, and 4 h for 2ClEVE, AE and AEE, respectively. The kinetic results are discussed in terms of the chemical structure of the unsaturated ethers by comparison with similar compounds. We also report ultraviolet (UV) and infrared (IR) absorption cross sections (σλ and σ(ν˜), respectively). We estimate the photolysis rate coefficients in the solar UV actinic region to be less than 10(-7) s(-1), implying that these compounds are not removed from the atmosphere by this process. In addition, from σ(ν˜) and τOH, the global warming potential of each unsaturated ether was calculated to be almost zero. A discussion on the atmospheric implications of the titled compounds is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. Inhalation anaesthesia: from diethyl ether to xenon.

    PubMed

    Bovill, J G

    2008-01-01

    Modern anaesthesia is said to have began with the successful demonstration of ether anaesthesia by William Morton in October 1846, even though anaesthesia with nitrous oxide had been used in dentistry 2 years before. Anaesthesia with ether, nitrous oxide and chloroform (introduced in 1847) rapidly became commonplace for surgery. Of these, only nitrous oxide remains in use today. All modern volatile anaesthetics, with the exception of halothane (a fluorinated alkane), are halogenated methyl ethyl ethers. Methyl ethyl ethers are more potent, stable and better anaesthetics than diethyl ethers. They all cause myocardial depression, most markedly halothane, while isoflurane and sevoflurane cause minimal cardiovascular depression. The halogenated ethers also depress the normal respiratory response to carbon dioxide and to hypoxia. Other adverse effects include hepatic and renal damage. Hepatitis occurs most frequently with halothane, although rare cases have been reported with the other agents. Liver damage is not caused by the anaesthetics themselves, but by reactive metabolites. Type I hepatitis occurs fairly commonly and takes the form of a minor disturbance of liver enzymes, which usually resolves without treatment. Type II, thought to be immune-mediated, is rare, unpredictable and results in a severe fulminant hepatitis with a high mortality. Renal damage is rare, and was most often associated with methoxyflurane because of excessive plasma fluoride concentrations resulting from its metabolism. Methoxyflurane was withdrawn from the market because of the high incidence of nephrotoxicity. Among the contemporary anaesthetics, the highest fluoride concentrations have been reported with sevoflurane, but there are no reports of renal dysfunction associated with its use. Recently there has been a renewed interest in xenon, one of the noble gases. Xenon has many of the properties of an ideal anaesthetic. The major factor limiting its more widespread is the high cost, about

  18. Degradation mechanism of sulfonated poly(ether ether ketone) (SPEEK) ion exchange membranes under vanadium flow battery medium.

    PubMed

    Yuan, Zhizhang; Li, Xianfeng; Hu, Jinbo; Xu, Wanxing; Cao, Jingyu; Zhang, Huamin

    2014-10-07

    The degradation mechanism of hydrocarbon ion exchange membranes under vanadium flow battery (VFB) medium was investigated and clarified for the first time. This work will be highly beneficial for improving the chemical stability of hydrocarbon ion exchange membranes, which is one of the most challenging issues for VFB application.

  19. Characterization of sulfonated poly(ether ether ketone)/silane nanocomposite membrane for high temperature polymer electrolyte membrane fuel cells.

    PubMed

    Ghil, Lee-Jin; Kim, Chang-Kyeom; Park, Na-Ri; Rhee, Hee-Woo

    2011-01-01

    The perfluorosulfonic acid polymer membrane is most widely used in PEMFCs. However, its some major drawbacks like high cost and performance limitation at high temperature are obstacles of its commercialization. The goal of this study was to develop low cost membranes which have good conductivity in the range of PEMFCs operating temperature. We fabricated new sPEEK/3-APTES nanocomposite membrane where inorganic particles were chemically bonded to sulfuric acid group of sPEEK. PEEK is a thermally stable, mechanically tough and very cheap polymer. And the addition of 3-APTES and phosphorous acid increased the proton conductivity of composite membranes at high temperatures. This nanocomposite membranes maintained good conductivity at 110 degrees C.

  20. 41. LOOKING WEST AT BUILDING NO. 519, ETHER AND ALCOHOL ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    41. LOOKING WEST AT BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, (LEFT) AND BUILDING NO. 521, ETHER VAULT, (RIGHT) IN FOREGROUND - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  1. 37. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, NORTHWEST ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    37. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, NORTHWEST CORNER OF BUILDING. BUILDING NO. 521 (ETHER VAULT) IN BACKGROUND LEFT. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  2. Quercetin-3-methyl ether inhibits lapatinib-sensitive and -resistant breast cancer cell growth by inducing G2/M arrest and apoptosis

    PubMed Central

    Li, Jixia; Zhu, Feng; Lubet, Ronald A.; De Luca, Antonella; Grubbs, Clinton; Ericson, Marna E.; D’Alessio, Amelia; Normano, Nicola; Dong, Zigang; Bode, Ann M.

    2012-01-01

    Lapatinib, an oral, small-molecule, reversible inhibitor of both EGFR and HER2, is highly active in HER2 positive breast cancer as a single agent and in combination with other therapeutics. However, resistance against lapatinib is an unresolved problem in clinical oncology. Recently, interest in the use of natural compounds to prevent or treat cancers has gained increasing interest because of presumed low toxicity. Quercetin-3-methyl ether, a naturally occurring compound present in various plants, has potent anticancer activity. Here, we found that quercetin-3-methyl ether caused in a significant growth inhibition of lapatinib-sensitive and -resistant breast cancer cells. Western blot data showed that quercetin-3-methyl ether had no effect on Akt or ERKs signaling in resistant cells. However, quercetin-3-methyl ether caused a pronounced G2/M block mainly through the Chk1-Cdc25c-cyclin B1/Cdk1 pathway in lapatinib-sensitive and -resistant cells. In contrast, lapatinib produced an accumulation of cells in the G1 phase mediated through cyclin D1, but only in lapatinib-sensitive cells. Moreover, quercetin-3-methyl ether induced significant apoptosis, accompanied with increased levels of cleaved caspase 3, caspase 7 and poly (ADP-ribose) polymerase (PARP) in both cell lines. Overall, these results suggested that quercetin-3-methyl ether might be a novel and promising therapeutic agent in lapatinib-sensitive or -resistant breast cancer patients. PMID:22086611

  3. High octane ethers from synthesis gas-derived alcohols

    SciTech Connect

    Klier, K.; Herman, R.G.; Johansson, M.; Feeley, O.C.

    1992-01-01

    The objective of the proposed research is to synthesize high octane ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from H{sub 2}/CO/CO{sub 2} coal-derived synthesis gas via alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers.

  4. High octane ethers from synthesis gas-derived alcohols

    SciTech Connect

    Klier, K.; Herman, R.G.; Johansson, M.A.; Feeley, O.C.

    1992-04-01

    The objective of the proposal research is to synthesize high octane ethers, primarily methyl isobutyl ether (MIBE) and methyl tertiary butyl ether (MTBE), directly from H{sub 2}/CO/CO{sub 2} coal-derived synthesis gas via alcohol mixtures that are rich in methanol and 2-methyl-1-propanol (isobutanol). The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers.

  5. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  6. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  7. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  8. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  9. 40 CFR 721.9663 - Poly(oxy-1,2-ethanediyl), alpha, alpha′-[thiobis (1-oxo-3,1-propanediyl)]bis [omega-hydroxy-,bis...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alphaâ²- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. 721.9663 Section 721.9663 Protection...(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis (C11-15 and C11-15-isoalkyl) ethers. (a... poly(oxy-1,2-ethanediyl), alpha, alpha′- bis [omega-hydroxy-,bis(C11-15 and C11-15-isoalkyl)...

  10. 40 CFR 721.3435 - Butoxy-substituted ether alkane.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butoxy-substituted ether alkane. 721... Substances § 721.3435 Butoxy-substituted ether alkane. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as butoxy-substituted ether...

  11. 40 CFR 721.3465 - Stilbene diglycidyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Stilbene diglycidyl ether. 721.3465... Substances § 721.3465 Stilbene diglycidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as stilbene diglycidyl ether (PMN P-96-1427) is subject...

  12. 39. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, LOOKING ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    39. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, LOOKING AT SOUTHWEST CORNER WITH BUILDING NO. 521, ETHER VAULT, AND BUILDING NO. 519-A, ETHER & ALOCOHL STORAGE TANKS, IN BACKGROUND RIGHT. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  13. Alkyl Aryl Ether Bond Formation with PhenoFluor**

    PubMed Central

    Shen, Xiao; Neumann, Constanze N.; Kleinlein, Claudia; Claudia, Nathaniel W.; Ritter, Tobias

    2015-01-01

    An alkyl aryl ether bond formation reaction between phenols and primary and secondary alcohols with PhenoFluor has been developed. The reaction features a broad substrate scope and tolerates many functional groups, and substrates that are challenging for more conventional ether bond forming processes may be coupled. A preliminary mechanistic study indicates reactivity distinct from conventional ether bond formation. PMID:25800679

  14. Review of glycol ether and glycol ether ester solvents used in the coating industry.

    PubMed Central

    Smith, R L

    1984-01-01

    Ethylene oxide-based glycol ether and glycol ether ester solvents have been used in the coatings industry for the past fifty years. Because of their excellent performance properties (evaporation rate, blush resistance, flow-out and leveling properties, solubility for coating resins, solvent activity, mild odor, good coupling ability, good solvent release) a complete line of ethylene oxide-based solvents of various molecular weights has been developed. These glycol ether and glycol ether ester solvents have better solvent activity for coating resin than ester or ketone solvents in their evaporation rate range. The gloss, flow and leveling, and general performance properties of many coating systems are dependent on the use of these products in the coating formula. Because of the concern about the toxicity of certain ethylene oxide-based solvents, other products are being evaluated as replacements in coating formulas. PMID:6499793

  15. Polycaprolactone-poly(ethylene glycol) multiblock copolymers as potential substitutes for di(ethylhexyl) phthalate in flexible poly(vinyl chloride) formulations.

    PubMed

    Ferruti, Paolo; Mancin, Ivan; Ranucci, Elisabetta; De Felice, Claudio; Latini, Giuseppe; Laus, Michele

    2003-01-01

    New high-molecular-weight hydrophobic/hydrophilic segmented copolymers of poly(ester ether carbonate) structure, containing poly(epsilon-caprolactone) (PCL) and poly(ethylene glycol) (PEG) segments in their main chain, were synthesized and characterized. These copolymers were obtained by a two-step chain-extension reaction carried out in the presence of alpha,omega-dihydroxy-oligoPCL of molecular weight 1250 and PEG samples of molecular weight 150, 400, 600, 1000, and 2000. The molecular structures of all synthesized materials were characterized by means of (1)H NMR and (13)C NMR spectroscopy, their molecular weights were determined by means of size exclusion chromatography, and their thermal properties were obtained by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The poly(ester ether carbonate)s of this study are partly or totally miscible at least up to 50 wt % with poly(vinyl chloride) (PVC) and could be used to produce flexible PVC formulations. The miscibility between PVC and the poly(ester ether carbonate)s reported in this paper was investigated by means of DSC and DMA analysis. PVC blends were also analyzed by determining their swellability and the amount of extractables in aqueous media. By comparison purposes, the chain-extension product of PCL1250, that is, PCL polycarbonate, was also synthesized and characterized. The results obtained demonstrated that the copolymers with shortest PEG segment length, i.e. PEG150, 400, and 600, give the best results in terms of miscibility with PVC and lead to blends with maximum resistance to extraction by water. Therefore, they represent, in principle, good substitutes for low-molecular-weight, leachable PVC plasticizers, such as di(ethylhexyl) phthalate.

  16. A novel biobased plasticizer of epoxidized cardanol glycidylether: Synthesis and application in soft poly(vinyl chloride) films

    USDA-ARS?s Scientific Manuscript database

    A novel plasticizer derived from cardanol, epoxied cardanol glycidyl ether (ECGE), was synthesized and characterized by 1H-NMR and 13C-NMR. Effects of the ECGE combined with dioctyl phthalate (DOP), a commercial plasticizer, in soft poly(vinyl chloride) (PVC) films were studied. Dynamic mechanical a...

  17. POLYBROMINATED DIPHENYL ETHERS IN US SOILS

    EPA Science Inventory

    Chemical analysis of thirty-three soil samples from 15 US states reveals Polybrominated Diphenyl Ethers (PBDEs), in every sample.PBDE concentrations rangefrom 0.09 to 1200 parts per billion by mass. These data are the first analysis of soil concentrations of PBDEs in soils from a...

  18. Methyl tert-butyl ether (MTBE)

    Integrated Risk Information System (IRIS)

    Methyl tert - butyl ether ( MTBE ) ; CASRN 1634 - 04 - 4 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments f

  19. Orphan enzymes in ether lipid metabolism.

    PubMed

    Watschinger, Katrin; Werner, Ernst R

    2013-01-01

    Ether lipids are an emerging class of lipids which have so far not been investigated and understood in every detail. They have important roles as membrane components of e.g. lens, brain and testis, and as mediators such as platelet-activating factor. The metabolic enzymes for biosynthesis and degradation have been investigated to some extent. As most involved enzymes are integral membrane proteins they are tricky to handle in biochemical protocols. The sequence of some ether lipid metabolising enzymes has only recently been reported and other sequences still remain obscure. Defined enzymes without assigned sequence are known as orphan enzymes. One of these enzymes with uncharacterised sequence is plasmanylethanolamine desaturase, a key enzyme for the biosynthesis of one of the most abundant phospholipids in our body, the plasmalogens. This review aims to briefly summarise known functions of ether lipids, give an overview on their metabolism including the most prominent members, platelet-activating factor and the plasmalogens. A special focus is set on the description of orphan enzymes in ether lipid metabolism and on the successful strategies how four previous orphans have recently been assigned a sequence. Only one of these four was characterised by classical protein purification and sequencing, whereas the other three required alternative strategies such as bioinformatic candidate gene selection and recombinant expression or development of an inhibitor and multidimensional metabolic profiling. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  20. POLYBROMINATED DIPHENYL ETHERS IN SOUTHERN MISSISSIPPI CATFISH

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a wide variety of consumer products. Concerns surrounding these compounds are primarily due do their ubiquitous presence in the environment as well as in human tissue, such as milk, coupled with evidence indi...

  1. Ethylene glycol monobutyl ether (EGBE) (2-Butoxyethanol)

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 08 / 006F www.epa.gov / iris TOXICOLOGICAL REVIEW OF ETHYLENE GLYCOL MONOBUTYL ETHER ( EGBE ) ( CAS No . 111 - 76 - 2 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) March 2010 U.S . Environmental Protection Agency Washington , DC DISCLAIMER Thi

  2. Dimensionally Stable Ether-Containing Polyimide Copolymers

    NASA Technical Reports Server (NTRS)

    Fay, Catharine C. (Inventor); St.Clair, Anne K. (Inventor)

    1999-01-01

    Novel polyimide copolymers containing ether linkages were prepared by the reaction of an equimolar amount of dianhydride and a combination of diamines. The polyimide copolymers described herein possess the unique features of low moisture uptake, dimensional stability, good mechanical properties, and moderate glass transition temperatures. These materials have potential application as encapsulants and interlayer dielectrics.

  3. Bis(2-chloro-1-methylethyl) ether

    Integrated Risk Information System (IRIS)

    Bis ( 2 - chloro - 1 - methylethyl ) ether ; CASRN 108 - 60 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

  4. 40 CFR 721.3380 - Anilino ether.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3380 Anilino ether. Link to an amendment published at 79 FR 34637, June 18, 2014. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as anilino...

  5. Biomonitoring Polybrominated Diphenyl Ethers in Lactating Women

    USDA-ARS?s Scientific Manuscript database

    Breast milk is a valuable biological specimen for biomonitoring lipid-soluble polybrominated diphenyl ethers (PBDEs). The goal of this project was to determine the levels of PBDEs in breast milk of lactating women from the Seacoast region of New Hampshire and to examine potential relationships betw...

  6. 21 CFR 868.5420 - Ether hook.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES... that fits inside a patient's mouth and that is intended to deliver vaporized ether. (b) Classification... the quality system regulation in part 820 of this chapter, with the exception of § 820.180,...

  7. POLYBROMINATED DIPHENYL ETHERS IN SOUTHERN MISSISSIPPI CATFISH

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a wide variety of consumer products. Concerns surrounding these compounds are primarily due do their ubiquitous presence in the environment as well as in human tissue, such as milk, coupled with evidence indi...

  8. Imide/arylene ether block copolymers

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Hergenrother, P. M.; Bass, R. G.

    1991-01-01

    Two series of imide/arylene either block copolymers were prepared using an arylene ether block and either an amorphous or semi-crystalline imide block. The resulting copolymers were characterized and selected physical and mechanical properties were determined. These results, as well as comparisons to the homopolymer properties, are discussed.

  9. Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

    NASA Astrophysics Data System (ADS)

    Li, Xiaomeng; Luan, Shifang; Yang, Huawei; Shi, Hengchong; Zhao, Jie; Jin, Jing; Yin, Jinghua; Stagnaro, Paola

    2012-01-01

    Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.

  10. Side chain engineering of poly-thiophene and its impact on crystalline silicon based hybrid solar cells

    SciTech Connect

    Zellmeier, M.; Rappich, J.; Nickel, N. H.; Klaus, M.; Genzel, Ch.; Janietz, S.; Frisch, J.; Koch, N.

    2015-11-16

    The influence of ether groups in the side chain of spin coated regioregular polythiophene derivatives on the polymer layer formation and the hybrid solar cell properties was investigated using electrical, optical, and X-ray diffraction experiments. The polymer layers are of high crystallinity but the polymer with 3 ether groups in the side chain (P3TOT) did not show any vibrational fine structure in the UV-Vis spectrum. The presence of ether groups in the side chains leads to better adhesion resulting in thinner and more homogeneous polymer layers. This, in turn, enhances the electronic properties of the planar c-Si/poly-thiophene hybrid solar cell. We find that the power conversion efficiency increases with the number of ether groups in the side chains, and a maximum power conversion efficiency of η = 9.6% is achieved even in simple planar structures.

  11. Side chain engineering of poly-thiophene and its impact on crystalline silicon based hybrid solar cells

    NASA Astrophysics Data System (ADS)

    Zellmeier, M.; Rappich, J.; Klaus, M.; Genzel, Ch.; Janietz, S.; Frisch, J.; Koch, N.; Nickel, N. H.

    2015-11-01

    The influence of ether groups in the side chain of spin coated regioregular polythiophene derivatives on the polymer layer formation and the hybrid solar cell properties was investigated using electrical, optical, and X-ray diffraction experiments. The polymer layers are of high crystallinity but the polymer with 3 ether groups in the side chain (P3TOT) did not show any vibrational fine structure in the UV-Vis spectrum. The presence of ether groups in the side chains leads to better adhesion resulting in thinner and more homogeneous polymer layers. This, in turn, enhances the electronic properties of the planar c-Si/poly-thiophene hybrid solar cell. We find that the power conversion efficiency increases with the number of ether groups in the side chains, and a maximum power conversion efficiency of η = 9.6% is achieved even in simple planar structures.

  12. Morphology and properties of amine terminated poly(arylene ether ketone) and poly(arylene ether sulfone) modified epoxy resin systems

    NASA Technical Reports Server (NTRS)

    Cecere, J. A.; Mcgrath, J. E.; Hedrick, J. L.

    1986-01-01

    Epoxy resin networks cured with DDS were modified by incorporating tough ductile thermoplastics such as the amine terminated polyether sulfones and amine terminated polyether ketones. Both linear copolymers were able to significantly improve the fracture toughness values at the 15 and 30 weight percent concentrations examined. These improvements in fracture toughness were achieved without any significant change in the flexural modulus.

  13. Inhibition of diethyl ether degradation in Rhodococcus sp. strain DEE5151 by glutaraldehyde and ethyl vinyl ether.

    PubMed

    Kim, Yong-Hak; Engesser, Karl-Heinrich

    2005-02-15

    Alkyl ether-degrading Rhodococcus sp. strain DEE5151, isolated from activated sewage sludge, has an activity for the oxidation of a variety of alkyl ethers, aralkyl ethers and dibenzyl ether. The whole cell activity for diethyl ether oxidation was effectively inhibited by 2,3-dihydrofurane, ethyl vinyl ether and glutaraldehyde. Glutaraldehyde of less than 30 microM inhibited the activity by a competitive manner with the inhibition constant, K(I) of 7.07+/-1.36 microM. The inhibition type became mixed at higher glutaraldehyde concentrations >30 microM, probably due to the inactivation of the cell activity by the Schiff-base formation. Structurally analogous ethyl vinyl ether inhibited the diethyl ether oxidation activity in a mixed manner with decreasing the apparent maximum oxidation rate, v(max)(app), and increasing the apparent Michaelis-Menten constant, K(M)(app). The mixed type inhibition by ethyl vinyl ether seemed to be introduced not only by the structure similarity with diethyl ether, but also by the reactivity of the vinyl ether with cellular components in the whole cell system.

  14. A high performance membrane for sorption and pervaporation separation of ethyl tert-butyl ether and ethanol mixtures

    SciTech Connect

    Luo, G.S.; Niang, M.; Schaetzel, P.

    1999-02-01

    A new kind of membrane was prepared by blending 5 wt% poly(1-vinylpyrrolidone-co-acrylic acid) with cellulose acetate propionate for the separation of ethyl tert-butyl ether and ethanol mixtures. The membrane properties were evaluated by pervaporation and sorption of mixtures of ethyl tert-butyl ether/ethanol. The experimental results show that the selectivity and the fluxes of this membrane depend upon the feed composition and upon the temperature. The minimum values of ethanol concentration in the permeate and in the sorption solution were obtained in the vicinity of the azeotropic point. Compared with the pure CAP membrane, the new membrane shows high performance for the separation of ETBE and EtOH mixtures, especially under high temperature conditions.

  15. A study on optical properties of poly (ethylene oxide) based polymer electrolyte with different alkali metal iodides

    NASA Astrophysics Data System (ADS)

    Rao, B. Narasimha; Suvarna, R. Padma

    2016-05-01

    Polymer electrolytes were prepared by adding poly (ethylene glycol) dimethyl ether (PEGDME), TiO2 (nano filler), different alkali metal iodide salts RI (R+=Li+, Na+, K+, Rb+, Cs+) and I2 into Acetonitrile gelated with Poly (ethylene oxide) (PEO). Optical properties of poly (ethylene oxide) based polymer electrolytes were studied by FTIR, UV-Vis spectroscopic techniques. FTIR spectrum reveals that the alkali metal cations were coordinated to ether oxygen of PEO. The optical absorption studies were made in the wavelength range 200-800 nm. It is observed that the optical absorption increases with increase in the radius of alkali metal cation. The optical band gap for allowed direct transitions was evaluated using Urbach-edges method. The optical properties such as optical band gap, refractive index and extinction coefficient were determined. The studied polymer materials are useful for solar cells, super capacitors, fuel cells, gas sensors etc.

  16. Ether bridge formation in loline alkaloid biosynthesis

    PubMed Central

    Pan, Juan; Bhardwaj, Minakshi; Faulkner, Jerome R.; Nagabhyru, Padmaja; Charlton, Nikki D.; Higashi, Richard M.; Miller, Anne-Frances; Young, Carolyn A.; Grossman, Robert B.; Schardl, Christopher L.

    2014-01-01

    Lolines are potent insecticidal agents produced by endophytic fungi of cool-season grasses. These alkaloids are composed of a pyrrolizidine ring system and an uncommon ether bridge linking carbons 2 and 7. Previous results indicated that 1-aminopyrrolizidine was a pathway intermediate. We used RNA interference to knock down expression of lolO, resulting in the accumulation of a novel alkaloid identified as exo-1-acetamidopyrrolizidine based on high-resolution MS and NMR. Genomes of endophytes differing in alkaloid profiles were sequenced, revealing that those with mutated lolO accumulated exo-1-acetamidopyrrolizidine but no lolines. Heterologous expression of wild-type lolO complemented a lolO mutant, resulting in the production of N-acetylnorloline. These results indicated that the non-heme iron oxygenase, LolO, is required for ether bridge formation, probably through oxidation of exo-1-acetamidopyrrolizidine. PMID:24374065

  17. Thrust measurement of dimethyl ether arcjet thruster

    NASA Astrophysics Data System (ADS)

    Kakami, Akira; Beppu, Shinji; Maiguma, Muneyuki; Tachibana, Takeshi

    2011-04-01

    The present paper describes thrust measurement results for an arcjet thruster using Dimethyl ether (DME) as the propellant. DME is an ether compound and can be stored as a liquid due to its relatively low freezing point and preferable vapor pressure. The thruster successfully produced high-voltage mode at DME mass flow rates above 30 mg/s, whereas it yielded low-voltage mode below 30 mg/s. Thrust measurements yielded a thrust of 0.15 N and a specific impulse of 270 s at a mass flow rate of 60 mg/s with a discharge power of 1300 W. The DME arcjet thruster was comparable to a conventional one for thrust and discharge power.

  18. Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers.

    PubMed

    Garcés, Karin; Lalrempuia, Ralte; Polo, Víctor; Fernández-Alvarez, Francisco J; García-Orduña, Pilar; Lahoz, Fernando J; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-10-04

    A series of rhodium-NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3 )] (Cy=cyclohexane) and [Rh(H)(CF3 SO3 )(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3 SO3 )(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3 SO3 )(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si-H bond by a metal-ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether.

  19. Promoting environmentally sound management of polybrominated diphenyl ethers in Asia.

    PubMed

    Li, Jinhui; Zhao, Nana; Liu, Xue; Wu, Xiaoyang

    2014-06-01

    Polybrominated diphenyl ethers with persistent organic pollutant properties are required to be controlled by the Stockholm Convention. Recently, polybrominated diphenyl ether contamination has become widespread in Asia, mainly because of the disposal and recycling processes of polybrominated diphenyl ether-containing wastes. The management status, production, usage, import/export, treatment, and disposal, as well as implementation deficiencies for the environmentally sound management of polybrominated diphenyl ethers and polybrominated diphenyl ether-containing materials in ten Asian countries were investigated and assessed in this study. This information could help the participating countries implement the Stockholm Convention and could promote the regional environmentally sound management of polybrominated diphenyl ether-containing articles and products. The results obtained were as follows. (1) Most of the countries studied lacked environmental policies and regulations, or even standards of polybrominated diphenyl ether pollution management and emission control actions. Accurate data on the consumption and importation of polybrominated diphenyl ether-containing materials, however, were not available for all the participating countries. In addition, there were no special treatment or disposal systems for polybrominated diphenyl ether-containing materials, or emission-cutting measures for the treatment of waste in these countries, owing to the lack of sufficient funding or technologies. (2) The improper dismantling of e-waste is a major source of polybrominated diphenyl ether emissions in these countries. (3) Proper e-waste management could result in a breakthrough in the environmentally sound management of this major polybrominated diphenyl ether-containing material flow, and could significantly reduce polybrominated diphenyl ether emissions. Finally, based on the study results, this article puts forward some recommendations for improving the environmentally

  20. Nikola Tesla, the Ether and his Telautomaton

    NASA Astrophysics Data System (ADS)

    Milar, Kendall

    2014-03-01

    In the nineteenth century physicists' understanding of the ether changed dramatically. New developments in thermodynamics, energy physics, and electricity and magnetism dictated new properties of the ether. These have traditionally been examined from the perspective of the scientists re-conceptualizing the ether. However Nikola Tesla, a prolific inventor and writer, presents a different picture of nineteenth century physics. Alongside the displays that showcased his inventions he presented alternative interpretations of physical, physiological and even psychical research. This is particularly evident in his telautomaton, a radio remote controlled boat. This invention and Tesla's descriptions of it showcase some of his novel interpretations of physical theories. He offered a perspective on nineteenth century physics that focused on practical application instead of experiment. Sometimes the understanding of physical theories that Tesla reached was counterproductive to his own inventive work; other times he offered new insights. Tesla's utilitarian interpretation of physical theories suggests a more scientifically curious and invested inventor than previously described and a connection between the scientific and inventive communities.

  1. Biodegradation of glycol ethers in soil

    SciTech Connect

    Gonsior, S.J.; West, R.J.

    1995-08-01

    Because of the widespread use of glycol ethers in applications ranging from consumer products to use as chemical intermediates, there is a need to better understand the fate of these compounds in the environment. Soil biodegradation studies were conducted for three propylene glycol ethers: 1-methoxy-2-propanol, 1-phenoxy-2-propanol, and 1-methoxy-2-propanol acetate. The test compounds were labeled with carbon-14 at either the methoxy or phenoxy substituents. Biodegradation of the three compounds was observed in two sandy loam soils. The time required for disappearance of 50% of the test compounds ranged from < 1 d at 0.2 ppm (w/w) to <7 d at 107 ppm. Degradation rates were slower in a sandy soil, reflecting the lower concentration of microorganisms present. No significant accumulation of intermediate products was observed, and ultimate yields of {sup 14}CO{sub 2} were in the range of 40 to 65% of the initial concentration. Results indicated that the glycol ethers were degraded in a variety of soils under aerobic conditions.

  2. Radiation-chemical synthesis of poly(vinyl alcohol) hydrogel containing dicyclohexano-18-crown-6

    NASA Astrophysics Data System (ADS)

    Zakurdaeva, O. A.; Nesterov, S. V.; Shmakova, N. A.; Semenova, G. K.; Sozontova, E. O.; Feldman, V. I.

    2007-12-01

    Radiation-chemical synthesis of poly(vinyl alcohol) hydrogels containing physically immobilized dicyclohexano-18-crown-6 was carried out. Remarkable gel fraction of 40-70% was observed at absorbed dose of about 5 kGy. Increasing degree of poly(vinyl alcohol) crosslinking led to growth of the efficiency of crown ether immobilization. Post-irradiation thermal annealing of the hydrogel samples at 120 °C for 0.5-5 h resulted in an increase of crown ether retention as compared with non-annealed samples by approximately 20% at the same absorbed dose. Preliminary results on a sorption behavior of the crown-containing hydrogels with respect to Sr 2+ cations in 2.4 M HNO 3 solution are presented.

  3. Synthesis and Structure-Property Relationships of Poly(sulfone)s for Anion Exchange Membranes

    SciTech Connect

    Yan, JL; Moore, HD; Hibbs, MR; Hickner, MA

    2013-10-05

    Membranes based on cationic polymers that conduct anions are important for enabling alkaline membrane fuel cells and other solid-state electrochemical devices that operate at high pH. Anion exchange membranes with poly(arylene ether sulfone) backbones are demonstrated by two routes: chloromethylation of commercially available poly(sulfone)s or radical bromination of benzylmethyl moieties in poly(sulfone)s containing tetramethylbisphenol A monomer residues. Polymers with tethered trimethylbenzyl ammonium moieties resulted from conversion of the halomethyl groups by quaternization with trimethyl amine. The water uptake of the chloromethylated polymers was dependent on the type of poly(sulfone) backbone for a given IEC. Bisphenol A-based Udel (R) poly(sulfone) membranes swelled in water to a large extent while membranes from biphenol-based Radel (R) poly(sulfone), a stiffer backbone than Udel, only showed moderate water uptake. The water uptake of cationic poly(sulfone)s was further reduced by synthesizing tetramethylbisphenol A and 4,4-biphenol-containing poly(sulfone) copolymers where the ionic groups were clustered on the tetramethylbisphenol A residues. The conductivity of all samples scaled with the bulk water uptake. The hydration number of the membranes could be increased by casting membranes from the ionic form polymers versus converting the halomethyl form cast polymers to ionic form in the solid state. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1790-1798, 2013

  4. From ether theory to ether theology: Oliver Lodge and the physics of immortality.

    PubMed

    Raia, Courtenay Grean

    2007-01-01

    This article follows the development of physicist Oliver Lodge's religio-scientific worldview, beginning with his reticent attraction to metaphysics in the early 1880s to the full formulation of his "ether theology" in the late 1890s. Lodge undertook the study of psychical phenomena such as telepathy, telekinesis, and "ectoplasm" to further his scientific investigations of the ether, speculating that electrical and psychical manifestations were linked phenomena that described the deeper underlying structures of the universe, beneath and beyond matter. For Lodge, to fully understand the ether was to force from the universe an ultimate Revelation, and psychical research, as the most modern and probatory science, was poised to replace religion as the means of that disclosure. (c) 2007 Wiley Periodicals, Inc.

  5. Electrochemical measurements of diffusion coefficients of redox-labeled poly(ethylene glycol) dissolved in poly(ethylene glycol) melts

    SciTech Connect

    Haas, O.; Velazquez, C.S.; Porat, Z.; Murray, R.W.

    1995-10-12

    Ferrocene labeled monomethoxy-poly(ethylene glycol)s (MPEG) with molecular weights of 1900 and 750 were used as redox probe solutes in poly(ethylene glycol) melt solvents of molecular weight 750, 2000, and 20000. Cyclic voltammetry and chronoamperometry at microdisk electrodes were employed to measure the diffusion coefficients of the redox probes, which were independent of the probe concentration and varied between 10{sup -7} and 10{sup -10} cm{sup 2}/s. Diffusional activation barrier results also suggest that the ferrocene label does not significantly influence the diffusivity of the probe molecule in the host solvent. Activation barrier, viscosity, and ionic conductivity results show that the LiClO{sub 4} electrolyte does not influence the diffusion barrier or viscosity as long as the ether O/Li{sup +} ratio is >=250 (ca. 0.1 M) which is still a sufficient electrolyte concentration to allow quantitative electrochemical diffusion measurements. 21 refs., 7 figs., 2 tabs.

  6. Synthesis of atactic and isotactic poly(1,2-glycerol carbonate)s: degradable polymers for biomedical and pharmaceutical applications.

    PubMed

    Zhang, Heng; Grinstaff, Mark W

    2013-05-08

    The synthesis and characterization of atactic and isotactic linear poly(benzyl 1,2-glycerol carbonate)s are reported. The poly(benzyl 1,2-glycerol carbonate)s were obtained via the ring-opening copolymerization of rac-/(R)-benzyl glycidyl ether with CO2 using [SalcyCo(III)X] complexes with high carbonate linkage selectivity and polymer/cyclic carbonate selectivity (>99%). Deprotection of the resultant polymers afforded poly(1,2-glycerol carbonate)s with a functionalizable pendant primary hydroxyl group. Poly(1,2-glycerol carbonate) showed a remarkable increase in degradation rate compared to poly(1,3-glycerol carbonate) with a t1/2 ≈ 2-3 days. These polymers fulfill an unmet need for a readily degradable biocompatible polycarbonate.

  7. Effect of acid labile ether protecting groups on the oxide etch resistance and lithographic performance of 248-nm resists

    NASA Astrophysics Data System (ADS)

    Varanasi, Pushkara R.; Cornett, Kathleen M.; Lawson, Margaret C.

    2000-06-01

    In our attempts to develop etch resistance 248 nm positive resists, we have designed and synthesized thermally stable and acid sensitive methylbenzyl ether (MBE) protected poly(hydroxystyrene) derivatives. Results presented in this paper clearly illustrate that the MBE protecting group provides superior etch resistance to conventional carbonate, ester and acetal/ketal based protecting groups. It is also shown that the MBE protecting group is thermally stable and undergoes acid catalyzed deprotection leading to preferential rearrangement products due to electrophilic ring substitution. Such a rearrangement is shown to provide a unique mechanism to reduce/eliminate resist shrinkage and improve lithographic performance.

  8. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  9. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  10. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  11. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  12. 40 CFR 721.10067 - Ether amine phosphonate salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ether amine phosphonate salt (generic... Specific Chemical Substances § 721.10067 Ether amine phosphonate salt (generic). (a) Chemical substances... ether amine phosphonate salt (PMNs P-05-57, P-05-58, P-05-59, P-05-61, P-05-62, P-05-63, P-05-64, and...

  13. IRIS Toxicological Review of Ethyl Tertiary Butyl Ether (Etbe) ...

    EPA Pesticide Factsheets

    EPA is conducting a peer review and public comment of the scientific basis supporting the human health hazard and dose-response assessment of ethyl tertiary butyl ether (ETBE) that when finalized will appear on the Integrated Risk Information System (IRIS) database. The draft Toxicological Review of Ethyl Tertiary Butyl Ether provides scientific support and rationale for the hazard and dose-response assessment pertaining to chronic exposure to ethyl tertiary butyl ether.

  14. Glycol ether/siloxane polymer penetrating and lubricating composition

    SciTech Connect

    MacIntosh, D.H.

    1981-02-03

    A penetrating and lubricating composition consists of a silicone lubricant dissolved in a glycol ether carrier having a very low surface tension. The glycol ether gives the composition the ability to penetrate into the cracks between two seized or corroded elements and dissolve any rust or corrosion present. The glycol ether then volitalizes leaving a coating of silicone on the parts to serve as a lubricant and prevent further corrosion.

  15. Synthesis and Characterization of a Poly(ethylene glycol)-Poly(simvastatin) Diblock Copolymer

    PubMed Central

    Asafo-Adjei, Theodora A.; Dziubla, Thomas D.; Puleo, David A.

    2014-01-01

    Biodegradable polyesters are commonly used as drug delivery vehicles, but their role is typically passive, and encapsulation approaches have limited drug payload. An alternative drug delivery method is to polymerize the active agent or its precursor into a degradable polymer. The prodrug simvastatin contains a lactone ring that lends itself to ring-opening polymerization (ROP). Consequently, simvastatin polymerization was initiated with 5 kDa monomethyl ether poly(ethylene glycol) (mPEG) and catalyzed via stannous octoate. Melt condensation reactions produced a 9.5 kDa copolymer with a polydispersity index of 1.1 at 150 °C up to a 75 kDa copolymer with an index of 6.9 at 250 °C. Kinetic analysis revealed first-order propagation rates. Infrared spectroscopy of the copolymer showed carboxylic and methyl ether stretches unique to simvastatin and mPEG, respectively. Slow degradation was demonstrated in neutral and alkaline conditions. Lastly, simvastatin, simvastatin-incorporated molecules, and mPEG were identified as the degradation products released. The present results show the potential of using ROP to polymerize lactone-containing drugs such as simvastatin. PMID:25431653

  16. Divinyl ether synthase gene, and protein and uses thereof

    DOEpatents

    Howe, Gregg A.; Itoh, Aya

    2006-12-26

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  17. Divinyl ether synthase gene and protein, and uses thereof

    DOEpatents

    Howe, Gregg A [East Lansing, MI; Itoh, Aya [Tsuruoka, JP

    2011-09-13

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  18. Ether Cleavage Re-Investigated: Elucidating the Mechanism of BBr3-Facilitated Demethylation of Aryl Methyl Ethers

    PubMed Central

    Kosak, Talon M; Conrad, Heidi A; Korich, Andrew L; Lord, Richard L

    2015-01-01

    One of the most well-known, highly utilized reagents for ether cleavage is boron tribromide (BBr3), and this reagent is frequently employed in a 1:1 stoichiometric ratio with ethers. Density functional theory calculations predict a new mechanistic pathway involving charged intermediates for ether cleavage in aryl methyl ethers. Moreover, these calculations predict that one equivalent of BBr3 can cleave up to three equivalents of anisole, producing triphenoxyborane [B(OPh)3] prior to hydrolysis. These predictions were validated by gas chromatography analysis of reactions where the BBr3:anisole ratio was varied. Not only do we confirm that sub-stoichiometric equivalents may be used for ether demethylation, but the findings also support our newly proposed three cycle mechanism for cleavage of aryl methyl ethers. PMID:26693209

  19. Molecular Engineering of Liquid Crystalline Polymers by Living Polymerization. 9. Living Cationic Polymerization of 5-((4-Cyano-4’-Biphenyl) oxy)pentyl Vinyl Ethers and 7-((4-Cyano-4’-Biphenyl)oxy)heptyl Vinyl Ether, and the Mesomorphic Behavior of the Resulting Polymers

    DTIC Science & Technology

    1990-10-16

    REPRODUCEDO A"? GOVERPNME14T EXPENSE AD 2979 T.pOCUMENTATION PiA,4j -* L E is RkEPoRT SC-R-Y CLA i.ATiO It lb RESTRiCTovE MARKiNGS 26 SECURITYr C...PROCuREMENT INSTRUMENT IDENTIFICATION NUMBER OGN IZAT7ION If picb & L . AZORE SS (Ciay, Sr, arad ZIP Coot) 10 SOURCE OF ’UNDING NUMBERS office of Naval...mesomorphic behavior of poly( L .-.) and poly(6-_7) is discussed and compared to that of 5-[(4-cyano-4’- biphenyl)oxy]pentyl ethyl ether (8)and 7-f (4-cyano

  20. Poly(N-isopropylacrylamide)/poly(dopamine) capsules.

    PubMed

    Zhang, Yan; Teo, Boon M; Goldie, Kenneth N; Städler, Brigitte

    2014-05-20

    Polymer capsules are an interesting concept considered in nanobiotechnology. Approaches that facilitate their assembly remain sought after. Poly(dopamine) (PDA) has been considered and successfully applied in this context. We recently demonstrated that PDA could be copolymerized with different types of poly(N-isopropylacrylamide) (pNiPAAm) to assemble mixed films on planar substrates. Herein, we transferred this approach onto colloidal substrates and characterized the film thickness depending on the film composition and template particles size. While the membrane of capsules assembled using 5 μm template particles exhibited strong dependency on the film composition, smaller templates led to capsules with similar membrane thickness. We then compared the permeability of different capsules using fluorescently labeled dextran and fluorescein. We found that the permeability of capsules was heavily dependent on the polymer composition and the template particle size. These fundamental findings contribute to the potential of these capsules, assembled in one-step, for biomedical applications.

  1. Unprecedented reactions: from epichlorohydrin to epoxyglycidyl substituted divinyl ether and its conversion into epoxyglycidyl propargyl ether.

    PubMed

    Yao, Yiwu; Li, Zheng; Qiu, Yatao; Bai, Jinhong; Su, Jinyue; Zhang, Dayong; Jiang, Sheng

    2015-09-18

    The reaction of epichlorohydrin with concentrated sodium hydroxide in hexane under phase transfer conditions has surprisingly led to the formation of the symmetrical di(3-epoxyglycidyl-1-propenyl) ether 1 which contains both nucleophilic and electrophilic moieties. When it was reacted with n-butyllithium, intermediate 1 once again surprisingly generated epoxyglycidyl propargyl ether, which was further reacted in situ with a variety of benzaldehydes to furnish the corresponding substituted propargylic alcohols in good yields. While the reaction is operationally simple, it provides a powerful method for the synthesis of the important products from commodity materials such as epichlorohydrin. Moreover, these reactions may have revealed that some fundamental properties of the hydroxide anion in those once thought straightforward reactions are not well understood. A careful analysis of the experimental data suggests that an unprecedented concerted elimination of the epoxyglycidyl ether with sodium hydroxide may be operative and an alpha deprotonation followed by alpha elimination of the di(3-epoxyglycidyl-1-propenyl) ether with alkyllithium may have been involved.

  2. Unprecedented reactions: from epichlorohydrin to epoxyglycidyl substituted divinyl ether and its conversion into epoxyglycidyl propargyl ether

    PubMed Central

    Yao, Yiwu; Li, Zheng; Qiu, Yatao; Bai, Jinhong; Su, Jinyue; Zhang, Dayong; Jiang, Sheng

    2015-01-01

    The reaction of epichlorohydrin with concentrated sodium hydroxide in hexane under phase transfer conditions has surprisingly led to the formation of the symmetrical di(3-epoxyglycidyl-1-propenyl) ether 1 which contains both nucleophilic and electrophilic moieties. When it was reacted with n-butyllithium, intermediate 1 once again surprisingly generated epoxyglycidyl propargyl ether, which was further reacted in situ with a variety of benzaldehydes to furnish the corresponding substituted propargylic alcohols in good yields. While the reaction is operationally simple, it provides a powerful method for the synthesis of the important products from commodity materials such as epichlorohydrin. Moreover, these reactions may have revealed that some fundamental properties of the hydroxide anion in those once thought straightforward reactions are not well understood. A careful analysis of the experimental data suggests that an unprecedented concerted elimination of the epoxyglycidyl ether with sodium hydroxide may be operative and an alpha deprotonation followed by alpha elimination of the di(3-epoxyglycidyl-1-propenyl) ether with alkyllithium may have been involved. PMID:26383123

  3. Unprecedented reactions: from epichlorohydrin to epoxyglycidyl substituted divinyl ether and its conversion into epoxyglycidyl propargyl ether

    NASA Astrophysics Data System (ADS)

    Yao, Yiwu; Li, Zheng; Qiu, Yatao; Bai, Jinhong; Su, Jinyue; Zhang, Dayong; Jiang, Sheng

    2015-09-01

    The reaction of epichlorohydrin with concentrated sodium hydroxide in hexane under phase transfer conditions has surprisingly led to the formation of the symmetrical di(3-epoxyglycidyl-1-propenyl) ether 1 which contains both nucleophilic and electrophilic moieties. When it was reacted with n-butyllithium, intermediate 1 once again surprisingly generated epoxyglycidyl propargyl ether, which was further reacted in situ with a variety of benzaldehydes to furnish the corresponding substituted propargylic alcohols in good yields. While the reaction is operationally simple, it provides a powerful method for the synthesis of the important products from commodity materials such as epichlorohydrin. Moreover, these reactions may have revealed that some fundamental properties of the hydroxide anion in those once thought straightforward reactions are not well understood. A careful analysis of the experimental data suggests that an unprecedented concerted elimination of the epoxyglycidyl ether with sodium hydroxide may be operative and an alpha deprotonation followed by alpha elimination of the di(3-epoxyglycidyl-1-propenyl) ether with alkyllithium may have been involved.

  4. Syntheses and GABA uptake properties of 6-ether- and 6-enol ether-substituted nipecotic acids.

    PubMed

    N'Goka, Victor; Bissantz, Caterina; Bisel, Philippe; Stenbøl, Tine B; Krogsgaard-Larsen, Povl; Schlewer, Gilbert

    2004-07-01

    6-aralkylether- and 6-arylenol-ether-substituted nipecotic acids were synthesized. These analogues are poor GABA uptake inhibitors. The electronegative region concept developed in the N-substituted nipecotic acid series cannot be transferred on the side chain of this series of 6-substituted analogues.

  5. Epoxy resin cure. [Phenyl glycidyl ether

    SciTech Connect

    Smith, R.E.; Woodburn, G.L.

    1986-07-01

    The reactions that occur between the model epoxy, phenyl glycidyl ether, and the cure agent dicyandiamide (DICY) have been investigated using nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), gel permeation chromatography (GPC), and high-performance liquid chromatography (HPLC) techniques. It is shown that the reaction at 130/sup 0/C requires 90 min for completion when catalyzed by boron trifluoride monoethyl amine (BF/sub 3/-MEA). At least three major products are formed. The identity of these products is based on previously published spectroscopic data. 3 refs., 5 figs.

  6. An Exposure Assessment of Polybrominated Diphenyl Ethers ...

    EPA Pesticide Factsheets

    EPA announced the availability of the final report, An Exposure Assessment of Polybrominated Diphenyl Ethers. This report provides a comprehensive assessment of the exposure of Americans to this class of persistent organic pollutants. Individual chapters in this document address: the production, use, and lifecycle of PBDEs; environmental fate; environmental levels; and human exposure. This final report addresses the exposure assessment needs identified in the OPBDE Workgroup project plan. It provides a comprehensive assessment of the exposure of Americans to this class of persistent organic pollutants. Individual chapters in this document address: the production, use, and lifecycle of PBDEs; environmental fate; environmental levels; and human exposure.

  7. Ultra-fast RAFT polymerisation of poly(ethylene glycol) acrylate in aqueous media under mild visible light radiation at 25 degrees C.

    PubMed

    Shi, Yi; Gao, Huan; Lu, Lican; Cai, Yuanli

    2009-03-21

    Mild visible light was sufficient to activate RAFT polymerisation of poly(ethylene glycol) methyl ether acrylate in 50 wt% water at 25 degrees C, leading to an ultra-fast and well-controlled living RAFT polymerisation with more than 80% monomer conversion; this is the first example of an ultra-fast RAFT polymerisation under such environmentally friendly mild aqueous conditions.

  8. Obstetric and Other Uses of Ether Before Ether Day, According to the Boston Medical and Surgical Journal of 1828-1846.

    PubMed

    Stoller, Sundrayah N; Minehart, Rebecca D; Alston, Theodore A

    2016-04-01

    From the inception of the Boston Medical and Surgical Journal in 1828 until the prominent public demonstration of surgical anesthesia on Ether Day of 1846, ether was often mentioned in the journal. Many of the examples were related to obstetrics. Because molecular structures were not available in the early 1800s, diverse volatile liquids were termed ethers. In addition to sulphuric ether, so-called ethers included cyanide-releasing propionitrile and ethanolic solutions of chloroform and of the potent vasodilator ethyl nitrite. Familiarity with anesthetically unsuitable ethers may have long deterred consideration of inhaled sulphuric ether for analgesia and anesthesia.

  9. PEEK (polyether-ether-ketone)-coated nitinol wire: Film stability for biocompatibility applications

    NASA Astrophysics Data System (ADS)

    Sheiko, Nataliia; Kékicheff, Patrick; Marie, Pascal; Schmutz, Marc; Jacomine, Leandro; Perrin-Schmitt, Fabienne

    2016-12-01

    High quality biocompatible poly-ether-ether-ketone (PEEK) coatings were produced on NiTi shape memory alloy wires using dipping deposition from colloidal aqueous PEEK dispersions after substrate surface treatment. The surface morphology and microstructure were investigated by Scanning Electron Microscopy at every step of the process from the as-received Nitinol substrate to the ultimate PEEK-coated NiTi wire. Nanoscratch tests were carried out to access the adhesive behavior of the polymer coated film to the NiTi. The results indicate that the optimum process conditions in cleaning, chemical etching, and electropolishing the NiTi, were the most important and determining parameters to be achieved. Thus, high quality PEEK coatings were obtained on NiTi wires, straight or curved (even with a U-shape) with a homogeneous microstructure along the wire length and a uniform thickness of 12 μm without any development of cracks or the presence of large voids. The biocompatibility of the PEEK coating film was checked in fibrobast cultured cells. The coating remains stable in biological environment with negligible Ni ion release, no cytotoxicity, and no delamination observed with time.

  10. Mitigated reactive oxygen species generation leads to an improvement of cell proliferation on poly[glycidyl methacrylate-co-poly(ethylene glycol) methacrylate] functionalized polydimethylsiloxane surfaces.

    PubMed

    Yu, Ling; Shi, ZhuanZhuan; Gao, LiXia; Li, ChangMing

    2015-09-01

    In vitro cell-based analysis is strongly affected by material's surface chemical properties. The cell spreading, migration, and proliferation on a substrate surface are initiated and controlled by successful adhesion, particularly for anchor-dependent cells. Unfortunately, polydimethylsiloxane (PDMS), one of the most used polymeric materials for construction of microfluidic and miniaturized biomedical analytic devices, is not a cell-friendly surface because of its inherent hydrophobic property. Herein, a poly[glycidyl methacrylate-co-poly(ethylene glycol) methacrylate] (poly(GMA-co-pEGMA)) polymer brush was synthesized on a PDMS surface through a surface-initiated atom-transfer radical polymerization method. Contact angle and Fourier transform infrared characterization show that the poly (GMA-co-pEGMA) polymer brush functionalization can increase wettability of PDMS and introduce epoxy, hydroxyl, and ether groups into PDMS surface. In vitro cell growth assay demonstrates that cell adhesion and proliferation on poly(GMA-co-pEGMA) polymer brush-functionalized PDMS (poly(GMA-co-pEGMA)@PDMS) are better than on pristine PDMS. Additionally, immobilization of collagen type I (CI) and fibronectin (FN) on poly(GMA-co-pEGMA)@PDMS is better than direct coating of CI and FN on pristine PDMS to promote cell adhesion. Furthermore, increased intracellular reactive oxygen species and cell mitochondrial membrane depolarization, two indicators of cell oxidative stress, are observed from cells growing on pristine PDMS, but not from those on poly(GMA-co-pEGMA)@PDMS. Collectively, we demonstrate that poly(GMA-co-pEGMA) functionalization can enhance cell adhesion and proliferation on PDMS, and thus can be potentially used for microfluidic cell assay devices for cellular physiology study or drug screening. © 2015 Wiley Periodicals, Inc.

  11. Biosynthesis of archaeal membrane ether lipids

    PubMed Central

    Jain, Samta; Caforio, Antonella; Driessen, Arnold J. M.

    2014-01-01

    A vital function of the cell membrane in all living organism is to maintain the membrane permeability barrier and fluidity. The composition of the phospholipid bilayer is distinct in archaea when compared to bacteria and eukarya. In archaea, isoprenoid hydrocarbon side chains are linked via an ether bond to the sn-glycerol-1-phosphate backbone. In bacteria and eukarya on the other hand, fatty acid side chains are linked via an ester bond to the sn-glycerol-3-phosphate backbone. The polar head groups are globally shared in the three domains of life. The unique membrane lipids of archaea have been implicated not only in the survival and adaptation of the organisms to extreme environments but also to form the basis of the membrane composition of the last universal common ancestor (LUCA). In nature, a diverse range of archaeal lipids is found, the most common are the diether (or archaeol) and the tetraether (or caldarchaeol) lipids that form a monolayer. Variations in chain length, cyclization and other modifications lead to diversification of these lipids. The biosynthesis of these lipids is not yet well understood however progress in the last decade has led to a comprehensive understanding of the biosynthesis of archaeol. This review describes the current knowledge of the biosynthetic pathway of archaeal ether lipids; insights on the stability and robustness of archaeal lipid membranes; and evolutionary aspects of the lipid divide and the LUCA. It examines recent advances made in the field of pathway reconstruction in bacteria. PMID:25505460

  12. Biosynthesis of archaeal membrane ether lipids.

    PubMed

    Jain, Samta; Caforio, Antonella; Driessen, Arnold J M

    2014-01-01

    A vital function of the cell membrane in all living organism is to maintain the membrane permeability barrier and fluidity. The composition of the phospholipid bilayer is distinct in archaea when compared to bacteria and eukarya. In archaea, isoprenoid hydrocarbon side chains are linked via an ether bond to the sn-glycerol-1-phosphate backbone. In bacteria and eukarya on the other hand, fatty acid side chains are linked via an ester bond to the sn-glycerol-3-phosphate backbone. The polar head groups are globally shared in the three domains of life. The unique membrane lipids of archaea have been implicated not only in the survival and adaptation of the organisms to extreme environments but also to form the basis of the membrane composition of the last universal common ancestor (LUCA). In nature, a diverse range of archaeal lipids is found, the most common are the diether (or archaeol) and the tetraether (or caldarchaeol) lipids that form a monolayer. Variations in chain length, cyclization and other modifications lead to diversification of these lipids. The biosynthesis of these lipids is not yet well understood however progress in the last decade has led to a comprehensive understanding of the biosynthesis of archaeol. This review describes the current knowledge of the biosynthetic pathway of archaeal ether lipids; insights on the stability and robustness of archaeal lipid membranes; and evolutionary aspects of the lipid divide and the LUCA. It examines recent advances made in the field of pathway reconstruction in bacteria.

  13. [Aerobic microbial degradation of polybrominated diphenyl ethers].

    PubMed

    Ding, Juan; Zhou, Juan; Jiang, Wei-Ying; Gao, Shi-Xiang

    2008-11-01

    The biodegradation of 4, 4'-dibromodipheny ether (BDE15) and decabromodiphenyl ether (BDE209) by white rot fungi under aerobic conditions was studied. Effects of non-ionic surfactant Tween 80 and beta-cyclodextrin as solubilizers on the apparent solubilities and biodegradation rates of BDE15 and BDE209 were also evaluated. The results showed that both BDE15 and BDE209 were efficiently degraded by white rot fungi. The degradation rates were 43.0% and 62.5% for BDE209 and BDE15, respectively, after 10 d incubation. The degradation of BDE209 was greatly enhanced by addition of Tween 80 (< or = 700 mg/L) and beta-cyclodextrin, which may own to their solubilization effects on BDE209. However, Tween 80 at a high concentration (900 mg/L) would restrain the fungal growth, thereby decrease the degradation of BDE209. Addition of Tween 80 and beta-cyclodextrin exhibited some negative effects on the degradation of BDE15, which may due to decreased concentration of free BDE15 in water solution resulted from inclusion function of Tween 80 micelles and beta-cyclodextrin cavity, although the apparent solubility of BDE15 was drastically increased by both of them.

  14. Process for producing dimethyl ether from synthesis gas

    DOEpatents

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  15. Process for producing dimethyl ether form synthesis gas

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  16. IRIS Toxicological Review of Decabromodiphenyl Ether (Final Report)

    EPA Science Inventory

    EPA announced the release of the final report, Toxicological Review of Decabromodiphenyl Ether: in support of the Integrated Risk Information System (IRIS). The updated Summary for Decabromodiphenyl Ether and accompanying toxicological review have been added to the IRIS Da...

  17. IRIS Toxicological Review of Decabromodiphenyl Ether (Final Report)

    EPA Science Inventory

    EPA is announcing the release of the final report, Toxicological Review of Decabromodiphenyl Ether: in support of the Integrated Risk Information System (IRIS). The updated Summary for Decabromodiphenyl Ether and accompanying Quickview have also been added to the IRIS Data...

  18. 48. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    48. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, 5TH LEVEL, LOOKING NORTH AT ETHER AND ALCOHOL CONDENSERS AT TOP OF TOWER. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  19. 46. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    46. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, CONTROL PANEL LEVEL (2ND DECK) OF ETHER AND ALCOHOL STILL BUILDING, LOOKING NORTH, SHOWING TWO ALCOHOL DISTILLATION TOWERS BEHIND 'MIXED SOLVENT UNIT' CONTROL PANEL. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ

  20. 47. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    47. BUILDING NO. 519, ETHER AND ALCOHOL RECOVERY HOUSE, INTERIOR, 4TH LEVEL, LOOKING NORTH AT TOPS OF ALCOHOL AND ETHER DISTILLATION TOWERS. - Picatinny Arsenal, 500 Area, Powder Factory & Power House, State Route 15 near I-80, Dover, Morris County, NJ