WorldWideScience

Sample records for acid-methyl vinyl ether

  1. Interpolymer complexses of vinyl ether copolymer with polyacrylic and polymethacrylic acids

    Directory of Open Access Journals (Sweden)

    E. Shaikhutdinov

    2012-03-01

    Full Text Available The interactions between macromolecules of copolymers based on vinyl ethers (vinyl ether of monoethanolamine and vinyl buthyl ether and 2-acryloilamido-2-methylpropanesulphonic acid with polyacrylic and polymethacrylic acid and, as well as study the effect of interpolymer interactions in the adsorption of polymers at the aqueous solution-air interface were investigated. The observed synergistic increase in surface activity of macromolecules into polyelectrolyte mixtures explained by the formation of interpolymer complexes polyacid - copolymer.

  2. Williamson alkylation approach to the synthesis of poly(alkyl vinyl ether) copolymers

    International Nuclear Information System (INIS)

    Markova, D.; Christova, D.; Velichkova, R.

    2008-01-01

    A method for synthesis of poly(alkyl vinyl ether-co-vinyl alcohol) copolymers was developed based on the Williamson's alkylation of poly(vinyl acetate) (PVAc) with alkyl iodides. The influence of the alkylating agent and the reaction conditions on the efficiency of the modification reaction was investigated. The copolymers obtained were characterized by means of 1 H NMR and GPC. It was proved that by applying the proposed method copolymers of different composition and properties containing methyl vinyl ether, ethyl vinyl ether as well as n-butyl vinyl ether units could be prepared. Poly(methyl vinyl ether-co-vinyl alcohol)s of high degree of methylation exhibit sharp temperature response at 38-39 deg C in aqueous solution typical of the so-called smart polymers. (authors)

  3. Production of methyl-vinyl ketone from levulinic acid

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A [Verona, WI; West,; Ryan, M [Madison, WI

    2011-06-14

    A method for converting levulinic acid to methyl vinyl ketone is described. The method includes the steps of reacting an aqueous solution of levulinic acid, over an acid catalyst, at a temperature of from room temperature to about 1100 K. Methyl vinyl ketone is thereby formed.

  4. Additive effects on phase transition and interactions in poly(vinyl methyl ether) solutions

    Czech Academy of Sciences Publication Activity Database

    Starovoytova, Larisa; Šťastná, J.; Šturcová, Adriana; Konefal, Rafal; Dybal, Jiří; Velychkivska, Nadiia; Radecki, M.; Hanyková, L.

    2015-01-01

    Roč. 7, č. 12 (2015), s. 2572-2583 ISSN 2073-4360 R&D Projects: GA ČR(CZ) GA13-23392S Institutional support: RVO:61389013 Keywords : additives * LCST * poly(vinyl methyl ether) Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.944, year: 2015

  5. Morphology in binary blends of poly(vinyl methyl ether) and epsilon-caprolactone-trimethylene carbonate diblock copolymer

    NARCIS (Netherlands)

    Luyten, MC; Bogels, EJF; vanEkenstein, GORA; tenBrinke, G; Bras, W; Komanschek, BE; Ryan, AJ

    The morphology of symmetric diblock copolymer of epsilon-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

  6. Morphology in binary blends of poly(vinyl methyl ether) and ε-caprolactone-trimethylene carbonate diblock copolymer

    NARCIS (Netherlands)

    Luyten, M.C.; Bögels, E.J.F.; Alberda van Ekenstein, G.O.R.; Brinke, G. ten; Bras, W.; Komanschek, B.E.; Ryan, A.J.

    1997-01-01

    The morphology of symmetric diblock copolymer of ε-caprolactone (PCL) and trimethylene carbonate (PTMC), in blends with poly(vinyl methyl ether) (PVME) is investigated with (modulated) differential scanning calorimetry (d.s.c.), time resolved small angle (SAXS) and wide angle (WAXS) X-ray

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

    Science.gov (United States)

    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.

  8. Convenient procedures for the α-metallation of vinylic ethers and thioethers

    NARCIS (Netherlands)

    Verkruijsse, H.D.; Brandsma, L.; Schleyer, P. von R.

    1987-01-01

    Ethyl vinyl ether H2C=CHOC2H5 and the analogous cyclic vinylic ethers dehydrofuran and 2,3-dihydropyran can be potassiated at −20°C in the α-position with a 1/1/1 molar mixture of BuLi, t-BuOK and TMEDA in hexane. Methyl vinyl sulfide is potassiated very smoothly by a 1/1 molar mixture of BuLi and

  9. Oil recovery with sulfomethylated poly (lower alkyl vinyl ether/maleic anhydride)

    Energy Technology Data Exchange (ETDEWEB)

    Norton, C.J.; Falk, D.O.

    1973-05-22

    Lower alkyl vinyl ether e.g., methyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, hexyl vinyl ether, is copolymerized conventionally with maleic anhydride, the resulting copolymer is treated with ammonia or ammonium hydroxide to form the partial amide-ammonium salt, and this salt is in turn treated with formaldehyde and thereafter or simultaneously with ammonium or alkali metal salt sulfite (including bisulfites, etc.) to form an at least partially sulfomethylated copolymer. Aqueous solutions of the sulfomethylated copolymer are useful in increasing the viscosity of drive fluids used in the supplemented recovery of petroleum from subterranean formations. In general, enhancing the polyionic character of mobility control agents used in supplemented recovery of petroleum provides enhanced recovery. Achieving this enhancement of polyionic character through use of sulfonate groups provides a mobility control agent with good ability to sustain viscosity in the presence of brine and lime, usually present in the connate waters of petroleum-bearing formations. (7 claims)

  10. Thermodynamic and Kinetic Behavior of the Polystyrene/Poly(vinyl methyl ether) Blend as Studied by Excimer Fluorescence.

    Science.gov (United States)

    1986-01-02

    AD-A±63 895 THERMODYNAMIC AND KINETIC BEHAVIOR OF THE / POLYSTYRENE/POLY(YINYL METHYL E..(U) STANFORD UNIY CALIFDEPT OF CHEMICAL ENGINEERING C N...Polystyrene/Poly(vinyl methyl ether) Blend 7. DEcFRMN 81 toOR 30USptE8 00~ as Studied by Excimer Fluorescence 6 EFRIGOG EOTNME *AUTHOR() a. CONTRACT OR GRANT...werea fondoare ihemoriisof * ~ Ex e sp fluodecositionsdu to deud Gen e and hoog Pinus Florsneis shownhase migrationprocSECURITY CLASIFICTIO OFd

  11. Synthesis and properties of the metallo-supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]·AgNO3: Ag+/Cu2+ ion exchange and effective antibacterial activity

    KAUST Repository

    Xu, Feng

    2014-01-01

    The commercial polymeric anhydride poly(methyl vinyl ether-alt-maleic anhydride) (PVM/MA) is converted by reaction with NaOH to give poly(methyl vinyl ether-alt-mono-sodium maleate) (PVM/Na-MA). By addition of AgNO 3-solution, the formation of the silver(i) supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]·AgNO 3 is reported. Freeze-dried samples of the hydrogel show a mesoporous network of polycarboxylate ligands that are crosslinked by silver(i) cations. In the intact hydrogel, ion-exchange studies are reported and it is shown that Ag+ ions can be exchanged by copper(ii) cations without disintegration of the hydrogel. The silver(i) hydrogel shows effective antibacterial activity and potential application as burn wound dressing. © the Partner Organisations 2014.

  12. Radiation-induced cationic curing of vinyl ethers

    International Nuclear Information System (INIS)

    Lapin, S.C.

    1992-01-01

    Recently there has been an increasing interest in nonacrylate radiation-curable coatings. Vinyl ethers are particularly reactive under cationic polymerization reaction conditions. The high efficiency of the photoacid initiators combined with the high reactivity of vinyl ether monomers makes this a potentially very useful system. This chapter discusses the preparation of vinyl ethers, introduces vinyl ether-functional monomers and oligomers, describes radiation-induced cationic polymerization of vinyl ethers, and discusses various coating systems. Throughout the chapter, an emphasis is placed on radiation-curable coating applications. 64 refs., 5 figs., 11 tabs

  13. Synthesis and Properties of the Metallo-Supramolecular Polymer Hydrogel Poly[methyl vinyl ether-alt-mono-sodium maleate]∙AgNO3

    KAUST Repository

    Al-Dossary, Mona S.

    2014-05-01

    Gels are a special class of materials which are composed of 3D networks of crosslinked polymer chains that encapsulate liquid/air in the matrix. They can be classified into organogels or hydrogels (organic solvent for organogel and water for hydrogel). For hydrogels that contain metallic elements in the form of ions, the term of metallo-supramolecular polymer hydrogel (MSPHG) is often used. The aim of this project is to develop a kind of new MSPHG and investigate its properties and possible applications. The commercial polymeric anhydride poly(methyl vinyl ether-alt-maleic anhydride) (PVM/MA) is converted by reaction with NaOH to give poly(methyl vinyl ether-alt-monosodium maleate) (PVM/Na-MA). By addition of AgNO3-solution, the formation of the silver(I) supramolecular polymer hydrogel poly[methyl vinyl ether-alt-mono-sodium maleate]∙AgNO3 is obtained. Freeze-dried samples of the hydrogel show a mesoporous network of polycarboxylate ligands that are crosslinked by silver(I) cations. The supercritical CO2 dried silver(I) hydrogel was characterized by FT-IR, SEM-EDAX, TEM, TGA and Physical adsorption (BET) measurements. The intact silver(I) hydrogel was characterized by cryo-SEM. In the intact hydrogel, ion-exchange studies are reported and it is shown that Ag+ ions can be exchanged by copper(II) cations without disintegration of the hydrogel. The silver(I) hydrogel shows effective antibacterial activity and potential application as burn wound dressing.

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

    Directory of Open Access Journals (Sweden)

    Charu Vashisth Rohatgi

    2015-03-01

    Full Text Available 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.

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

    Science.gov (United States)

    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

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

    Directory of Open Access Journals (Sweden)

    J. Varshosaz

    2014-01-01

    Full Text Available 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.

  17. Densities and derived thermodynamic properties of the binary systems of 1,1-dimethylethyl methyl ether with allyl methacrylate, butyl methacrylate, methacrylic acid, and vinyl acetate at T = (298.15 and 308.15) K

    International Nuclear Information System (INIS)

    Wisniak, Jaime; Peralta, Rene D.; Infante, Ramiro; Cortez, Gladis

    2005-01-01

    Densities of the binary systems of 1,1-dimethylethyl methyl ether (MTBE) with allyl methacrylate, butyl methacrylate, methacrylic acid, and vinyl acetate have been measured as a function of the composition, at 298.15 and 308.15 K and atmospheric pressure, using an Anton Paar DMA 5000 oscillating U-tube densimeter. The calculated excess molar volumes were correlated with the Redlich-Kister equation and with a series of Legendre polynomials. The excess molar volumes are negative for the binaries of MTBE + methacrylates; the system MTBE with vinyl acetate presents near ideal behavior. The excess coefficient of thermal expansion is positive for all the systems studied here; the value of the coefficient for the system MTBE + allyl methacrylate is at least three times larger than that for the other systems

  18. Thermodynamic and kinetic analysis of phase separation of temperature-sensitive poly(vinyl methyl ether) in the presence of hydrophobic tert-butyl alcohol

    Czech Academy of Sciences Publication Activity Database

    Velychkivska, Nadiia; Bogomolova, Anna; Filippov, Sergey K.; Starovoytova, Larisa; Labuta, J.

    2017-01-01

    Roč. 295, č. 8 (2017), s. 1419-1428 ISSN 0303-402X R&D Projects: GA ČR(CZ) GC15-10527J Institutional support: RVO:61389013 Keywords : phase separation * coil-globule transition * poly(vinyl methyl ether) Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.723, year: 2016

  19. NMR study of temperature-induced phase separation and polymer-solvent interactions in poly(vinyl methyl ether)/D.sub.2./sub.O/ethanol solutions

    Czech Academy of Sciences Publication Activity Database

    Hanyková, L.; Labuta, J.; Spěváček, Jiří

    2006-01-01

    Roč. 47, č. 17 (2006), s. 6107-6116 ISSN 0032-3861 Grant - others:GA UK 294/2004/B Institutional research plan: CEZ:AV0Z40500505 Keywords : poly(vinyl methyl ether)/D2O/ ethanol solutions * temperature-induced phase separation * 1H and 13C NMR spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.773, year: 2006

  20. Synthesis of Poly(vinyl ether) Thermoplastic Elastomers Having Functional Soft Segments

    OpenAIRE

    今枝, 嗣人; 漆崎, 美智遠; 阪口, 壽一; 橋本, 保; Tsuguto, IMAEDA; Michio, URUSHISAKI; Toshikazu, SAKAGUCHI; Tamotsu, HASHIMOTO

    2013-01-01

    The ABA-type triblock copolymers consisting of poly(2-adarnantyl vinyl ether) [poly(2-AdVE) as outer hard segments and poly(6-acetoxyhexyl vinyl ether) [poly(AcHVE)] poly(6-hydroxyhexyl vinyl ether) [poly(H HVE)], or poly(2-(2-methoxyethoxy)ethyl vinyl ether [poly(MOEOVE)] as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxy, and oxyethylene units in their soft segments, the two polymer seg...

  1. Thermogravimetric analysis of the polymer acrylate-vinyl ether mixture cured by radiation

    International Nuclear Information System (INIS)

    Danu, Sugiarto

    1998-01-01

    An experiment on thermal stability of the polymer acrylate-vinyl ether mixture cured by radiation have been done using thermogravimetric analysis. Three kinds of acrylic oligomers i.e., epoxy acrylate, urethane acrylate, and polypropylene glycol diacrylate, and vinyl ether monomers i.e., triethylene glycol divinyl ether (DVE-3), 1,4-cyclohexane dimethanol divinyl ether (CHVE), and butanediol monovinyl ether (HBVE) were used in the experiment. Reaction was taken via radical and cationic polymerisation. In case of cationic polymerisation, diphenyliodonium hexafluorophosphate fotoinisiator was used in the formulation. Thermogravimetric analysis was conducted in a nitrogen atmosphere at a flow rate of 40 ml/minute with a constant heating rate 10 o C and evaluation range were done from 25 to 500 o C. The results of thermogravimetric analysis showed that acrylate and DVE-3 mixture produced the polymer films with higher thermal stability than the mixture of acrylate with CHVE or HBVE. The composition of acrylate-vinyl ether mixture and degree of unsaturation of vinyl ether monomers influenced the thermal stability of polymer. The mixture of epoxy acrylate-vinyl ether and polypropylene glycol diacrylate-vinyl ether have 1 initial decomposition temperature whereas the urethane acrylate-vinyl ether mixture has 2 initial decomposition temperatures. (authors)

  2. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers.

    Science.gov (United States)

    2010-04-01

    ... in powder form having a particle size such that 100 percent will pass through a U.S. Standard Sieve No. 40 and such that not more than 10 percent will pass through a U.S. Standard Sieve No. 200. (1... analysis. (e) Other specifications and limitations. The vinyl chloride-lauryl vinyl ether copolymers...

  3. Fabrication and properties of poly(polyethylene glycol n-alkyl ether vinyl ether)s as polymeric phase change materials

    International Nuclear Information System (INIS)

    Pei, Dong-fang; Chen, Sai; Li, Shu-qin; Shi, Hai-feng; Li, Wei; Li, Xuan; Zhang, Xing-xiang

    2016-01-01

    A series of poly(polyethylene glycol n-alkyl ether vinyl ether)s (PC m E n VEs) with various lengths of alkyl chains and polyethylene glycol spacers as side chain (m = 16,18; n = 1,2) were synthesized via two steps. First, monomers-ethylene glycol hexadecyl ether vinyl ether (C 16 E 1 VE), ethylene glycol octadecyl ether vinyl ether (C 18 E 1 VE), diethylene glycol hexadecyl ether vinyl ether (C 16 E 2 VE) and diethylene glycol octadecyl ether vinyl ether (C 18 E 2 VE) were synthesized by a modified Williamson etherification. Then, four new types of phase change materials were successfully fabricated by a living cationic polymerization. Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were employed to characterize their composition, thermal properties and crystallization behavior. The results show that, the side chains of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are in a hexagonal lattice, and the onset temperatures for melting of PC 16 E 1 VE, PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are 39.8 °C, 37.4 °C, 51.0 °C and 48.9 °C, the onset temperatures for crystallization are 36.7 °C, 35.2 °C, 47.4 °C and 46.3 °C, respectively. The enthalpy changes of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 100 J/g; on the contrary, it is 96 J/g for PC 16 E 1 VE. The enthalpy decrease is no more than 11% after 10 heating and cooling cycles. The 5 wt% mass loss temperatures of PC 18 E 1 VE, PC 16 E 2 VE and PC 18 E 2 VE are higher than 300 °C; on the contrary, it’s 283 °C for PC 16 E 1 VE. Using a weak polarity, flexible alkyl ether chain (-OCH 2 CH 2 O-) as a spacer to link the main chain and side chain is conducive to the crystallization of the alkyl side chain. These new phase change materials can be applied in heat storage, energy conservation, and environmental protection.

  4. Hydrolysis of strained bridgehead bicyclic vinyl ethers and sulfides

    International Nuclear Information System (INIS)

    Chwang, W.K.; Kresge, A.J.; Wiseman, J.R.

    1979-01-01

    Rates of hydrolysis of the bridgehead bicyclic vinyl ether 9-oxabicyclo[3.3.1]non-1-ene(6) and its vinyl sulfide counterpart 9-thiabicyclo[3.3.1]non-1-ene(7), catalyzed by the hydronium ion, were measured in H 2 O and in D 2 O solution. These data give isotope effects, k/sub H//k/sub D/ = 2.4 and 1.9 respectively, which show that these reactions occur by the normal, rate-determining carbon protonation, mechanism. The vinyl ether 6 is less reactive than its olefin analogue, bicyclo[3.3.1]non-1-ene (relative rate 1:1/1400), as may have been expected for a constrained bicyclic system such as this, where stabilization of the bridgehead carbocation intermediate by conjugation with oxygen is severely impaired. The vinyl sulfide 7, however, is even less reactive than the vinyl ether (relative rates 1:1/140); this is a remarkable result in view of the fact that conjugation between the sulfur atom and the cationic center is presumably also strongly inhibited. 1 figure, 3 tables

  5. Decoration of a Poly(methyl vinyl ether-co-maleic anhydride)-Shelled Selol Nanocapsule with Folic Acid Increases Its Activity Against Different Cancer Cell Lines In Vitro.

    Science.gov (United States)

    Ganassin, Rayane; Souza, Ludmilla Regina de; Py-Daniel, Karen Rapp; Longo, João Paulo Figueiró; Coelho, Janaína Moreira; Rodrigues, Mosar Correa; Jiang, Cheng-Shi; Gu, Jinsong; Morais, Paulo César de; Mosiniewicz-Szablewska, Ewa; Suchocki, Piotr; Báo, Sônia Nair; Azevedo, Ricardo Bentes; Muehlmann, Luis Alexandre

    2018-01-01

    Due to the low therapeutic index of different chemotherapeutic drugs used for cancer treatment, the development of new anticancer drugs remains an intense field of research. A recently developed mixture of selenitetriacylglycerides, selol, was shown to be active against different cancer cells in vitro. As this compound is highly hydrophobic, it was encapsulated, in a previous study, into poly(methyl vinyl ether-co-maleic anhydride)-shelled nanocapsules in order to improve its dispersibility in aqueous media. Following this line of research, the present report aimed at enhancing the In Vitro activity of the selol nanocapsules against cancerous cells by decorating their surface with folic acid. It is known that several cancer cells overexpress folate receptors. Stable folic acid-decorated selol nanocapsules (SNP-FA) were obtained, which showed to be spherical, with a hydro-dynamic diameter of 364 nm, and zeta potential of -24 mV. In comparison to non-decorated selol nanocapsules, SNP-FA presented higher activity against 4T1, MCF-7 and HeLa cells. Moreover, the decoration of the nanocapsules did not alter their toxicity towards fibroblasts, NIH-3T3 cells. These results show that the decoration with folic acid increased the toxicity of selol nanocapsules to cancer cells. These nanocapsules, besides enabling to disperse selol in an aqueous medium, increased the toxicity of this drug In Vitro, and may be useful to treat cancer in vivo, potentially increasing the specificity of selol towards cancer cells.

  6. The breakdown of vinyl ethers as a two-center synchronous reaction

    Science.gov (United States)

    Pokidova, T. S.; Shestakov, A. F.

    2009-11-01

    The experimental data on the molecular decomposition of vinyl ethers of various structures to alkanes and the corresponding aldehydes or ketones in the gas phase were analyzed using the method of intersecting parabolas. The enthalpies and kinetic parameters of decomposition were calculated for 17 reactions. The breakdown of ethers is a two-center concerted reaction characterized by a very high classical potential barrier to the thermally neutral reaction (180-190 kJ/mol). The kinetic parameters (activation energies and rate constants) of back reactions of the formation of vinyl ethers in the addition of aldehydes or ketones to alkanes were calculated using the method of intersecting parabolas. The factors that influenced the activation energy of the decomposition and formation of ethers were discussed. Quantum-chemical calculations of several vinyl ether decomposition reactions were performed. Ether formation reactions were compared with the formation of unsaturated alcohols as competitive reactions, which can occur in the interaction of carbonyl compounds with alkenes.

  7. Poly(vinyl methyl ether/maleic anhydride)-Doped PEG-PLA Nanoparticles for Oral Paclitaxel Delivery To Improve Bioadhesive Efficiency.

    Science.gov (United States)

    Wang, Qian; Li, Chan; Ren, Tianyang; Chen, Shizhu; Ye, Xiaoxia; Guo, Hongbo; He, Haibing; Zhang, Yu; Yin, Tian; Liang, Xing-Jie; Tang, Xing

    2017-10-02

    Bioadhesive nanoparticles based on poly(vinyl methyl ether/maleic anhydride) (PVMMA) and poly(ethylene glycol) methyl ether-b-poly(d,l-lactic acid) (mPEG-b-PLA) were produced by the emulsification solvent evaporation method. Paclitaxel was utilized as the model drug, with an encapsulation efficiency of up to 90.2 ± 4.0%. The nanoparticles were uniform and spherical in shape and exhibited a sustained drug release compared with Taxol. m-NPs also exhibited favorable bioadhesive efficiency at the same time. Coumarin 6 or DiR-loaded nanoparticles with/without PVMMA (C6-m-NPs/DiR-m-NPs or C6-p-NPs/DiR-p-NPs) were used for cellular uptake and intestinal adhesion experiments, respectively. C6-m-NPs were shown to enhance cellular uptake, and caveolae/lipid raft mediated endocytosis was the primary route for the uptake of the nanoparticles. Favorable bioadhesive efficiency led to prolonged retention in the intestine reflected by the fluorescence in isolated intestines ex vivo. In a ligated intestinal loops model, C6-m-NPs showed a clear advantage for transporting NPs across the mucus layer over C6-p-NPs and free C6. The apparent permeability coefficient (Papp) of PTX-m-NPs through Caco-2/HT29 monolayers was 1.3- and 1.6-fold higher than PTX-p-NPs and Taxol, respectively, which was consistent with the AUC 0-t of different PTX formulations after oral administration in rats. PTX-m-NPs also exhibited a more effective anticancer efficacy, with an IC 50 of 0.2 ± 1.4 μg/mL for A549 cell lines, further demonstrating the advantage of bioadhesive nanoparticles. The bioadhesive nanoparticles m-NPs demonstrated both mucus permeation and epithelial absorption, and thus, this bioadhesive drug delivery system has the potential to improve the bioavailability of drugs that are insoluble in the gastrointestinal environment.

  8. Synthesis of methyl acetate from dimethyl ether using group VIII metal salts of phosphotungstic acid

    Energy Technology Data Exchange (ETDEWEB)

    Sardesai, A.; Lee, S.; Tartamella, T.

    2002-04-01

    Dimethyl ether (DME) can be produced much more efficiently in a single-stage, liquid-phase process from natural gas-based syngas as compared to the conventional process via dehydration of methanol. This process, based on dual catalysts slurried in inert oil, alleviates the chemical equilibrium limitation governing the methanol synthesis reaction and concurrently improves per-pass syngas conversion and reactor productivity. The potential, therefore, for production of methyl acetate via dimethyl ether carbonylation is of industrial importance. In the present study, conversion of dimethyl ether and carbon monoxide to methyl acetate is investigated over a variety of group VIII metal-substituted phosphotungstic acid salts. Experimental results of this catalytic reaction using rhodium, iridium, ruthenium, and palladium catalysts are evaluated and compared in terms of selectivity toward methyl acetate. The effects of active metal, support types, multiple metal loading, and feed conditions on carbonylation activity of DME are examined. Iridium metal substituted phosphotungstic acid supported on Davisil type 643 (pore size 150 A, surface area 279 m{sup 2}/g, mesh size 230-425) silica gel shows the highest activity for DME carbonylation. (author)

  9. Ambient gold-catalyzed O-vinylation of cyclic 1,3-diketone: A vinyl ether synthesis

    Directory of Open Access Journals (Sweden)

    Yumeng Xi

    2013-11-01

    Full Text Available Gold-catalyzed O-vinylation of cyclic 1,3-diketones has been achieved for the first time, which provides direct access to various vinyl ethers. A catalytic amount of copper triflate was identified as the significant additive in promoting this transformation. Both aromatic and aliphatic alkynes are suitable substrates with good to excellent yields.

  10. Synthesis of carboxylic acids, esters, alcohols and ethers containing a tetrahydropyran ring derived from 6-methyl-5-hepten-2-one.

    Science.gov (United States)

    Hanzawa, Yohko; Hashimoto, Kahoko; Kasashima, Yoshio; Takahashi, Yoshiko; Mino, Takashi; Sakamoto, Masami; Fujita, Tsutomu

    2012-01-01

    3-hydroxy acids, 3-hydroxy-3,7-dimethyloct-6-enoic acid (1) and 3-hydroxy-2,2,3,7-tetramethyloct-6-enoic acid (2), were prepared from 6-methyl-5-hepten-2-one, and they were subsequently used to prepare (2,6,6-trimethyltetrahydropyran-2-yl)acetic acid (3) and 2-methyl-2-(2,6,6-trimethyltetrahydropyran-2-yl)propanoic acid (4), respectively, via cyclization with an acidic catalyst such as boron trifluoride diethyl etherate or iodine. The reaction of carboxylic acids 3 and 4 with alcohols, including methanol, ethanol, and 1-propanol, produced the corresponding methyl, ethyl, and propyl esters, which all contained a tetrahydropyran ring. Reduction of carboxylic acids 3 and 4 afforded the corresponding alcohols. Subsequent reactions of these alcohols with several acyl chlorides produced novel esters. The alcohols also reacted with methyl iodide and sodium hydride to provide novel ethers. A one-pot cyclization-esterification of 1 to produce esters containing a tetrahydropyran ring, using iodine as a catalyst, was also investigated.

  11. Solid-phase synthesis of isoxazoles using vinyl ethers as chameleon catches.

    Science.gov (United States)

    Barrett, A G; Procopiou, P A; Voigtmann, U

    2001-10-04

    [reaction: see text] Regioselective 1,3-dipolar cycloadditions of supported vinyl ethers R(1)C(=CH(2))O-CH(2)-polymer, prepared by the Tebbe olefination of R(1)CO(2)-CH(2)-polymer, with ethyl cyanoformate N-oxide gave supported isoxazoline derivatives. Release from the support under mild acidic conditions gave the isoxazoles ethyl 5-R(1)-isoxazole-3-carboxylates. Alternatively, further on-resin functionalization of the R(1) substituent using Suzuki coupling reactions and release from the support under acidic conditions gave more structurally diverse isoxazoles.

  12. Vinyl ether hydrolysis. VII. Isotope effects on catalysis by aqueous hydrofluoric acid

    International Nuclear Information System (INIS)

    Kresge, A.J.; Chen, H.J.; Chiang, Y.

    1977-01-01

    Comparison of rates of hydrolysis of three vinyl ethers catalyzed by HF in H 2 O and DF in D 2 O at 25 0 C gives primary isotope effects in the range k/sub H//k/sub D/ = 3.3 to 3.5. The unexpectedly small size of these effects may be attributed to strong, ω = 1325 to 1450 cm -1 , hydrogenic bending vibrations in the proton transfer transition states of these reactions along with the lack of compensatory bending vibrations in the diatomic proton donor

  13. Improving the Performances of Poly(vinylphosphonic acid) by Compositing or Copolymerization with Poly(4-(α-methyl)vinyl-1H-1,2,3-triazole)

    International Nuclear Information System (INIS)

    Han, Shuaiyuan; Yue, Baohua; Yan, Liuming

    2014-01-01

    Graphical abstract: - Highlights: • Poly(4-(α-methyl)vinyl-1H-1,2,3-triazole) is synthesized • PVPA/PMVTri polymeric composite proton conducting membranes are prepared • The proton conductivity of PVPA is improved by compositing with PMVTri • The water resistance of PVPA is improved by compositing with PMVTri • The oxidative stability is greatly improved - Abstract: The poly(vinylphosphonic acid) (PVPA), poly(4-(α-methyl)vinyl-1H-1,2,3-triazole) (PMVTri), and poly(VPA-co-MVTri) were synthesized, and proton exchange membranes were prepared based on the acid-base polymeric composite of PVPA and PMVTri, and acid-base amphoteric copolymer of poly(VPA-co-MVTri). The overall performances of PVPA, proton conductivity, thermal and oxidative stability, and water resistance, are greatly improved by compositing of PMVTri or copolymerization with 4-(α-methyl)vinyl-1H-1,2,3-triazole (MVTri). About four or eight folds improvement in maximum proton conductivity was observed in the polymeric composite of PVPA/PMVTri or acid-base amphoteric copolymer poly(VPA-co-MVTri) because of the redistribution of ions in the heterostructures of PVPA and PMVTri, respectively, compared with the pristine PVPA. At the same time, the oxidative stability and the water resistance of PVPA were also greatly improved attributing to the absent of α-H in the main chain of PMVTri and the acid-base interaction between the phosphonic acid groups and the triazolyl groups, respectively

  14. The Formation of Polycomplexes of Poly(Methyl Vinyl Ether-Co-Maleic Anhydride and Bovine Serum Albumin in the Presence of Copper Ions

    Directory of Open Access Journals (Sweden)

    Karahan Mesut

    2014-09-01

    Full Text Available The binary and ternary complex formations of poly(methyl vinyl ether-co-maleic anhydride (PMVEMA with copper ions and with bovine serum albumin (BSA in the presence of copper ions in phosphate buffer solution at pH = 7 were examined by the techniques of UV-visible, fluorescence, dynamic light scattering, atomic force microscopy measurements. In the formation of binary complexes of PMVEMA-Cu(II, the addition of copper ions to the solution of PMVEMA in phosphate buffer solution at pH = 7 forms homogeneous solutions when the molar ratio of Cu(II/MVEMA is 0.5. Then the formations of ternary complexes of PMVEMA-Cu(II-BSA were examined. Study analysis revealed that the toxicities of polymer-metal and polymer-metal-protein mixture solutions depend on the nature and ratio of components in mixtures.

  15. Interaction parameters of poly(vinyl methyl ether) in 2-propanol-water mixture as determined by small-angle neutron scattering

    International Nuclear Information System (INIS)

    Takada, Masako; Kurita, Kimio; Okano, Koji; Furusaka, Michihiro.

    1994-01-01

    The small-angle neutron scattering from semidilute solutions of poly(vinyl methyl ether)(PVME) in a 2-propanol-water mixture has been measured, the volume concentration of 2-propanol in the aqueous solvent being 10%, in the temperature range just below the lower critical solution temperature(LCST). The binary and ternary cluster integrals of polymer segments were determined from the concentration dependence of the correlation length at each temperature. We have calculated the contribution of segment-segment interaction to the entropy, S int and enthalpy, U int from the measured temperature dependences of these interaction parameters and found that both values are positive in accordance with the previously measured PVME-water system and PVME-(water+methanol) system. However, the value of S int for PVME-(water+2-propanol) system is larger than that for PVME-(water+methanol) system having the same alcohol concentration, and it is even larger than that for PVME-water system. This anomalous behavior is explained as due to the preferential solvation of 2-propanol molecules to the segments of PVME. (author)

  16. γ-Rays-induced synthesis of hydrogels of vinyl ethers with stimuli-sensitive behavior

    International Nuclear Information System (INIS)

    Nam, I.K.; Mun, G.A.; Urkimbaeva, P.I.; Nurkeeva, Z.S.

    2003-01-01

    γ-Radiation method was applied to synthesize novel water-soluble and water-swelling polymers. Vinyl ether of ethylene glycol (VEEG), vinyl butyl (VBE) and vinyl isobutyl (VIBE) ethers were used as monomers. The synthesis of VEEG-VBE and VEEG-VIBE copolymers was carried out in a wide range of feed composition and absorbed dose. It was found that the hydrophobic-hydrophilic balance of the copolymers could be delicately varied by the copolymer composition as well as by the chemical structure of the alkyl substitute in the hydrophobic moiety. The copolymers exhibit thermo-sensitive behavior in water solutions. The value of transition temperature is considerably decreased at a higher concentration of the hydrophobic component in the copolymer composition

  17. Poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers with Various Molecular Weights as Phase Change Materials

    Directory of Open Access Journals (Sweden)

    Dongfang Pei

    2018-02-01

    Full Text Available At present, research on the relationship of comb-like polymer phase change material structures and their heat storage performance is scarce. Therefore, this relationship from both micro and macro perspectives will be studied in this paper. In order to achieve a high phase change enthalpy, ethylene glycol segments were introduced between the vinyl and the alkyl side chains. A series of poly(mono/diethylene glycol n-tetradecyl ether vinyl ethers (PC14EnVEs (n = 1, 2 with various molecular weights were polymerized by living cationic polymerization. The results of PC14E1VE and PC14E2VE showed that the minimum number of carbon atoms required for side-chain crystallization were 7.7 and 7.2, which were lower than that reported in the literature. The phase change enthalpy 89 J/g (for poly(mono ethylene glycol n-tetradecyl ether vinyl ethers and 86 J/g (for poly(hexadecyl acrylate were approximately equal. With the increase of molecular weight, the melting temperature, the melting enthalpy, and the initial thermal decomposition temperature of PC14E1VE changed from 27.0 to 28.0 °C, from 95 to 89 J/g, and from 264 to 287 °C, respectively. When the number average molar mass of PC14EnVEs exceeded 20,000, the enthalpy values remained basically unchanged. The introduction of the ethylene glycol chain was conducive to the crystallization of alkyl side chains.

  18. Investigation of Complexation of Linear Poly(N-vinyl-2-pyrrolidone) with Poly(methacrylic acid-co-methyl methacrylate) Gel

    OpenAIRE

    Liu, Guoqin; Yan, Guojin; Zou, Wenjun; Li, Zhengxin

    2011-01-01

    The contraction of poly(methacrylic acid-co-methyl methacrylate) (P(MAA-co-MMA)) gel induced by complexation with linear poly(N-vinyl-2-pyrrolidone) (PVP) is quite different from that of poly(acrylic acid) (PAA) or poly(methacrylic acid) (PMAA) gel. It was found that the concentration of PVP has a strong effect on the complexation with P(MAA-co-MMA) gel. When PVP was introduced into the P(MAA-co-MMA) network, its dynamic mechanic properties vary greatly between complexed and uncomplexed netwo...

  19. SYNTHESIS OF METHYL TERT-BUTYL ETHER CATALYZED BY ACIDIC ION-EXCHANGE RESINS - INFLUENCE OF THE PROTON ACTIVITY

    NARCIS (Netherlands)

    PANNEMAN, HJ; BEENACKERS, AACM

    1995-01-01

    The catalytic activity of various strong acid ion-exchange resins on the synthesis of methyl tert-butyl ether (MtBE) from methanol and isobutene has been investigated. Relative to Amberlyst 15, Kastel CS 381 and Amberlyst CSP have similar rate constants, whereas Duolite ES 276 and Amberlyst XE 307

  20. Radiation grafting from binary monomer mixtures. II. Vinyl ether of monoethanolamine and N-vinylpyrrolidone

    International Nuclear Information System (INIS)

    Nurkeeva, Zauresh S.; Abdel Aal, A.-S.; Kupchishin, Anatoliy I.; Khutoryanskiy, Vitaliy V.; Mun, Grigoriy A.; Beksyrgaeva, Aida G.

    2003-01-01

    Radiation grafting from binary monomer mixtures of vinyl ether of monoethanolamine and N-vinylpyrrolidone onto polyethylene films has been studied. The structure of the grafted films was characterized by FTIR spectroscopy. Water uptake and contact angle measurements confirmed that the grafting leads to a considerable hydrophilization of the films surface. The presence of the more active N-vinylpyrrolidone enhances the grafting of the less active vinyl ether of monoethanolamine. Sorption properties of grafted films with respect to copper (II) ions have been studied

  1. Radiation grafting from binary mixtures of vinyl ether of mono ethanol amine with N-vinylpyrrolidone and vinyl ether of ethylene glycol onto polyolefins films and metallization of obtained films

    International Nuclear Information System (INIS)

    Al'-Saed Abdel' Aal'; Nurkeeva, Z.; Khutoryanskij, V.; Mun, G.; Sangajlo, M.

    2003-01-01

    Radiation grafting from binary mixtures of vinyl ether of mono ethanol amine with N-vinylpyrrolidone and vinyl ether of ethylene glycol onto polyolefins films using γ-radiation and accelerated electrons has been studied. IR-spectroscopy is used to confirm the structure of grafted films. A combination of and metallization of obtained films. A combination of gravimetric and potentiometric techniques is applied to determine the fraction of each monomer in graft copolymer. Water uptake and contact angle measurements confirmed that the grafting process improve the hydrophilic properties of obtained films. The obtained materials are metallized by electroless copper plating. The metallized films have good electro conductive properties. (author)

  2. Investigation of Complexation of Linear Poly(N-vinyl-2-pyrrolidone with Poly(methacrylic acid-co-methyl methacrylate Gel

    Directory of Open Access Journals (Sweden)

    Guoqin Liu

    2011-01-01

    Full Text Available The contraction of poly(methacrylic acid-co-methyl methacrylate (P(MAA-co-MMA gel induced by complexation with linear poly(N-vinyl-2-pyrrolidone (PVP is quite different from that of poly(acrylic acid (PAA or poly(methacrylic acid (PMAA gel. It was found that the concentration of PVP has a strong effect on the complexation with P(MAA-co-MMA gel. When PVP was introduced into the P(MAA-co-MMA network, its dynamic mechanic properties vary greatly between complexed and uncomplexed networks. It had the following results: (1 the higher modulus ratio; (2 a slight contraction of gel.

  3. Preparation of H3-labelled methyl ethers of saturated fatty acids by heterogeneous catalytic isotope exchange in solution with gaseous tritium

    International Nuclear Information System (INIS)

    Shevchenko, V.P.; Myasoedov, N.F.

    1980-01-01

    A simple method of preparing 3 H-labelled methyl ethers of saturated fatty acids in the dioxane solution using the method of isotopic heterogenous catalytic exchange with gaseous tritium, is suggested. 3 H-labelled natural fatty acids (C 12 -C 18 ) are prepared by alkaline hydrolysis [ru

  4. Triblock and pentablock terpolymers by sequential base-assisted living cationic copolymerization of functionalized vinyl ethers

    KAUST Repository

    Bouchekif, Hassen; Sulhami, A. I.; AlGhamdi, Rayed D.; Gnanou, Yves; Hadjichristidis, Nikolaos

    2015-01-01

    A series of novel, well-defined triblock (PnBVE-b-PCEVE-b-PSiDEGVE) and pentablock (PSiDEGVE-b-PCEVE-b-PnBVE-b-PCEVE-b-PSiDEGVE) terpolymers of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiEGVE) were synthesized by sequential base-assisted living cationic polymerization. The living character of the homopolymerization of the three VE monomers and the crossover reaction resulting in the formation of well-defined block copolymers were investigated in various solvents (toluene, dichloromethane and n-hexane) using either a monofunctional [nBVE-acetic acid adduct (nBEA), CEVE-acetic acid adduct (CEEA) and SiDEGVE-acetic acid adduct (SiDEGEA)] or a difunctional [1,4-cyclohexane-1,4-diyl bis(2-methoxyethyl acetate) (cHDMEA)] initiator. All initiators are structurally equivalent to the dormant species of the corresponding monomers in order to achieve fast initiation. The optimal conditions of polymerization were achieved in n-hexane at -20 °C, in the presence of 1 M AcOEt (base). Good control over the number average molecular weight (Mn) and the polydispersity index (PDI) was obtained only at [Et3Al2Cl3]0 = [Chain-end]0 ≤ 10 mM. 2,6-Di-tert-butylpyridine (DtBP) was used as a non-nucleophilic proton trap to suppress any protonic initiation from moisture (i.e., Et3Al2Cl3·H2O). Well-defined PnBVEn-b-PCEVEp-b-PSiDEGVEq and PSiDEGVEq-b-PCEVEp-b-PnBVEn-b-PCEVEp-b-PSiDEGVEq terpolymers with a high crossover efficiency, no PCEVE-induced physical gelation, and predictable Mn and PDI < 1.15 were synthesized successfully provided that the targeted DPCEVE/DPnBVE ratio (i.e., p/n) did not exceed 2 and 0.2, respectively. The quantitative desilylation of the PSiEGVE by n-Bu4N+F- in THF at 0 °C led to triblock and pentablock terpolymers in which the PCEVE is the central block and the polyalcohol is the outer block. The thermal properties of the synthesized materials were examined by differential scanning

  5. Preparation of vinyl chloride – vinyl ether copolymers via partial etherification from PVC

    Directory of Open Access Journals (Sweden)

    2007-08-01

    Full Text Available The chemical modifications of poly (vinyl chloride with aliphatic and aromatic alcohols compounds have been investigated at room temperature and atmospheric pressure, catalysed by a new green basic catalyst, the Maghnite-K+. The presence of ether groups in the products is proven by infra red spectroscopy (IR as well as by nuclear magnetic resonance spectroscopy (1H NMR, and characterized by intrinsic viscosity as well as by gel permeation chromatography (GPC.

  6. Solid polymer electrolytes based on alternating copolymers of vinyl ethers with methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate

    International Nuclear Information System (INIS)

    Itoh, Takahito; Fujita, Katsuhito; Inoue, Kentaro; Iwama, Hiroki; Kondoh, Kensaku; Uno, Takahiro; Kubo, Masataka

    2013-01-01

    Graphical abstract: - Highlights: • Synthesis of alternating copolymers of vinyl ethers and vinylene carbonate. • Preparation of polymer electrolytes based on the alternating copolymers with LiTFSI. • Structure-property relationship for alternating copolymers-based electrolytes. • Interfacial stability between polymer electrolytes with lithium metal electrode. - Abstract: Alternating copolymers (poly(1a-g-alt-VC)) of vinyl ethers with various methoxy oligo(ethyleneoxy)ethyl groups and vinylene carbonate (VC) were prepared, and the thermal and electrochemical properties of their polymer electrolytes with LiTFSI and interfacial stability between the polymer electrolyte and Li metal electrode were investigated. T g 's increased linearly with salt contents, and decreased with an increase in the chain length of methoxy oligo(ethyleneoxy)ethyl groups in the vinyl ethers at constant salt concentration. The slopes of T g vs. [Li]/[O] were identical, independent of the polymer structure. The ionic conductivities of the polymer electrolytes increased with increasing the side-chain ethyleneoxy (EO) unit length of the vinyl ether unit in the alternating copolymers, and also their temperature dependences became relatively smaller in the polymer electrolytes having longer EO units in the vinyl ethers. The highest ionic conductivity, 1.2 × 10 −4 S/cm at 30 °C, was obtained in the alternating copolymer with a side-chain EO unit length of 23.5 in the vinyl ether unit. Ion transport coupled with the segmental motion of the polymer is dominant in these polymer electrolytes. Interfacial resistance increased gradually with contact time, indicative of the formation of passivation films on the Li metal electrode. These polymer electrolytes are thermally stable and have large electrochemical windows of use

  7. A Convenient and Efficient Method for Demethylation of Aryl Methyl Ethers with Magnesium Iodide in Ionic Liquid

    International Nuclear Information System (INIS)

    Lee, Kwan Soo; Kim, Kee D.

    2010-01-01

    We have developed a new and efficient method for the demethylation of various types of aryl methyl ethers using readily available, stable, and easily handled magnesium iodide in [BMIM]BF 4 ionic liquid. Owing to its simplicity and mild reaction conditions the protocol reported herein may serve as a useful alternative to the existing methods for the deprotection of aryl methyl ethers to the corresponding phenolic derivatives. Demethylation of aryl methyl ethers to the corresponding phenols are very important reactions in organic synthesis. A number of methods have been reported for the cleavage of highly stable aryl methyl ethers utilizing strong acids or bases such as aluminum chloride, boron tribromide, cerium chloride, alkaline thiolate, methyl magnesium iodide, and L-Selectride. However, all of these methods invariably suffered from one or more drawbacks such as harsh reaction conditions, long reaction times, difficulty of manipulation, use of exotic reagents, and low reaction yields. Furthermore, in the most of known methods for demethylation of aryl methyl ethers, use of large excess amounts of demethylating agents have been generally required. Thus, it is highly desirable to develop an improved convenient and efficient procedure for demethylation reactions of aryl methyl ethers

  8. A Convenient and Efficient Method for Demethylation of Aryl Methyl Ethers with Magnesium Iodide in Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kwan Soo [KAIST, Daejeon (Korea, Republic of); Kim, Kee D. [Sangji University, Wonju (Korea, Republic of)

    2010-12-15

    We have developed a new and efficient method for the demethylation of various types of aryl methyl ethers using readily available, stable, and easily handled magnesium iodide in [BMIM]BF{sub 4} ionic liquid. Owing to its simplicity and mild reaction conditions the protocol reported herein may serve as a useful alternative to the existing methods for the deprotection of aryl methyl ethers to the corresponding phenolic derivatives. Demethylation of aryl methyl ethers to the corresponding phenols are very important reactions in organic synthesis. A number of methods have been reported for the cleavage of highly stable aryl methyl ethers utilizing strong acids or bases such as aluminum chloride, boron tribromide, cerium chloride, alkaline thiolate, methyl magnesium iodide, and L-Selectride. However, all of these methods invariably suffered from one or more drawbacks such as harsh reaction conditions, long reaction times, difficulty of manipulation, use of exotic reagents, and low reaction yields. Furthermore, in the most of known methods for demethylation of aryl methyl ethers, use of large excess amounts of demethylating agents have been generally required. Thus, it is highly desirable to develop an improved convenient and efficient procedure for demethylation reactions of aryl methyl ethers.

  9. Synthesis of water-soluble poly [acrylic acid-co-vinyl butyl ether] and its applications in cement admixtures

    International Nuclear Information System (INIS)

    Negim, S.M.; Mun, G.A.; Nurkeeva, Z.S.; Danveesh, H.H.M.

    2005-01-01

    Three composition ratios of poly[acrylic acid (AA)-co-vinyl butyl ether)] were prepared in alcoholic solution using azo-bis-isobutyro-nitrile as initiator (ABIN). The water-soluble copolymers were characterized through FT-IR, 1 H NMR, Mass spectra, ESEM as well as viscosity. The effect of water-soluble copolymers and their sodium salts on the physico-mechanical properties of Ordaniary Portland Cement (O.P.C) pastes was investigated. The results showed that the addition of aqueous solutions from the prepared copolymers and their sodium salts to the cement improve most of the specific characteristics of (O.P.C). As the concentration of the water-soluble copolymer increases, the setting time increases. The combined water content enhances the addition of copolymer to the mixing water. The compressive strength was she increased at all any hydration. The results of the solution of the prepared sodium salt copolymers are better than its copolymers. (author)

  10. Synthesis of [11C]-labelled methyl esters: transesterification of enol esters versus BF3 etherate catalysed esterification - a comparative study

    International Nuclear Information System (INIS)

    Ackermann, U.; Falzon, C.; Issa, W.; Tochon-Danguy, H.J.; Sachinidis, J.I.; Blanc, P.; White, J.; Scott, A.M.

    2005-01-01

    An important issue in Positron Emission Tomography (PET) is the development of labelling techniques to incorporate positron emitting radionuclides into biologically active compounds. When labelling with 11C, the short 20 minutes half-life of the radionuclide significantly limits the number of synthetic protocols available to the radiochemist. C-l synthons such as [HCJ-methyl iodide (1) or methyl triflate (2) are readily available and are frequently used as alkylating agents for the preparation of radiopharmaceuticals. However, the use of these alkylating agents often makes it necessary to introduce protecting groups in order to prevent labelling at unwanted sites on the molecule. Since the removal of protecting groups is a time-consuming process, a more direct synthesis strategy is desirable. This has prompted us to investigate the esterification of carboxylic acids using [1 lC]-mcthanol and BF3 etherate as Lewis acid catalyst. Our results have demonstrated that the reaction conditions necessary to promote the esterification can cleave functional groups such as ethers. We have therefore shifted our attention towards the irreversible transesterification of enol esters using [HCl-methanol and a tin catalyst as an alternative strategy to [HC]-methyl ester formation. We have prepared a series of 5 aromatic ethoxy vinyl esters bearing various functional groups. The transesterification (radiolabelling) was carried out in DMSO at 150 Degrees C for 7 minutes in the presence of [HQMeOH and 1.3-dichlo-rotetrabutyldistannoxane as catalyst. We have found that the transesterification of enol esters is a mild and efficient labelling method for the formation of [HCl-methyl esters. The reaction proceeds smoothly and leaves functional groups intact. It requires only one synthesis step compared to two steps for the conventional method, and gives a radiochemical yields of 25%

  11. Graft polymerization of vinyl acetate onto starch. Saponification to starch-g-poly(vinyl alcohol)

    International Nuclear Information System (INIS)

    Fanta, G.F.; Burr, R.C.; Doane, W.M.; Russell, C.R.

    1979-01-01

    Graft polymerizations of vinyl acetate onto granular cornstarch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinyl acetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. Over half of the polymer was present as ungrafted poly(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficency. Grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate--methyl methacrylate was carried out near 0 0 C; although conversion of monomers to polymer was low and grafted polymer contained 40 to 50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch-g-poly(vinyl acetate) to starch-g-poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch-g-poly(vinyl alcohol) in hot water was less than 50; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch-g-poly

  12. Atmospheric fate of methyl vinyl ketone

    DEFF Research Database (Denmark)

    Praske, Eric; Crounse, John D; Bates, Kelvin H

    2015-01-01

    First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl...

  13. Structure of pyridine and quinoline vinyl ethers according to data from 1H and 13C NMR spectra and quantum-chemical calculations

    International Nuclear Information System (INIS)

    Afonin, A.V.; Voronov, V.K.; Andriankov, M.A.; Danovich, D.K.

    1987-01-01

    A systematic investigation of the structure of the vinyl ethers of heterocyclic compounds has not been undertaken. The present work was devoted to investigation of the stereochemical and electronic structure of the vinyl ethers of pyridine and quinoline. The PMR spectra of the samples were recorded for 5% solutions in deuterochloroform on a Tesla BS-497 spectrometer at 100 MHz. The 13 C NMR spectra were recorded on a Tesla BS-567A spectrometer at 25.1 MHz in deuterochloroform with the samples at concentrations of 30%. The internal standard was HMDS. The vinyl ethers of pyridine and quinoline exist preferentially in the nonplanar S-trans conformation. In the vinyl esters of pyridine and quinoline the p-π conjugation is concurrent in nature and depends on the position of the vinyloxy group in the heterocycle

  14. On the some reactions of mixed ethers of phosphorus acid with acrylonitrile and methyl iodide

    International Nuclear Information System (INIS)

    Gusev, Yu.K.; Chistokletov, V.N.; Petrov, A.A.

    1977-01-01

    The bimolecular mechanism has been confirmed of the redgrouping stage of Arbuzov's classical reactions for phosphites containing primary and secondary radicals in reactions of acrylonitrile and methyl iodide with some mixed ethers of phosphoric acid. It is suggested that dealcylation of the intermediate products formed on interaction of olefins activated by electron-acceptor groups with phosphites containing primary radicals occurs according to the Ssub(N)2-mechanism, secondary radicals, according to the mixed Ssub(N)2 and Ssub(N)1-mechanism,and radicals capable of forming stable carbonium ions, according to the Ssub(N)1-mechanism

  15. Effect of trimethylcolchicinic acid methyl ether d-tartrate (TMCA) on Hodgkin's and non-Hodgkin's lymphoma.

    Science.gov (United States)

    Stolinsky, D C; Jacobs, E M; Irwin, L E; Pajak, T F; Bateman, J R

    1976-01-01

    Trimethylcolchicinic acid methyl ether d-tartrate (TMCA; NSC-36351) was administered daily by mouth to 71 patients with malignant lymphomas. Partical (greater than 50%) responses were observed in eleven of 37 patients with Hodgkin's disesse, two of 22 patients with lymphocytic lymphoma, and one of two patients with mixed cell lymphoma. One complete and three partial responses were noted in nine patients with histiocytic lymphoma. Responses lasted from one to 91+ months (median: four months) and occurred in patients whose disease was resistant to alkylating agents, vinblastine, vincristine, procarbazine, prednisone or BCNU. Toxic effects included leukopenia, thrombocytopenia, nausea, diarrhea, stomatitis, alopecia and dermatitis.

  16. Synthesis of tritium labelled methyl vinyl ketone and its use in copolymer analysis

    International Nuclear Information System (INIS)

    Burfield, D.R.; Savariar, C.M.

    1980-01-01

    The synthesis of tritiated methyl vinyl ketone by base catalysed exchange and its use in determining the ketone content of styrene/methyl vinyl ketone copolymers are reported. Methods of assay are described in detail and the general applicability of the method is discussed. (author)

  17. Fatty acid methyl esters synthesis from non-edible vegetable oils using supercritical methanol and methyl tert-butyl ether

    International Nuclear Information System (INIS)

    Lamba, Neha; Modak, Jayant M.; Madras, Giridhar

    2017-01-01

    Highlights: • FAMEs were synthesized from non-edible oils using supercritical MeOH and MTBE. • Effect of time, temperature, pressure and molar ratio on conversions was studied. • Rate constants of reaction with methanol and MTBE differ by an order of magnitude. • Non-catalytic supercritical reactions are one order faster than acid catalyzed synthesis. - Abstract: Fatty acid methyl esters (FAMEs) are useful as biodiesel and have environmental benefits compared to conventional diesel. In this study, these esters were synthesized non-catalytically from non-edible vegetable oils: neem oil and mahua oil with two different methylating agents: methanol and methyl tert-butyl ether (MTBE). The effects of temperature, pressure, time and molar ratio on the conversion of triglycerides were studied. The temperature was varied in the range of 523–723 K with molar ratios upto 50:1 and a reaction time of upto 150 min. Conversion of neem and mahua oil to FAMEs with supercritical methanol was found to be 83% in 15 min and 99% in 10 min, respectively at 698 K. Further, a conversion of 46% of mahua oil and 59% of neem oil was obtained in 15 min at 723 K using supercritical MTBE. The rate constants evaluated using pseudo first order reaction kinetics were in the range of 4.7 × 10"−"6 to 1.0 × 10"−"3 s"−"1 for the investigated range of temperatures. The activation energies obtained were in the range of 62–113 kJ/mol for the reaction systems investigated. The supercritical synthesis was found to be superior to the catalytic synthesis of the corresponding FAMEs.

  18. On the predictive capabilities of CPA for applications in the chemical industry: Mulficomponent mixtures containing methyl-methacrylate, dimethyl-ether or acetic acid

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2014-01-01

    mixtures exhibiting vapor-liquid (VLE) and/or liquid-liquid (LLE) equilibrium. The first two cases include mixtures of methyl-methacrylate with acetone or methanol and dimethyl-ether with ethanol, respectively. In these two cases, the classical form of CPA is used. The third case involves aqueous mixtures...... for the acetic acid-water system for which different parameter sets at different temperatures can be recommended. Even with the use of CPA-HV mixing rules, modeling of the acetic acid-water system with few interaction parameters remains a challenging task. Excellent simultaneous VLE and LLE correlation...... is obtained for complex systems such as aqueous mixtures with ethers and esters. The multicomponent results are, with a few exceptions, very satisfactory, especially for the vapor-liquid equilibrium cases. For the demanding aqueous acetic acid-water containing systems, one parameter set is recommended...

  19. 13C n.m.r. study of solvation mechanisms in the radiation-induced polymerization of vinyl ethers

    International Nuclear Information System (INIS)

    Deffieux, A.; Subira, F.; Stannett, V.T.

    1984-01-01

    A 13 C n.m.r. study of the microstructure of ethyl vinyl ether (EVE) and isopropyl vinyl ether (IPVE) polymers prepared under various experimental conditions and using chemical or γ-ray initiation has been made. Long stereo-sequence assignments were conducted for poly EVE allowing determination of the configurational statistics of propagation in the radiation-induced polymerization of EVE in low polar solvents. Stereo-sequence intensities are found in good agreement with the Markovian model. The results are considered as further support for the occurrence of a specific interaction between the growing active centres and the polymer chains. In the case of IPVE polymers much more important overlappings of the resonance patterns are observed thus preventing any similar detailed study. (author)

  20. Isothermal (vapor + liquid) equilibria and excess enthalpy data of {1-hexene + methyl butyl ether (MBE)} and {1-hexene + methyl tert-butyl ether (MTBE)} binary systems at several temperatures

    International Nuclear Information System (INIS)

    Hani, Rachida; Solimando, Roland; Negadi, Latifa; Jose, Jacques; Ait Kaci, Ahmed

    2012-01-01

    Highlights: ► Vapor pressures of (1-hexene + methyl butyl ether) or (1-hexene + methyl tert-butyl ether) are reported between (263 and 363) K. ► The two mixtures exhibit positive G E . ► Additionally, molar excess enthalpies, H E , for the two binary systems have been measured at 303.15. - Abstract: The vapor pressures of {1-hexene + methyl butyl ether (MBE)} and {1-hexene + methyl tert-butyl ether (MTBE)} binary mixtures and of the three pure components were measured by means of a static device at temperatures between (263 and 333) K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions were calculated for several constant temperatures and fitted to a third-order Redlich–Kister equation using the Barker’s method. Additionally, molar excess enthalpies, H E , for the two binary systems have been measured at 303.15 K using an isothermal flow calorimeter.

  1. Cyclic α-Alkoxyphosphonium Salts from (2-(Diphenylphosphino)phenyl)methanol and Aldehydes and Their Application in Synthesis of Vinyl Ethers and Ketones via Wittig Olefination.

    Science.gov (United States)

    Huang, Wenhua; Rong, Hong-Ying; Xu, Jie

    2015-07-02

    Cyclic α-alkoxyphosphonium salts have been synthesized from (2-(diphenylphosphino)phenyl)methanol and aldehydes in 36-89% yields. These phosphonium salts are bench-stable solids and undergo Wittig olefination with aldehydes under basic conditions (K2CO3 or t-BuOK) to form benzylic vinyl ethers, which are readily hydrolyzed to 1,2-disubstituted ethanones under acidic conditions. The formation mechanism of these phosphonium salts via hemiacetal is also proposed.

  2. Investigation of nanocomposites made with poly(methacrylic acid-co-methyl methacrylate/poly(N-vinyl-2-pyrrolidone/multi-walled carbon nanotubes

    Directory of Open Access Journals (Sweden)

    Liu Guoqin

    2014-01-01

    Full Text Available Poly(methacrylic acid-co-methyl methacrylate (P(MAA-co-MMA was prepared in the presence of poly(N-vinyl-2-pyrrolidone (PVP and multiwalled carbon nanotubes (MWNTs via ultrasonic assisted solution free radical polymerization, i.e., P(MAA-co-MMA/PVP/MWNTs nanocomposites. The morphology, glassy-state storage modulus, thermal behavior and swelling characteristics of P(MAA-co-MMA/PVP/MWNTs nanocomposites were investigated. Scanning electron micrographs (SEM revealed that MWNTs at low concentration could be uniformly dispersed into P(MAA-co-MMA/PVP blends. With increasing MWNTs weight fraction, the average glassy-state modulus, glass transition temperatures and decomposition temperature of the nanocomposites increased, but their swelling characteristics decreased.

  3. Investigation of nanocomposites made with poly(methacrylic acid-co-methyl methacrylate)/poly(N-vinyl-2-pyrrolidone)/multi-walled carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Guoqin, Liu; Wei, Miao [College of Material Science and Engineering, Henan University of Technology (China); Lin-Jian, Shangguan, E-mail: mikepolymer@126.com [School of Mechanical Engineering, North China University of Water Conservancy and Electric Power (China)

    2014-06-01

    Poly(methacrylic acid-co-methyl methacrylate) (P(MAA-co-MMA)) was prepared in the presence of poly(N-vinyl-2-pyrrolidone) (PVP) and multi-walled carbon nanotubes (MWNTs) via ultrasonic assisted solution free radical polymerization, i.e., P(MAA-co-MMA)/PVP/MWNTs nanocomposites. The morphology, glassy-state storage modulus, thermal behavior and swelling characteristics of P(MAA-co-MMA)/PVP/MWNTs nanocomposites were investigated. Scanning electron micrographs (SEM) revealed that MWNTs at low concentration could be uniformly dispersed into P(MAA-co-MMA)/PVP blends. With increasing MWNTs weight fraction, the average glassy-state modulus, glass transition temperatures and decomposition temperature of the nanocomposites increased, but their swelling characteristics decreased. (author)

  4. /sup 13/C-/sup 13/C spin-spin coupling constants in structural investigations. II. Conformational structure of vinyl ethers

    Energy Technology Data Exchange (ETDEWEB)

    Krivdin, L.B.; Shcherbakov, V.V.; Bzhezovskii, V.M.; Kalabin, G.A.

    1986-10-10

    The /sup 13/C-/sup 13/C spin-spin coupling constants between the carbon nuclei of the vinyl group were measured for a series of vinyl ethers. It was established that the unshared electron pairs of the oxygen atom can make a substantial stereospecific contribution to the direct /sup 13/C-/sup 13/C constants of the adjacent nuclei. The observed effect was used to establish the conformational structure of the compounds.

  5. APPLICATION OF PHOTOCATALYTIC PROCESS FOR REMOVAL OF METHYL TERT-BUTYL ETHER FROM HIGHLYCONTAMINATED WATER

    Directory of Open Access Journals (Sweden)

    A. Mesdaghinia

    2007-09-01

    Full Text Available The oxygenate methyl tert-butyl ether is added to gasoline to increase the octane level and to reduce carbon monoxide and hydrocarbon emissions by vehicles. The high mobility, water solubility, and resistance to natural attenuation associated with methyl tert-butyl ether may result in contamination of ground and surface waters. In this research the degradation of aqueous methyl tert-butyl ether at relatively high concentrations was investigated by UV-vis/TiO2/H2O2 photocatalytic process. The effect of important operational parameters such as pH, amount of H2O2, catalyst loading, and irradiation time were also studied. Concentrations of methyl tert-butyl ether and intermediates such as tert-butyl formate and tert-butyl alcohol were measured over a 180 min period using a gas chromatograph equipped with flame ionization detector and combined with headspace sampler. Results showed that the time required for complete degradation increased from 30 to 180min, when the initial concentration was increased from 10 to 500mg/L. The first order rate constant for degradation of methyl tert-butyl ether from the hydroxyl radical was estimated to be 0.177 to 0.022 1/min as the concentration increased from 10 to 500mg/L. Study on the overall mineralization monitored by total organic carbon (TOC analysis showed that in the initial concentration of 100mg/L methyl tert-butyl ether, complete mineralization was obtained after 110min under UV-vis/TiO2/H2O2 photocatalytic process.

  6. Reactivity of vinyl ethers and vinyl ribosides in UV-initiated free radical copolymerization with acceptor monomers.

    Science.gov (United States)

    Pichavant, Loic; Guillermain, Céline; Coqueret, Xavier

    2010-09-13

    The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

  7. The Microwave Spectrum of Methyl Vinyl Ketone Revisited

    Science.gov (United States)

    Wilcox, David S.; Shirar, Amanda J.; Williams, Owen L.; Dian, Brian C.

    2011-06-01

    A chirped-pulse Fourier transform microwave spectrometer was used to record the rotational spectrum of methyl vinyl ketone (MVK, 3-butene-2-one) from 6 to 18.9 GHz. Two stable conformations were identified: the previously documented antiperiplanar (ap) conformer and synperiplanar (sp), which is reported for the first time in this microwave study. Methyl torsional analysis with XIAM resulted in V3 barrier heights of 433.8(1) and 376.6(2) Cm-1 for ap- and sp-MVK, respectively. Heavy atom isotopic species were detected in natural abundance allowing bond lengths and angles of the molecular frames to be calculated through Kraitchman analysis. A comparison with ab initio calculations is included.

  8. EFFECTS OF STIMULATOR SUBSTANCES ON AEROBIC METHYL TERT-BUTYL ETHER BIODEGRADATION BY MICROBIAL CONSORTIUM

    Directory of Open Access Journals (Sweden)

    M. Farrokhi ، S. Ahmadizad

    2009-04-01

    Full Text Available In this study dissolved humic substances and yeast extract were tested in different concentrations for enhancing methyl tert-butyl ether mineralization by isolated microorganisms from a variety of sources. All experiments were conducted at a constant temperature of 25ºC. Vials of 50 mL and 125 mL volume sealed with Teflon-lined Mini-Nert caps was used for microcosm experiments. In all experiments 1% sodium azide were used as control. Samples of bacterial cultures that metabolize methyl tert-butyl ether have been analysed by direct GC analysis using flame ionization detector. Cultures able to metabolize have been found in activated sludge and soils. These microorganisms weregram-positive bacterium. An aerobic microbial consortium was enriched in laboratory for four months. Methyl tert-butyl ether has been shown to biodegrade under aerobic and co-metabolic conditions. A microbial consortium isolated from activated sludges was identified as Cocobacillus. The concentration of the initial attached biomass was about 0.11 g/L of dry weight. The maximum mineralization rate and beneficial effects of stimulator substances on aerobic biodegradation of methyl tert-butyl ether occurred with the culture by combined concentrations of 500 mg/L of yeast extract and 20 mg/L of peat humic growth support of microbial consortium within 216 h and in presence of high oxygen levels and well mixing conditions. It was shown that adding, peat humic and yeast extract together, had better stimulatory effect on methyl tert-butyl ether biodegradation. Results clearly showed a stimulatory effect on methyl tert-butyl ether consumption higher than 20%. Consortium was capable of degrading concentrations of ≤1000 mg/L, whereas concentrations of >1000 mg/L, were not degraded.

  9. TAME (tertiary-amyl-methyl ether) gasoline additive production process development; Desenvolvimento do processo de producao de TAME-aditivo para gasolina

    Energy Technology Data Exchange (ETDEWEB)

    Lovisi, Humberto [Petroflex Industria e Comercio S.A., Duqye de Caxias, RJ (Brazil); Piccoli, Ricardo [COPESUL, Companhia Petroquimica do Sul, Triunfo, RS (Brazil)

    1992-12-31

    PETROFLEX and COPESUL jointly developed a TAME production process. Tertiary-amyl-methyl ether (TAME) is obtained by the methoxylation of isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) in a C{sub s} cut over a sulfonic acid resin. Process was developed on the basis of pilot plant and batch experiments. A simplified process flow-sheet and pilot plant data are presented. Isoamylenes conversions higher than 70% were achieved with low by-products formation. (author) 22 refs., 2 figs., 2 tabs.

  10. TAME (tertiary-amyl-methyl ether) gasoline additive production process development; Desenvolvimento do processo de producao de TAME-aditivo para gasolina

    Energy Technology Data Exchange (ETDEWEB)

    Lovisi, Humberto [Petroflex Industria e Comercio S.A., Duqye de Caxias, RJ (Brazil); Piccoli, Ricardo [COPESUL, Companhia Petroquimica do Sul, Triunfo, RS (Brazil)

    1993-12-31

    PETROFLEX and COPESUL jointly developed a TAME production process. Tertiary-amyl-methyl ether (TAME) is obtained by the methoxylation of isoamylenes (2-methyl-1-butene and 2-methyl-2-butene) in a C{sub s} cut over a sulfonic acid resin. Process was developed on the basis of pilot plant and batch experiments. A simplified process flow-sheet and pilot plant data are presented. Isoamylenes conversions higher than 70% were achieved with low by-products formation. (author) 22 refs., 2 figs., 2 tabs.

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

    International Nuclear Information System (INIS)

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

    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. (paper)

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

    Science.gov (United States)

    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

  13. Development and Applications of Fluorogenic Probes for Mercury(II) Based on Vinyl Ether Oxymercuration

    OpenAIRE

    Ando, Shin; Koide, Kazunori

    2011-01-01

    Mercury is a major threat to the environment and to human health. It is highly desirable to develop a user-friendly kit for on-site mercury detection. Such a method must be able to detect mercury below the threshold levels for drinking water, 1–2 ppb. We developed a fluorescence method based on the oxymercuration of vinyl ethers to detect mercury in dental and environmental samples. Chloride ions interfered with the oxymercuration reaction, but the addition of AgNO3 solved this problem. Fine ...

  14. Radiation-induced glycoside bond breaking in cellulose methyl ethers

    International Nuclear Information System (INIS)

    Petryaev, E.P.; Boltromeyuk, V.V.; Kovalenko, N.I.; Shadyro, O.I.

    1988-01-01

    Radiation-induced destruction of cellulose methyl ethers of different degree of esterification in aqueous solutions with and without acceptors: (N 2 O, O 2 , H 2 O + , Co(2), Cu(2)) is investigated. It is established that OH radicals make main contribution into radiolytic transformations of cellulose ethers in aqueous solutions. Reactions of radicals with free valency on carbon atoms containing secondary nonsubstituted hydroxyl groups lead also to glycoside bond breaking besides the reaction of β-fragmentation and hydrolysis of radicals with an unpaired electron localized near C 1 , C 4 , C 5 aroms

  15. Estimation of the fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample

    DEFF Research Database (Denmark)

    Waul, Christopher Kevin; Arvin, Erik; Schmidt, Jens Ejbye

    2008-01-01

    The fraction of biologically active methyl tert-butyl ether degraders in reactors is just as important for prediction of removal rates as knowledge of the kinetic parameters. The fraction of biologically active methyl tert-butyl ether degraders in a heterogeneous biomass sample, taken from a packed...... bed reactor, was determined using a batch kinetic based approach. The procedure involved modeling of methyl tert-butyl ether removal rates from batch experiments followed by parameter estimations. It was estimated to be 5-14% (w/w) of the measured volatile suspended solids concentration in the reactor....

  16. Preparation of poly (vinyl alcohol) membranes grafted with n-vinyl pyridine/ acrylic acid binary monomers

    International Nuclear Information System (INIS)

    Ajji, A.; Ali, A.

    2014-03-01

    Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl pyridine. The influence of different parameters on the grafting yield was investigated as: the comonomer concentration and composition, and irradiation dose. The suitable conditions of the process had been determined to prepare PVA membranes have both properties of the two monomers, acrylic acid and vinyl pyridine as comonomer concentration and composition, and irradiation dose. Some properties of the membranes had been investigated as maximum swelling and grafting. Also the ability of the grafted films to adsorb some heavy metals and dyes was elaborated and discussed.(author)

  17. NIOSH Manual of Analytical Methods (third edition). Fourth supplement

    Energy Technology Data Exchange (ETDEWEB)

    1990-08-15

    The NIOSH Manual of Analytical Methods, 3rd edition, was updated for the following chemicals: allyl-glycidyl-ether, 2-aminopyridine, aspartame, bromine, chlorine, n-butylamine, n-butyl-glycidyl-ether, carbon-dioxide, carbon-monoxide, chlorinated-camphene, chloroacetaldehyde, p-chlorophenol, crotonaldehyde, 1,1-dimethylhydrazine, dinitro-o-cresol, ethyl-acetate, ethyl-formate, ethylenimine, sodium-fluoride, hydrogen-fluoride, cryolite, sodium-hexafluoroaluminate, formic-acid, hexachlorobutadiene, hydrogen-cyanide, hydrogen-sulfide, isopropyl-acetate, isopropyl-ether, isopropyl-glycidyl-ether, lead, lead-oxide, maleic-anhydride, methyl-acetate, methyl-acrylate, methyl-tert-butyl ether, methyl-cellosolve-acetate, methylcyclohexanol, 4,4'-methylenedianiline, monomethylaniline, monomethylhydrazine, nitric-oxide, p-nitroaniline, phenyl-ether, phenyl-ether-biphenyl mixture, phenyl-glycidyl-ether, phenylhydrazine, phosphine, ronnel, sulfuryl-fluoride, talc, tributyl-phosphate, 1,1,2-trichloro-1,2,2-trifluoroethane, trimellitic-anhydride, triorthocresyl-phosphate, triphenyl-phosphate, and vinyl-acetate.

  18. Method for determination of methyl tert-butyl ether and its degradation products in water

    Science.gov (United States)

    Church, C.D.; Isabelle, L.M.; Pankow, J.F.; Rose, D.L.; Tratnyek, P.G.

    1997-01-01

    An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method can also give simultaneous identification of polar compounds that might occur as degradation products of gasoline oxygenates, such as TBA, TBF, TAA, methyl acetate, and acetone. When the method was applied to effluent from a column microcosm prepared with core material from an urban site in New Jersey, conversion of MTBE to TBA was observed after a lag period of 35 days. However, to date, analyses of water samples from six field sites using the DAI-GC/MS method have not produced evidence for the expected products of in situ degradation of MTBE.An analytical method is described that can detect the major alkyl ether compounds that are used as gasoline oxygenates (methyl tert-butyl ether, MTBE; ethyl tert-butyl ether, ETBE; and tert-amyl methyl ether, TAME) and their most characteristic degradation products (tert-butyl alcohol, TBA; tert-butyl formate, TBF; and tert-amyl alcohol, TAA) in water at sub-ppb concentrations. The new method involves gas chromatography (GC) with direct aqueous injection (DAI) onto a polar column via a splitless injector, coupled with detection by mass spectrometry (MS). DAI-GC/MS gives excellent agreement with conventional purge-and-trap methods for MTBE over a wide range of environmentally relevant concentrations. The new method

  19. Radiation induced ionic polymerisation and grafting of vinyl monomers

    International Nuclear Information System (INIS)

    Stannett, V.T.

    1981-01-01

    Some special aspects of the radiation induced ionic polymerisation and grafting of vinyl monomers will be described. In particular the effects of solvents on the cationic polymerisation of the vinyl ethers will be discussed in detail. The unequivocal free ion nature of the polymerisation makes such information of considerable general interest. Estimates of the propagation rate constants with free cation polymerisation in solvents of different dielectric constants and solvation powers will be presented. Finally, some observations on the radiation induced graft polymerisation of ethyl vinyl ether to poly(vinyl chloride) and to polypropylene will be presented. (author)

  20. Acidolysis small molecular phenolic ether used as accelerator in photosensitive diazonaphthaquinone systems

    Science.gov (United States)

    Zhou, Haihua; Zou, Yingquan

    2006-03-01

    The photosensitive compounds in the photosensitive coatings of positive PS plates are the diazonaphthaquinone derivatives. Some acidolysis small molecular phenolic ethers, which were synthesized by some special polyhydroxyl phenols with vinyl ethyl ether, are added in the positive diazonaphthaquinone photosensitive composition to improve its sensitivity, composed with photo-acid-generators. The effects to the photosensitivity, anti-alkali property, anti-isopropyl alcohol property, dot resolution and line resolution of the coatings are studied with different additive percent of the special phenolic ethers. In the conventional photosensitive diazonaphthaquinone systems for positive PS plates, the photosensitivity is improved without negative effects to resolution, anti-alkali and anti-isopropyl alcohol properties when added about 5% of the special acidolysis phenolic ethers, EAAE or DPHE, composed with photo-acid-generators.

  1. A Tetrazine-Labile Vinyl Ether Benzyloxycarbonyl Protecting Group (VeZ): An Orthogonal Tool for Solid-Phase Peptide Chemistry.

    Science.gov (United States)

    Staderini, Matteo; Gambardella, Alessia; Lilienkampf, Annamaria; Bradley, Mark

    2018-06-01

    The vinyl ether benzyloxycarbonyl (VeZ) protecting group is selectively cleaved by treatment with tetrazines via an inverse electron-demand Diels-Alder reaction. This represents a new orthogonal protecting group for solid-phase peptide synthesis, with Fmoc-Lys(VeZ)-OH as a versatile alternative to Fmoc-Lys(Alloc)-OH and Fmoc-Lys(Dde)-OH, as demonstrated by the synthesis of two biologically relevant cyclic peptides.

  2. Preparation of poly(vinyl alcohol) membranes grafted with N-vinyl imidazole/acrylic acid binary monomers

    International Nuclear Information System (INIS)

    Ajji, Zaki; Ali, Ali

    2006-01-01

    Poly(vinyl alcohol) films were grafted with two monomers using gamma radiation, acrylic acid and N-vinyl imidazole. The influence of different parameters on the grafting yield was investigated as: type of solvent and solvent composition, comonomer concentration and composition, addition of mineral acids, and irradiation dose. Water uptake in respect to the grafting yield was also evaluated. The ability of the grafted films to adsorb copper ions was elaborated and discussed for different grafting yields and ph values of the solution. (authors)

  3. Accumulation of long-chain bases in yeast promotes their conversion to a long-chain base vinyl ether

    OpenAIRE

    Martínez-Montañés, Fernando; Lone, Museer A.; Hsu, Fong-Fu; Schneiter3, Roger

    2017-01-01

    Long-chain bases (LCBs) are the precursors to ceramide and sphingolipids in eukaryotic cells. They are formed by the action of serine palmitoyl-CoA transferase (SPT), a complex of integral membrane proteins located in the endoplasmic reticulum. SPT activity is negatively regulated by Orm proteins to prevent the toxic overaccumulation of LCBs. Here we show that overaccumulation of LCBs in yeast results in their conversion to a hitherto undescribed LCB derivative, an LCB vinyl ether. The ...

  4. Additional conformer observed in the microwave spectrum of methyl vinyl ketone

    Science.gov (United States)

    Wilcox, David S.; Shirar, Amanda J.; Williams, Owen L.; Dian, Brian C.

    2011-05-01

    A chirped-pulse Fourier transform microwave spectrometer was used to record the rotational spectrum of methyl vinyl ketone (MVK, 3-butene-2-one). Two stable conformations were identified: the previously documented antiperiplanar (ap) conformer and synperiplanar (sp), which is reported for the first time in this microwave study. Methyl torsional analysis resulted in V3 barrier heights of 433.8(1) and 376.6(2) cm-1 for ap- and sp-MVK, respectively. Heavy atom isotopic species of both conformers were detected in natural abundance allowing bond lengths and angles of the molecular frames to be calculated through Kraitchman analysis. A comparison with ab initio calculations is included.

  5. Thermotolerant cyclamen with reduced acrolein and methyl vinyl ketone.

    Science.gov (United States)

    Kai, Hiroomi; Hirashima, Keita; Matsuda, Osamu; Ikegami, Hidetoshi; Winkelmann, Traud; Nakahara, Takao; Iba, Koh

    2012-06-01

    Reduced levels of trienoic fatty acids (TAs) in chloroplast membranes induce thermotolerance in several plant species, but the underlying mechanisms remain unclear. TA peroxidation in plant cell membranes generates cytotoxic, TA-derived compounds containing α,β-unsaturated carbonyl groups. The relationship between low TA levels and the amounts of cytotoxic TA-derived compounds was examined using thermotolerant transgenic cyclamen (Cyclamen persicum Mill.) with low TA contents. Changes in the levels of the cytotoxic TA-derived acrolein (ACR), methyl vinyl ketone (MVK), (E)-2-hexenal, 4-hydroxy-2-nonenal, and malondialdehyde were analysed in the leaf tissues of wild-type (WT) and thermotolerant transgenic cyclamen under heat stress. Levels of ACR and MVK in the WT increased in parallel with the occurrence of heat-induced tissue damage, whereas no such changes were observed in the thermotolerant transgenic lines. Furthermore, exogenous ACR and MVK infiltrated into leaves to concentrations similar to those observed in heat-stressed WT leaves caused similar disease symptoms. These results suggest that thermotolerance in transgenic cyclamen depends on reduced production rates of ACR and MVK under heat stress, due to the low level of TAs in these plants.

  6. U.S. Geological Survey laboratory method for methyl tert-Butyl ether and other fuel oxygenates

    Science.gov (United States)

    Raese, Jon W.; Rose, Donna L.; Sandstrom, Mark W.

    1995-01-01

    Methyl tert-butyl ether (MTBE) was found in shallow ground-water samples in a study of 8 urban and 20 agricultural areas throughout the United States in 1993 and 1994 (Squillace and others, 1995, p. 1). The compound is added to gasoline either seasonally or year round in many parts of the United States to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The U.S. Geological Survey (USGS) National Water Quality Laboratory (NWQL), near Denver, uses state-of-the-art technology to analyze samples for MTBE as part of the USGS water-quality studies. In addition, the NWQL offers custom analyses to determine two other fuel oxygenates--ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME). The NWQL was not able to obtain a reference standard for tert-amyl ethyl ether (TAEE), another possible fuel oxygenate (Shelley and Fouhy, 1994, p. 63). The shallow ground-water samples were collected as part of the USGS National Water-Quality Assessment Program. These samples were collected from 211 urban wells or springs and 562 agricultural wells sampled by the USGS in 1993 and 1994. The wells were keyed to specific land-use areas to assess the effects of different uses on ground-water quality (Squillace and others, 1995, p. 2). Ground-water samples were preserved on site to pH less than or equal to 2 with a solution of 1:1 hydrochloric acid. All samples were analyzed at the NWQL within 2 weeks after collection. The purpose of this fact sheet is to explain briefly the analytical method implemented by the USGS for determining MTBE and other fuel oxygenates. The scope is necessarily limited to an overview of the analytical method (instrumentation, sample preparation, calibration and quantitation, identification, and preservation of samples) and method performance (reagent blanks, accuracy, and precision).

  7. Preparation, Characterization and Permeation Behavior of Poly(methyl acrylate-Poly(dimethyl siloxane-Poly(methyl acrylate Block Copolymer/Poly(vinyl acetate Blend Membranes

    Directory of Open Access Journals (Sweden)

    Mohammad Ali Semsarzadeh

    2015-03-01

    Full Text Available Structure of polymeric materials is of the most important factors in determination of the characteristics and properties of the membranes. Various research and developments on polymeric membranes confirm the direct correlation between structure-properties of polymeric membranes. In this research, the structural outcome of poly(methyl acrylate-poly(dimethyl siloxane-poly(methyl acrylate/poly(vinyl acetate blend membranes and its relationship with gas permeation behavior of the blends were investigated. The flexible block copolymer of poly(methyl acrylate-poly(dimethyl siloxane-poly(methyl acrylate (PMA-PDMS-PMA was synthesized via atom transfer radical polymerization. Morphology and chemical structure of the synthesized block copolymer was investigated by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, gel permeation chromatography, X-ray diffraction analysis, differential scanning calorimetry and scanning electron microscopy. Blend membranes of PMA-PDMS-PMA and poly(vinyl acetate (PVAc were prepared by solution casting method in different compositions. By adding poly(vinyl acetate to PMA-PDMS-PMA block copolymer, the selectivity of the membranes for carbon dioxide/methane pair gases were increased by 55%. Fractional free volume (an indication of chain packing efficiency in blend membranes and dielectric constant (an indication of the molar volume and molar polarization of the blend membranes were obtained as the factors reflected the microstructural effect of PMA-PDMS-PMA and PVAc blend membranes. The efforts were directed toward expressing more precise structure-properties relationship of PMA-PDMS-PMA/PVAc blend membranes. The experimental permeability values of the blend membranes reported in this research were compared with the modified logarithmic model. The modified logarithmic model was evaluated for other blend membranes.

  8. Photochemical generation of highly destabilized vinyl cations: the effects of alpha- and beta-trifluoromethyl versus alpha- and beta-methyl substituents

    NARCIS (Netherlands)

    Alem, van K.; Belder, G.; Lodder, G.; Zuilhof, H.

    2005-01-01

    The photochemical reactions in methanol of the vinylic halides 1-4, halostyrenes with a methyl or a trifluoromethyl substituent at the - or -position, have been investigated quantitatively. Next to E/Z isomerization, the reactions are formation of vinyl radicals, leading to reductive dehalogenation

  9. Percutaneous Dissolution of Gallstones using Methyl Tert-Butyl Ether

    OpenAIRE

    1990-01-01

    Radiolucent cholesterol gallstones can be dissolved rapidly by methyl terc-buryl ether (MTBE) introduced directly into the gallbladder. Percutaneous transhepatic catheter placement is a well established interventional radiology procedure and is the preferred route for MTBE administration. A small number of patients have been treated using nasobiliary placement of a gallbladder catheter. Rapid stirring automatic pump systems allow dissolution of most cholesterol stones, but s...

  10. Solution of a gallstone with methyl-tertiary butyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Brambs, H J; Roeren, T; Holstege, A; Raedecke, J

    1987-08-01

    Methyl-t-butyl ether is a new agent to dissolve gallstones. The substance proves to be very successful and acts very rapidly. A percutaneous transhepatic drainage supplies an adequate access route to dissolve calculi within the bile ducts. We report the case of a patient where before insertion of an internal stent a stone in the common bile duct was dissolved within 3 1/2 hours.

  11. Synthesis of Poly(N-vinyl-2-pyrrolidone-co-methyl methacrylate by Maghnite-H+ a Non-toxic Catalyst

    Directory of Open Access Journals (Sweden)

    Mohamed Benadda

    2014-10-01

    Full Text Available In the present work poly (N-vinyl-2-pyrrolidone-co-methyl methacrylate copolymers were prepared successfully and cleanly by a one step process via cationic copolymerization of N-vinyl-2-pyrrolidone (NVP with methyl methacrylate (MMA, in heterogeneous phase using “Maghnite-H+” (Mag-H+ as catalyst in bulk, Maghnite is a montmorillonite sheet silicate clay exchanged with protons to produce Maghnite-H+. Temperature is varied between 20 and 80 °C. The effects of reaction temperature, amount of Mag-H+ on the yield and the intrinsic viscosity (η were investigated. A typical reaction product of poly (NVP-co- MMA was analyzed by infra red spectroscopy (FTIR and 1H-NMR, 13C-NMR spectroscopy as well as by viscosimetry. © 2014 BCREC UNDIP. All rights reservedReceived: 24th November 2013; Revised: 30th June 2014; Accepted: 8th July 2014How to Cite: Benadda, M., Ferrahi, M.I., Belbachir, M. (2014. Synthesis of Poly(N-vinyl-2-pyrrolidone-co-methyl methacrylate by Maghnite-H+ a Non-toxic Catalyst. Bulletin of Chemical Reaction Engineering & Catalysis, 9 (3: 201-206. (doi: 10.9767/bcrec.9.3.5743.201-206Permalink/DOI: http://dx.doi.org/10.9767/bcrec.9.3.5743.201-206

  12. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

    2016-01-01

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel

  13. Sulfonated poly(ether ether ketone)/poly(vinyl alcohol) sensitizing system for solution photogeneration of small Ag, Au, and Cu crystallites.

    Science.gov (United States)

    Korchev, A S; Shulyak, T S; Slaten, B L; Gale, W F; Mills, G

    2005-04-28

    Illumination of air-free aqueous solutions containing sulfonated poly(ether ether ketone) and poly(vinyl alcohol) with 350 nm light results in benzophenone ketyl radicals of the polyketone. The polymer radicals form with a quantum yield 0.02 and decay with a second-order rate constant 6 orders of magnitude lower than that of typical alpha-hydroxy radicals. Evidence is presented that the polymeric benzophenone ketyl radicals reduce Ag+, Cu2+, and AuCl4- to metal particles of nanometer dimensions. Decreases in the reduction rates with increasing Ag(I), Cu(II), and Au(III) concentrations are explained using a kinetic model in which the metal ions quench the excited state of the polymeric benzophenone groups, which forms the macromolecular radicals. Quenching is fastest for Ag+, whereas Cu2+ and AuCl4- exhibit similar rate constants. Particle formation becomes more complex as the number of equivalents needed to reduce the metal ions increases; the Au(III) system is an extreme case where the radical reactions operate in parallel with secondary light-initiated and thermal reduction channels. For each metal ion, the polymer-initiated photoreactions produce crystallites possessing distinct properties, such as a very strong plasmon in the Ag case or the narrow size distribution exhibited by Au particles.

  14. PHYSIOLOGICALLY BASED PHARMACOKINETIC MODEL FOR HUMAN EXPOSURES TO METHYL TERTIARY-BUTYL ETHER

    Science.gov (United States)

    Humans can be exposed by inhalation, ingestion, or dermal absorption to methyl tertiary-butyl ether (MTBE), an oxygenated fuel additive, from contaminated water sources. The purpose of this research was to develop a physiologically based pharmacokinetic model describing in human...

  15. Miscibility and Hydrogen Bonding in Blends of Poly(4-vinylphenol/Poly(vinyl methyl ketone

    Directory of Open Access Journals (Sweden)

    Hana Bourara

    2014-10-01

    Full Text Available The miscibility and phase behavior of poly(4-vinylphenol (PVPh with poly(vinyl methyl ketone (PVMK was investigated by differential scanning calorimetry (DSC, Fourier transform infrared spectroscopy (FTIR and scanning electron microscopy (SEM. It was shown that all blends of PVPh/PVMK are totally miscible. A DSC study showed the apparition of a single glass transition (Tg over their entire composition range. When the amount of PVPh exceeds 50% in blends, the obtained Tgs are found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are capable of forming interpolymer complexes. FTIR analysis revealed the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and carbonyl groups, which intensified when the amount of PVPh was increased in blends. Furthermore, the quantitative FTIR study carried out for PVPh/PVMK blends was also performed for the vinylphenol (VPh and vinyl methyl ketone (VMK functional groups. These results were also established by scanning electron microscopy study (SEM.

  16. IRON(III) NITRATE-CATALYZED FACILE SYNTHESIS OF DIPHENYLMETHYL (DPM) ETHERS FROM ALCOHOLS

    Science.gov (United States)

    Diphenyl methyl (DPM) ethers constitute important structural portion of some pharmaceutical entities and also as protective group for hydroxyl groups in synthetic chemistry. DPM ethers are normally prepared using concentrated acids or base as catalysts, which may result in the fo...

  17. LOCATION OF ACYL GROUPS ON TWO PARTLY ACYLATED GLYCOLIPIDS FROM STRAINS OF USTILAGO (SMUT FUNGI),

    Science.gov (United States)

    erythritol from Ustilago sp. (probably U. nuda (Jens.) Rostr. = U. tritici (Pers.) Rostr.) PRL-627 were acetalated with methyl vinyl ether, deacylated...Partly acylated ustilagic acids 8 (from Ustilago maydis (DC) Corda (= U. zeae Unger) PRL-119), consisting of partially esterified beta-cellobiosyl

  18. Preparation and characterization of poly (methyl methacrylate) and sulfonated poly (ether ether ketone) blend ultrafiltration membranes for protein separation applications

    International Nuclear Information System (INIS)

    Arthanareeswaran, G.; Thanikaivelan, P.; Raajenthiren, M.

    2009-01-01

    Poly (methyl methacrylate) (PMMA) and poly (methyl methacrylate)/sulfonated poly (ether ether ketone) (SPEEK) blend membranes were prepared by phase inversion technique in various composition using N,N'-dimethylformamide as solvent. The prepared membranes were characterized in terms of pure water flux, water content, porosity and thermal stability. The addition of SPEEK to the casting solution resulted in membranes with high pure water flux, water content, porosity and slightly low thermal stability. The cross sectional views of the blend membranes under electron microscope confirm the porosity and water flux results. The effect of the addition of SPEEK into the PMMA matrix on the extent of bovine serum albumin (BSA) separation was studied. It was found that the permeate flux increased significantly while the rejection of BSA from aqueous solution reduced moderately during ultrafiltration (UF) process. The effect was attributed to the increase in porosity and charge of the membrane due to the addition of SPEEK into the PMMA blend solution

  19. Application of Computational Methods Mm2 and Gussian for Studing Unimolecular Decomposition of Vinil Ethers based on the Mechanism of Hydrogen Bonding

    OpenAIRE

    Behnaz Shahrokh; Garnik N. Sargsyan; Arkadi B. Harutyunyan

    2012-01-01

    Investigations of the unimolecular decomposition of vinyl ethyl ether (VEE), vinyl propyl ether (VPE) and vinyl butyl ether (VBE) have shown that activation of the molecule of a ether results in formation of a cyclic construction - the transition state (TS), which may lead to the displacement of the thermodynamic equilibrium towards the reaction products. The TS is obtained by applying energy minimization relative to the ground state of an ether under the program MM2 when...

  20. Photosynthesis involvement in the mechanism of action of diphenyl ether herbicides.

    Science.gov (United States)

    Ensminger, M P; Hess, F D

    1985-05-01

    Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1'-dimethyl-4,4'-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity.

  1. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    Science.gov (United States)

    Smith, L.A. Jr.

    1983-03-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C[sub 4] hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether. 1 fig.

  2. Influence of acrylonitrile butadiene rubber on recyclability of blends prepared from poly(vinyl chloride) and poly(methyl methacrylate).

    Science.gov (United States)

    Suresh, Sunil S; Mohanty, Smita; Nayak, Sanjay K

    2018-06-01

    The current investigation deals with the recycling possibilities of poly(vinyl chloride) and poly(methyl methacrylate) in the presence of acrylonitrile butadiene rubber. Recycled blends of poly(vinyl chloride)/poly(methyl methacrylate) are successfully formed from the plastic constituents, those are recovered from waste computer products. However, lower impact performance of the blend and lower stability of the poly(vinyl chloride) phase in the recycled blend restricts its further usage in industrial purposes. Therefore, effective utilisation acrylonitrile butadiene rubber in a recycled blend was considered for improving mechanical and thermal performance. Incorporation of acrylonitrile butadiene rubber resulted in the improvement in impact performance as well as elongation-at-break of the recycled blend. The optimum impact performance was found in the blend with 9 wt% acrylonitrile butadiene rubber, which shows 363% of enhancement as compared with its parent blend. Moreover, incorporated acrylonitrile butadiene rubber also stabilises the poly(vinyl chloride) phase present in the recycled blend, similarly Fourier transform infrared spectroscopy studies indicate the interactions of various functionalities present in the recycled blend and acrylonitrile butadiene rubber. In addition to this, thermogravimetric analysis indicates the improvement in the thermal stability of the recycled blend after the addition of acrylonitrile butadiene rubber into it. The existence of partial miscibility in the recycled blend was identified using differential scanning calorimetry and scanning electron microscopy.

  3. Effect of monomer concentration on the kinetics of emulsifier-free emulsion polymerization of Vinyl Acetate and Methyl Acrylate

    International Nuclear Information System (INIS)

    Mohammad Beigi, H. R.

    2001-01-01

    The effect of monomer concentration on the kinetics of the emulsifier-free emulsion polymerization of vinyl acetate and methyl acrylate were studied. The polymerizations were carried out using potassium persulfate as the initiator. Form the electron micrographs of the resulting lattices, monodisperse PVAc and PMA lattices with particle diameters varying between 149-443 mm and 112-497 nm, respectively were processed. Uniformity of particle size indicated that nucleation of stable particle occurs early in the polymerization process. The polymerization rate was found to be proportional to the 0.88 and 1.5 power of the initial monomer concentration of vinyl acetate and methyl acrylate, respectively. Higher monomer concentration results in fewer particles and larger final particle diameter. With increasing monomer solubility in water the size of particle decreases and its distribution broadens

  4. Ternary and binary LLE measurements for solvent (2-methyltetrahydrofuran and cyclopentyl methyl ether) + furfural + water between 298 and 343 K

    International Nuclear Information System (INIS)

    Männistö, Mikael; Pokki, Juha-Pekka; Fournis, Ludivine; Alopaeus, Ville

    2017-01-01

    Highlights: • Novel LLE of 2-methyltetrahydrofuran or cyclopentyl methyl ether + furfural + water. • High performance solvents for liquid-liquid extraction exhibited. • Modelled with UNIQUAC-HOC activity coefficient model. • Comparison to other industrial solvents with distribution coefficient and selectivity. - Abstract: The suitability of two solvents for the extraction of furfural from aqueous streams is assessed through novel ternary and binary liquid-liquid equilibria data for mixtures of solvent (2-methyltetrahydrofuran or cyclopentyl methyl ether) + furfural + water. The measured data are reported along with regressed binary interaction parameters for UNIQUAC-HOC activity coefficient model and further analyzed through distribution coefficients and selectivity for furfural. Out of the two solvents, cyclopentyl methyl ether presents a very high selectivity along with good distribution coefficient in the entire temperature range.

  5. An efficient and highly selective ortho-tert-butylation of p-cresol with methyl tert-butyl ether catalyzed by sulfonated ionic liquids

    Directory of Open Access Journals (Sweden)

    Alamdari Reza Fareghi

    2014-01-01

    Full Text Available A novel series of sulfonic acid-functionalized ionic liquids (SFILs was found to act as efficient catalysts for ortho-tert-butylation of p-cresol with methyl tert-butyl ether (MTBE as the tert-butylating agent without an added solvent. The mono o-tert-butylated product was obtained in up to 80.4% isolated yield and 95.2% selectivity under such green conditions. No O-tert-butylated byproducts were formed.

  6. Role of distonic dimer radical cations in the radiation-induced polymerisation of vinyl ethers

    International Nuclear Information System (INIS)

    Naumov, Sergej; Janovsky, Igor; Knolle, Wolfgang; Mehnert, Reiner

    2005-01-01

    The experimental low-temperature EPR results and the quantum chemical calculations suggest that dimer radical cations of cyclic and aliphatic vinyl ethers (VE) plays a key role in starting of radiation-induced polymerisation. The main species observed at high 2,3-dihydrofuran (DHF), 2,3-dihydropyran (DHP) and VE concentration is the dimer radical cation. In the case of cyclic VE the dimer radical cation transforms through H-abstraction from neutral molecule into a carbocation and radical, which could start both cationic and free-radical polymerisation. However, in the case of aliphatic VE no further reactive species, which could start polymerisation, were observed. This is caused (in agreement with experiment and quantum chemical calculations) by the very high stability of dimer radical cation and calculated endothermity of H-abstraction reaction by dimer radical cation from monomer

  7. Photosynthesis Involvement in the Mechanism of Action of Diphenyl Ether Herbicides 1

    Science.gov (United States)

    Ensminger, Michael P.; Hess, F. Dan

    1985-01-01

    Photosynthesis is not required for the toxicity of diphenyl ether herbicides, nor are chloroplast thylakoids the primary site of diphenyl ether herbicide activity. Isolated spinach (Spinacia oleracea L.) chloroplast fragments produced malonyl dialdehyde, indicating lipid peroxidation, when paraquat (1,1′-dimethyl-4,4′-bipyridinium ion) or diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were added to the medium, but no malonyl dialdehyde was produced when chloroplast fragments were treated with the methyl ester of acifluorfen (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid), oxyfluorfen [2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene], or MC15608 (methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate). In most cases the toxicity of acifluorfen-methyl, oxyfluorfen, or MC15608 to the unicellular green alga Chlamydomonas eugametos (Moewus) did not decrease after simultaneous treatment with diuron. However, diuron significantly reduced cell death after paraquat treatment at all but the highest paraquat concentration tested (0.1 millimolar). These data indicate electron transport of photosynthesis is not serving the same function for diphenyl ether herbicides as for paraquat. Additional evidence for differential action of paraquat was obtained from the superoxide scavenger copper penicillamine (copper complex of 2-amino-3-mercapto-3-methylbutanoic acid). Copper penicillamine eliminated paraquat toxicity in cucumber (Cucumis sativus L.) cotyledons but did not reduce diphenyl ether herbicide toxicity. PMID:16664206

  8. Geissoschizine methyl ether, a corynanthean-type indole alkaloid from Uncaria rhynchophylla as a potential acetylcholinesterase inhibitor.

    Science.gov (United States)

    Yang, Zhong-Duo; Duan, Dong-Zhu; Du, Juan; Yang, Ming-Jun; Li, Shuo; Yao, Xiao-Jun

    2012-01-01

    Geissoschizine methyl ether (1), a newly discovered strong acetylcholinesterase (AChE) inhibitor, along with six weakly active alkaloids, vallesiachotamine (2), hisuteine (3), hirsutine (4), isorhynchophylline (5), cisocorynoxeine (6) and corynoxeine (7) have been isolated from Uncaria rhynchophylla. Geissoschizine methyl ether (1) inhibited 50% of AChE activity at concentrations of 3.7 ± 0.3 µg mL(-1) while the IC(50) value of physostigmine as a standard was 0.013 ± 0.002 µg mL(-1). The mode of AChE inhibition by 1 was reversible and non-competitive. In addition, molecular modelling was performed to explore the binding mode of inhibitor 1 at the active site of AChE.

  9. DERMAL, ORAL, AND INHALATION PHARMACOKINETICS OF METHYL TERTIARY BUTYL ETHER (MTBE) IN HUMAN VOLUNTEERS

    Science.gov (United States)

    Methyl tertiary butyl ether (MTBE), a gasoline additive, used to increase octane and reduce carbon monoxide emissions and ozone precursors has contaminated drinking water leading to exposure by oral, inhalation, and dermal routes. To determine its dermal, oral, and inhalation ki...

  10. (1-Adamantyl)methyl glycidyl ether: a versatile building block for living polymerization.

    Science.gov (United States)

    Moers, Christian; Wrazidlo, Robert; Natalello, Adrian; Netz, Isabelle; Mondeshki, Mihail; Frey, Holger

    2014-06-01

    (1-Adamantyl)methyl glycidyl ether (AdaGE) is introduced as a versatile monomer for oxyanionic polymerization, enabling controlled incorporation of adamantyl moieties in aliphatic polyethers. Via copolymerization with ethoxyethyl glycidyl ether (EEGE) and subsequent cleavage of the acetal protection groups of EEGE, hydrophilic linear polyglycerols with an adjustable amount of pendant adamantyl moieties are obtained. The adamantyl unit permits control over thermal properties and solubility profile of these polymers (LCST). Additionally, AdaGE is utilized as a termination agent in carbanionic polymerization, affording adamantyl-terminated polymers. Using these structures as macroinitiators for the polymerization of ethylene oxide affords amphiphilic, in-chain adamantyl-functionalized block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. DERMAL, ORAL AND INHALATION PHARMACOKINETICS OF METHYL TERTIARY-BUTYL ETHER (MTBE) IN HUMAN VOLUNTEERS

    Science.gov (United States)

    Methyl tertiary butyl ether (MTBE), a gasoline additive used to increase octane and reduce carbon monoxide emissions and ozone precursors, has contaminated drinking water and can lead to exposure by oral, inhalation, and dermal routes. To determine its dermal, oral, and inhal...

  12. Compatibility of polyvinyl alcohol and poly(methyl vinyl ether-co-maleic acid) blends estimated by molecular dynamics

    CSIR Research Space (South Africa)

    Moolman, FS

    2005-07-25

    Full Text Available are not dissociated (ionized). At pH below pKa (negative logarithm of acid dissociation constant) of maleic acid (first and second dissociation constants at 25 8C are pKa1Z1.91 and pKa 2Z6.33, respectively [22]), ioniz- ation of the carboxylic acid groups in the PMVE...-MA. Decreasing pH also reduces absolute viscosities and broadens the optimum blend ratio peak. Fig. 2. Density of a selected number of runs (11?15) as a function of time. F.S. Moolman et al. / Polymer 46 (2005) 6192?6200 6195 The cohesive energy densities display...

  13. Methyl vinyl glycolate as a diverse platform molecule

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Taarning, Esben; Madsen, Robert

    2016-01-01

    and various long-chain terminal olefins give unsaturated α-hydroxy fatty acid methyl esters in good yields. [3,3]-Sigmatropic rearrangements of MVG also proceed in good yields to give unsaturated adipic acid derivatives. Finally, rearrangement of the allylic acetate of MVG proceeds in acceptable yield...

  14. Hydrogels Prepared from Cross-Linked Nanofibrillated Cellulose

    Science.gov (United States)

    Sandeep S. Nair; J.Y. Zhu; Yulin Deng; Arthur J. Ragauskas

    2014-01-01

    Nanocomposite hydrogels were developed by cross-linking nanofibrillated cellulose with poly(methyl vinyl ether-co-maleic acid) and polyethylene glycol. The cross-linked hydrogels showed enhanced water absorption and gel content with the addition of nanocellulose. In addition, the thermal stability, mechanical strength, and modulus increased with an increase in the...

  15. Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    T.A. Semelsberger

    2004-10-01

    The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

  16. Risicogrenzen voor MTBE (Methyl tertiair-Butyl Ether) in bodem, sediment, grondwater, oppervlaktewater en voor drinkwaterbereiding

    NARCIS (Netherlands)

    Swartjes FA; Baars AJ; Fleuren RHLJ; Otte PF; LER

    2004-01-01

    Recentelijk is politieke commotie ontstaan ten gevolge van de mogelijke schadelijke gezondheidseffecten van Methyl tertiair-Butyl Ether (MTBE). Dit was reden voor het ministerie van VROM om het RIVM te verzoeken risicogrenzen voor MTBE in bodem, sediment, grondwater, oppervlaktewater, drinkwater en

  17. Searching for trans ethyl methyl ether in Orion KL.

    Science.gov (United States)

    Tercero, B; Cernicharo, J; López, A; Brouillet, N; Kolesniková, L; Motiyenko, R A; Margulès, L; Alonso, J L; Guillemin, J-C

    2015-10-01

    We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH 3 CH 2 OCH 3 , through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH 3 CH 2 CH 2 OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 10 15 cm -2 and ≤(1.0 ± 0.2)× 10 15 cm -2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH 3 OCOH, CH 3 CH 2 OCOH, CH 3 OCH 3 , CH 3 OH, and CH 3 CH 2 OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N (CH 3 OCH 3 )/ N (tEME) ≥ 150 in the compact ridge of Orion.

  18. Cytotoxicity of S-conjugates of the sevoflurane degradation product fluoromethyl-2,2-difluoro-1-(trifluoromethyl) vinyl ether (Compound A) in a human proximal tubular cell line

    International Nuclear Information System (INIS)

    Altuntas, T. Gul; Zager, Richard A.; Kharasch, Evan D.

    2003-01-01

    Fluoromethyl-2,2-difluoro-1-(trifluoromethyl)vinyl ether (FDVE) is a fluorinated alkene formed by degradation of the volatile anesthetic sevoflurane in anesthesia machines. FDVE is nephrotoxic in rats but not humans. Rat FDVE nephrotoxicity is attributed to FDVE glutathione conjugation and bioactivation of subsequent FDVE-cysteine S-conjugates, in part by renal β-lyase. Although FDVE conjugation and metabolism occur in both rats and humans, the mechanism for selective toxicity in rats and lack of effect in humans is incompletely elucidated. This investigation measured FDVE S-conjugate cytotoxicity in cultured human proximal tubular HK-2 cells, and compared this with known cytotoxic S-conjugates. HK-2 cells were incubated with FDVE and its GSH, cysteine S-mercapturic acid, cysteine S-sulfoxide, and mercapturic acid sulfoxide conjugates (0.1-2.7 mM) for 24 h. Cytotoxicity was determined by lactate dehydrogenase (LDH) release, total LDH, and the ability of viable cells to reduce a tetrazolium-based compound (MTT). FDVE was cytotoxic only at concentrations ≥0.9 mM. No increase in LDH release was observed with either FDVE-GSH conjugate. The FDVE-cysteine conjugates S-(1,1-difluoro-2-fluoromethoxy-2-(trifluoromethyl) ethyl)-L-cysteine (DFEC) and (Z)-S-(1-fluoro-2-fluoromethoxy-2-(trifluoromethyl) vinyl)-L-cysteine ((Z)-FFVC) caused significant differences in LDH release and MTT reduction only at 2.7 mM; (Z)-FFVC was slightly more cytotoxic. Both S-(1,1-difluoro-2-fluoromethoxy-2-(trifluoromethyl) ethyl)-L-cysteine sulfoxide (DFEC-SO) and (Z)-N-acetyl-S-(1-fluoro-2-fluoromethoxy-2-(trifluoromethyl) vinyl)-L-cysteine sulfoxide ((Z)-N-Ac-FFVC-SO) caused slightly greater changes in LDH release or total LDH than the corresponding equimolar DFEC and (Z)-N-acetyl-S-(1-fluoro-2-fluoromethoxy-2-(trifluoromethyl) vinyl)-L-cysteine ((Z)-N-Ac-FFVC) conjugates. In contrast to FDVE S-conjugates, S-(1,2-dichlorovinyl)-L-cysteine was markedly cytotoxic, at concentrations as low as 0

  19. New biphasic solvent system based on cyclopentyl methyl ether for the purification of a non-polar synthetic peptide by pH-zone refining centrifugal partition chromatography.

    Science.gov (United States)

    Amarouche, Nassima; Boudesocque, Leslie; Borie, Nicolas; Giraud, Matthieu; Forni, Luciano; Butte, Alessandro; Edwards, Florence; Renault, Jean-Hugues

    2014-06-01

    A new type 1 ternary biphasic system composed of cyclopentyl methyl ether, dimethylformamide and water was developed, characterized and successfully used for the purification of a lipophilic, protected peptide by pH-zone refining centrifugal partition chromatography. The protected peptide is an 8-mer, key intermediate in bivalirudin (Angiomax®) synthesis and shows a very low solubility in the solvents usually used in liquid chromatography. All ionic groups, except the N-terminal end of the peptide, are protected by a benzyl group. The purification of this peptide was achieved with a purity of about 99.04% and a recovery of 94% using the new ternary biphasic system cyclopentyl methyl ether/dimethylformamide/water (49:40:11, v/v) in the descending pH-zone refining mode with triethylamine (28 mM) as the retainer and methanesulfonic acid (18 mM) as the eluter. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Methyl internal rotation in the microwave spectrum of vinyl acetate.

    Science.gov (United States)

    Nguyen, Ha Vinh Lam; Jabri, Atef; Van, Vinh; Stahl, Wolfgang

    2014-12-26

    The rotational spectrum of vinyl acetate, CH3(CO)OCH═CH2, was measured using two molecular beam Fourier transform microwave spectrometers operating in the frequency range from 2 to 40 GHz. Large splittings up to 2 GHz occurred due to the internal rotation of the acetyl methyl group CH3CO with a V3 potential of 151.492(34) cm(-1), much larger than the barrier of approximately 100 cm(-1) often found in acetates. The torsional transitions were fitted using three different programs XIAM, ERHAM, and BELGI-Cs, whereby the rotational constants, centrifugal distortion constants, and the internal rotation parameters could be determined with very high accuracy. The experimental results were supported by quantum chemical calculations. For a conformational analysis, potential energy surfaces were calculated.

  1. Wax inhibitor based on ethylene vinyl acetate with methyl methacrylate and diethanolamine for crude oil pipeline

    Science.gov (United States)

    Anisuzzaman, S. M.; Abang, S.; Bono, A.; Krishnaiah, D.; Karali, R.; Safuan, M. K.

    2017-06-01

    Wax precipitation and deposition is one of the most significant flow assurance challenges in the production system of the crude oil. Wax inhibitors are developed as a preventive strategy to avoid an absolute wax deposition. Wax inhibitors are polymers which can be known as pour point depressants as they impede the wax crystals formation, growth, and deposition. In this study three formulations of wax inhibitors were prepared, ethylene vinyl acetate, ethylene vinyl acetate co-methyl methacrylate (EVA co-MMA) and ethylene vinyl acetate co-diethanolamine (EVA co-DEA) and the comparison of their efficiencies in terms of cloud point¸ pour point, performance inhibition efficiency (%PIE) and viscosity were evaluated. The cloud point and pour point for both EVA and EVA co-MMA were similar, 15°C and 10-5°C, respectively. Whereas, the cloud point and pour point for EVA co-DEA were better, 10°C and 10-5°C respectively. In conclusion, EVA co-DEA had shown the best % PIE (28.42%) which indicates highest percentage reduction of wax deposit as compared to the other two inhibitors.

  2. QSPR models of n-octanol/water partition coefficients and aqueous solubility of halogenated methyl-phenyl ethers by DFT method.

    Science.gov (United States)

    Zeng, Xiao-Lan; Wang, Hong-Jun; Wang, Yan

    2012-02-01

    The possible molecular geometries of 134 halogenated methyl-phenyl ethers were optimized at B3LYP/6-31G(*) level with Gaussian 98 program. The calculated structural parameters were taken as theoretical descriptors to establish two new novel QSPR models for predicting aqueous solubility (-lgS(w,l)) and n-octanol/water partition coefficient (lgK(ow)) of halogenated methyl-phenyl ethers. The two models achieved in this work both contain three variables: energy of the lowest unoccupied molecular orbital (E(LUMO)), most positive atomic partial charge in molecule (q(+)), and quadrupole moment (Q(yy) or Q(zz)), of which R values are 0.992 and 0.970 respectively, their standard errors of estimate in modeling (SD) are 0.132 and 0.178, respectively. The results of leave-one-out (LOO) cross-validation for training set and validation with external test sets both show that the models obtained exhibited optimum stability and good predictive power. We suggests that two QSPR models derived here can be used to predict S(w,l) and K(ow) accurately for non-tested halogenated methyl-phenyl ethers congeners. Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. INHALATION EXPOSURE TO METHYL TERT-BUTYL ETHER (MTBE) AND DIBROMOCHLOROMETHANE (DBCM) USING CONTINUOUS BREATH ANALYSIS

    Science.gov (United States)

    The oxygenate methyl tert-butyl ether (MTBE) has been added to gasoline to help meet national ambient air quality standards in those parts of the U.S. that are non-compliant for carbon monoxide. Although MTBE has provided important health benefits in terms of reduced haza...

  4. Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Francois, A

    2002-11-01

    Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

  5. Life test of DMFC using poly(ethylene glycol)bis(carboxymethyl)ether plasticized PVA/PAMPS proton-conducting semi-IPNs

    Energy Technology Data Exchange (ETDEWEB)

    Qiao, Jinli [National Institute of Advanced Industrial Science and Technology, Higashi 1-1-1, Central 5, Tsukuba, Ibaraki 305-8565 (Japan); New Energy Technology Research Center, Tongji University, Shanghai 201804 (China); Ikesaka, Shinya; Saito, Morihiro; Kuwano, Jun [Department of Industrial Chemistry, Faculty of Engineering, Tokyo University of Science, 12-1 Ichigayafunagawara-machi, Shinjuku-ku, Tokyo 162-0826 (Japan); Okada, Tatsuhiro [National Institute of Advanced Industrial Science and Technology, Higashi 1-1-1, Central 5, Tsukuba, Ibaraki 305-8565 (Japan)

    2007-08-15

    A novel, low-cost proton-conducting semi-IPN (semi-interpenetrating polymer network) has been successfully prepared from PVA/PAMPS (poly(vinyl alcohol) and poly(2-acrylamindo-2-methyl-1-propanesulfonic acid))blends by incorporating poly(ethylene glycol)bis(carboxymethyl)ether (PEGBCME) as a novel plasticizer. Although, the polymer is based on a relatively low content of PAMPS as a component of ion conducting sites, the resulting semi-IPN exhibited high proton conductivity (0.1 S cm{sup -1}) at 25 C, which afforded a higher power density of 51 mW cm{sup -2} at 80 C. A striking feature is that a long-term initial performance is achieved with a 130 h of stable fuel cell operation in DMFC mode due to effectively suppressed methanol crossover. This is a new record for a fully hydrocarbon membrane in DMFC, seeing that the PVA-PAMPS proton-conducting semi-IPNs are made simply of aliphatic skeletons. (author)

  6. Degradation of a recalcitrant xenobiotic compound: methyl tert-butyl ether (MTBE) metabolism by mycobacterium austroafricanum; Degradation d'un compose xenobiotique recalcitrant: metabolisme du methyl tert-butyl ether (MTBE) par mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Francois, A.

    2002-11-01

    Methyl tert-butyl ether (MTBE) is introduced up to 15% (vol/vol) in gasoline in order to obtain a good octane number and to prevent carbon monoxide emissions. However, as a consequence of storage tanks leakage, MTBE became one of the major pollutants of aquifers because of its very low biodegradability. The present study aimed at investigating the biodegradation of MTBE by Mycobacterium austroafricanum IFP 2012. The MTBE metabolic pathway was partially elucidated owing to the identification of some intermediates (tert-butyl formate (TBF), tert-butyl alcohol (TBA), a-hydroxy-isobutyric acid and acetone) and some enzymatic activities (MTBE/TBA monooxygenase (non hemic and inducible), TBF esterase, 2-propanol: NDMA oxidoreductase and another monooxygenase involved in acetone degradation). The involvement of TBF and the requirement of cobalt could be explanations for the low natural attenuation of MTBE; whereas the methoxy group does not seem to be implicated. (author)

  7. Simultaneous Determination of Salicylic Acid, Jasmonic Acid, Methyl Salicylate, and Methyl Jasmonate from Ulmus pumila Leaves by GC-MS

    Directory of Open Access Journals (Sweden)

    Zhi-hong Huang

    2015-01-01

    Full Text Available Salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate are important phytohormones and defensive signaling compounds, so it is of great importance to determine their levels rapidly and accurately. The study uses Ulmus pumila leaves infected by Tetraneura akinire Sasaki at different stages as materials; after extraction with 80% methanol and ethyl acetate and purification with primary secondary amine (PSA and graphitized carbon blacks (GCB, the contents of signal compounds salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate were determined by GC-MS. The results showed that the level of salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate increased remarkably in U. pumila once infected by T. akinire Sasaki, but the maximums of these four compounds occurred at different times. Salicylic acid level reached the highest at the early stage, and jasmonic acid level went to the maximum in the middle stage; by contrast, change of content of methyl salicylate and methyl jasmonate was the quite opposite.

  8. Simultaneous Determination of Salicylic Acid, Jasmonic Acid, Methyl Salicylate, and Methyl Jasmonate from Ulmus pumila Leaves by GC-MS.

    Science.gov (United States)

    Huang, Zhi-Hong; Wang, Zhi-Li; Shi, Bao-Lin; Wei, Dong; Chen, Jian-Xin; Wang, Su-Li; Gao, Bao-Jia

    2015-01-01

    Salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate are important phytohormones and defensive signaling compounds, so it is of great importance to determine their levels rapidly and accurately. The study uses Ulmus pumila leaves infected by Tetraneura akinire Sasaki at different stages as materials; after extraction with 80% methanol and ethyl acetate and purification with primary secondary amine (PSA) and graphitized carbon blacks (GCB), the contents of signal compounds salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate were determined by GC-MS. The results showed that the level of salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate increased remarkably in U. pumila once infected by T. akinire Sasaki, but the maximums of these four compounds occurred at different times. Salicylic acid level reached the highest at the early stage, and jasmonic acid level went to the maximum in the middle stage; by contrast, change of content of methyl salicylate and methyl jasmonate was the quite opposite.

  9. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C−O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination

    KAUST Repository

    Liu, Xiangqian

    2016-04-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process.

  10. Effect of gamma ray on poly(lactic acid)/poly(vinyl acetate-co-vinyl alcohol) blends as biodegradable food packaging films

    International Nuclear Information System (INIS)

    Razavi, Seyed Mohammad; Dadbin, Susan; Frounchi, Masoud

    2014-01-01

    Poly(lactic acid) (PLA)/poly(vinyl acetate-co-vinyl alcohol) [P(VAc-co-VA)] blends as new transparent film packaging materials were prepared at various blend compositions and different vinyl alcohol contents. The blends and pure PLA were irradiated by gamma rays to investigate the extent of changes in the packaging material during gamma ray sterilization process. The miscibility of the blends was dependent on the blend composition and vinyl alcohol content; gamma irradiation had little effect on the extent of miscibility. The glass transition temperature of pure PLA and PLA/P(VAc-co-VA) miscible blends reduced after irradiation. On the other hand in PLA/P(VAc-co-VA) immiscible blends, while the glass transition temperature of the PLA phase decreased; that of the copolymer phase slightly increased. The reduction in the glass transition was about 10 percent for samples irradiated with 50 kGy indicating dominance of chain scission of PLA molecules at high irradiation dose. The latter was verified by drop in mechanical properties of pure PLA after exposing to gamma irradiation at 50 kGy. Blending of PLA with the copolymer P(VAc-co-VA) compensated greatly the adverse effects of irradiation on PLA. The oxygen-barrier property of the blend was superior to the neat PLA and remained almost intact with irradiation. The un-irradiated and irradiated blends had excellent transparency. Gamma ray doses used for sterilization purposes are usually less than 20 kGy. It was shown that gamma irradiation at 20 kGy had no or little adverse effects on PLA/P(VAc-co-VA) blends mechanical and gas barrier properties. - Highlights: • Poly(lactic acid)/poly(vinyl acetate-co-vinyl alcohol) blends were prepared as new packaging film. • The blends are superior to PLA in oxygen gas barrier property. • The blends are suitable for gamma ray sterilization and maintain useful mechanical properties. • The blends are perfectly transparent

  11. Poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) membranes

    Energy Technology Data Exchange (ETDEWEB)

    Hwang, Mi-Lim; Choi, Jisun; Woo, Hyun-Su; Kumar, Vinod; Sohn, Joon-Yong; Shin, Junhwa, E-mail: shinj@kaeri.re.kr

    2014-02-15

    Highlights: • PEEK-g-PVBSA, a polymer electrolyte membrane was prepared by a radiation grafting technique. • Poly(ether ether ketone) (PEEK), an aromatic hydrocarbon polymer was used as a grafting backbone film. • The water uptake, proton conductivity, and methanol permeability of the membranes were evaluated. • PEEK-g-PVBSA membranes show considerably lower methanol permeability compared to a Nafion membrane. -- Abstract: In this study, an aromatic hydrocarbon based polymer electrolyte membrane, poly(vinylbenzyl sulfonic acid)-grafted poly(ether ether ketone) (PEEK-g-PVBSA), has been prepared by the simultaneous irradiation grafting of vinylbenzyl chloride (VBC) monomer onto a PEEK film and subsequent sulfonation. Each chemical conversion was monitored by FT-IR and SEM–EDX instruments. The physicochemical properties including IEC, water uptake, proton conductivity, and methanol permeability of the prepared membranes were also investigated and found that the values of these properties increase with the increase of degree of grafting. It was observed that the IEC values of the prepared PEEK-g-PVBSA membranes with 32%, 58%, and 80% DOG values were 0.50, 1.05, and 1.22 meq/g while the water uptakes were 14%, 20%, and 21%, respectively. The proton conductivities (0.0272–0.0721 S/cm at 70 °C) were found to be somewhat lower than Nafion 212 (0.126 S/cm at 70 °C) at a relative humidity of 90%. However, the prepared membranes showed a considerably lower methanol permeability (0.61–1.92 × 10{sup −7} cm{sup 2}/s) compared to a Nafion 212 membrane (5.37 × 10{sup −7} cm{sup 2}/s)

  12. SYNTHESIS OF CHIRAL BINAPHTHYL CROWN ETHERS AND THEIR USE IN ANIONIC POLYMERIZATION OF METHYL METHACRYLATE AS INITIATOR LIGANDS

    Institute of Scientific and Technical Information of China (English)

    Hong-wei Liu; Chuan-fu Chen; Fu Xi

    2004-01-01

    Some chiral binaphthyl crown ethers were synthesized. The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of t-BuOK, Ph2CHK or Ph2CHNa (RM), and RM coordination initiator by using chiral binaphthyl crown ethers as ligands, respectively. The results showed that in the former case the PMMA obtained has mainly isotactic structure but without optical activity, while in the later case the PMMA produced predominately has syndiotactic suucture also without optical activity.

  13. Poly(aniline-co-m-aminobenzoic acid) deposited on poly(vinyl ...

    Indian Academy of Sciences (India)

    Abstract. In this work, we have deposited poly(aniline-co-m-aminobenzoic acid) on poly(vinyl alcohol) (PVA) by in situ ... along the polyaniline (PANI) chain results in self dop- ing of PANI and ..... The value of electrical conductivity is found to be ...

  14. Geissoschizine methyl ether N-oxide, a new alkaloid with antiacetylcholinesterase activity from Uncaria rhynchophylla.

    Science.gov (United States)

    Jiang, Wei-Wei; Su, Jia; Wu, Xing-De; He, Juan; Peng, Li-Yan; Cheng, Xiao; Zhao, Qin-Shi

    2015-01-01

    Geissoschizine methyl ether N-oxide, a new oxindole alkaloid, along with 14 known alkaloids, was isolated from the aerial part of Uncaria rhynchophylla. Their structures were identified by comprehensive spectral methods, including 2D NMR experiments, and confirmed by comparing with the literature data. In vitro acetylcholinesterase (AChE) inhibitory activity assay showed that the new compound exhibited anti-AChE activity with IC₅₀ value of 23.4 μM.

  15. Searching for trans ethyl methyl ether in Orion KL★,★★

    Science.gov (United States)

    Tercero, B.; Cernicharo, J.; López, A.; Brouillet, N.; Kolesniková, L.; Motiyenko, R. A.; Margulès, L.; Alonso, J. L.; Guillemin, J.-C.

    2015-01-01

    We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm−2 and ≤(1.0 ± 0.2)× 1015 cm−2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion. PMID:26869726

  16. Biotransformation of ferulic acid to 4-vinyl guaiacol by Lactobacillus ...

    African Journals Online (AJOL)

    Continuously growing demand for natural flavors has led to a tremendous increase in biotransformation process employing microorganisms of different genera using ferulic acid (FA) as the precursor. In this study, potential of Lactobacillus farciminis (ATCC 29644) for biotransformation of FA to 4-vinyl guaiacol (4VG) was ...

  17. Miconidin and miconidin methyl ether from Primula obconica Hance: new allergens in an old sensitizer

    DEFF Research Database (Denmark)

    Paulsen, Evy; Christensen, Lars P; Andersen, Klaus Ejner

    2006-01-01

    . obconica. 12 primin-positive persons were patch tested with miconidin 0.01% petrolatum (pet.), miconidin in 96% ethanol incorporated into 0.01% pet., and miconidin methyl ether 1.0% pet. All persons were positive to miconidin 0.01% pet., with the strength of reactions very similar to those...

  18. Rotation of methyl side groups in polymers: A Fourier transform approach to quasielastic neutron scattering. 1: Homopolymers

    International Nuclear Information System (INIS)

    Arrighi, V.; Higgins, J.S.; Howells, W.S.

    1995-01-01

    The rotational motion of the ester methyl group in poly(methyl methacrylate) (PMMA) was investigated using quasielastic neutron scattering (QENS). A comparison between the authors results and the QENS data reported in the literature for PMMA-d 5 indicates that the amount of quasielastic broadening is highly dependent upon the energy resolution of the spectrometer. This anomalous behavior is here attributed to the method of analysis, namely, the use of a single rotational frequency. Such a procedure leads to a non-Arrhenius temperature dependence, to a temperature-dependent elastic incoherent structure factor, and to values of rotational frequency which are resolution dependent. They propose an alternative approach to the analysis of the QENS data which accounts for the existence of a distribution of rotational frequencies. The frequency data are Fourier transformed to the time domain, and the intermediate scattering function is fitted using a stretched exponential or Kohlraush-Williams-Watts function. The excellent overlap between data from different spectrometers leaves no doubt on the adequacy of their procedure. Measurements of the ether methyl group rotation in poly(vinyl methyl ether) (PVME) are also reported. The PVME data confirm that the behavior observed for PMMA-d 5 is likely to be a common feature to all polymeric systems

  19. Observation on the biodegradation and bioremediation potential of methyl t-butyl ether

    International Nuclear Information System (INIS)

    Salanitro, J.; Wisniewski, H.; McAllister, P.

    1995-01-01

    There have been few reports documenting evidence for the biodegradation of the fuel oxygenate alkyl ether, methyl t-butyl ether (MTBE) in groundwater, soils, and biosludges. Partial (or complete) microbial breakdown of MTBE has been observed in an anaerobic subsoil, a river sediment under methanogenic conditions, a cyclohexane-degrading bacterial consortium and a pure culture of the methylotroph, Methylisnus trichosporium OB3b. An aerobic bacterial enrichment (BC-1) isolated from an industrial transient (non-accumulating) metabolic intermediate. The studies suggest that MTBE is cleaved by BC-1 to TBA which is then metabolized via isopropanol and acetone. There is little information on the occurrence of indigenous MTBE-degraders in groundwater, soils and activated sludges. Preliminary evidence has been obtained, however, from a marketing terminal groundwater site that naturally-occurring MTBE-degraders are present in some monitoring wells. Microcosm experiments with groundwater from this aquifer show that MTBE is aerobically degraded (no TBA formed) with a first-order decay rate (0.31/day) similar to BTEX. Also, MTBE did not inhibit the intrinsic biodegradation potential of BTEX in groundwater microcosms. In summary, the data presented indicate that MTBE biodegradation has been observed in some environmental media. Further work is needed to assess the feasibility of using indigenous or derived aerobic and anaerobic MTBE-degrading cultures for treating fuel ethers in groundwaters or wastewater with in-situ or ex-situ bioremediation technologies

  20. DEVELOPMENT OF PHYSIOLOGICAL-BASED PHARMACOKINETIC MODEL FOR DERMAL ABSORPTION NAD PENETRATION OF METHYL TERTIARY BUTYL ETHER IN HUMANS

    Science.gov (United States)

    Background: Methyl tertiary butyl ether (MTBE) is a volatile organic chemical that is added to gasoline as an octane booster and to reduce vehicular emissions of carbon monoxide. MTBE is introduced into the environment through fuel spills, leakage of storage tanks, and evaporat...

  1. TOXICITY OF METHYL-TERT BYTYL ETHER (MTBE) TO PLANTS (AVENA SATIVA, ZEA MAYS, TRITICUM AESTIVUM, AND LACTUCA SATIVA)

    Science.gov (United States)

    Effects of Methyl tert-butyl ether (MTBE) on the germination of seeds and growth of the plant were studied in some laboratory experiments. Test plants were wild oat (Avena sative), sweet corn (Zea mays), wheat (Triticum aestivum), and lettuce (Lactuca sativa). Seed germination,...

  2. Synthesis of (E)-9-Oxo-2-decenoic acid (the queen substance of honeybee) from methyl 3-formylpropionate; 3-horumiruporopion san mechiru wo mochiita (E)-9-okiso-2-desen san (Mitsubachi joo busshitsu) no gosei

    Energy Technology Data Exchange (ETDEWEB)

    Tsukasa, H. [Toyotama Koryo Co. Ltd., Tokyo (Japan)

    1997-05-20

    The queen substance, (E)-9-oxo-2-decenoic acid (1) is a pheromone secreted by queen honeybee (Apis mellifera) and inhibits reproductive ability of worker bees. Several synthesese have been reported. It was synthesized starting from methyl-3-formylpropionate this time. Methyl 7,7-ethylenedioxy-4-oxooctanoate was prepared by radical addition reaction from (2) and 2-methyl-2-vinyl-1,3-dioxolane and reduced to an ethyelenedioxy carboxylic acid with hydrazine and KOH. This compound was converted to an alcohol by reduction with sodium bis(2-methoxyethoxy)aluminum hydride, followed by oxidation with pyridinium chlorochromate to an acetal aldehyde, which was condensed with malonic acid and (1) was obtained after the hydrolysis with hydrochloric acid. 7 refs., 1 tab.

  3. CF3+ fragmentation by electron impact ionization of perfluoro-propyl-vinyl-ethers, C5F10O, in gas phase

    Science.gov (United States)

    Kondo, Yusuke; Ishikawa, Kenji; Hayashi, Toshio; Miyawaki, Yudai; Takeda, Keigo; Kondo, Hiroki; Sekine, Makoto; Hori, Masaru

    2015-04-01

    The gas phase fragmentations of perfluoro-propyl-vinyl ether (PPVE, C5F10O) are studied experimentally. Dominant fragmentations of PPVE are found to be the result of a dissociative ionization reaction, i.e., CF3+ via direct bond cleavage, and C2F3O- and C3F7O- via electron attachment. Regardless of the appearance energy of around 14.5 eV for the dissociative ionization of CF3+, the observed ion efficiency for the CF3+ ion was extremely large the order of 10-20 cm-2, compared with only 10-21 cm-2 for the other channels. PPVE characteristically generated CF3+ as the largest abundant ion are advantageous for use of feedstock gases in plasma etching processes.

  4. Experimental vapor pressures (from 1 Pa to 100 kPa) of six saturated Fatty Acid Methyl Esters (FAMEs): Methyl hexanoate, methyl octanoate, methyl decanoate, methyl dodecanoate, methyl tetradecanoate and methyl hexadecanoate

    International Nuclear Information System (INIS)

    Sahraoui, Lakhdar; Khimeche, Kamel; Dahmani, Abdallah; Mokbel, Ilham; Jose, Jacques

    2016-01-01

    Highlight: • Vapor-liquid equilibria, Enthalpy of Vaporization, saturated Fatty Acid Methyl Ester. - Abstract: Vapor pressures of six saturated Fatty Acid Methyl Esters (FAMEs), methyl hexanoate (or methyl caproate), methyl octanoate (or methyl caprylate), Methyl decanoate (or methyl caprate), methyl dodecanoate (or methyl laurate), methyl tetradecanoate (or methyl myristate), and methyl hexadecanoate (or methyl palmitate) were measured from 1 Pa to 100 kPa and at temperature range between 262 and 453 K using a static apparatus. The experimental data (P-T) were compared with the available literature data.

  5. Naturally occurring methyl salicylate glycosides.

    Science.gov (United States)

    Mao, Ping; Liu, Zizhen; Xie, Meng; Jiang, Rui; Liu, Weirui; Wang, Xiaohong; Meng, Shen; She, Gaimei

    2014-01-01

    As an important part of non steroids anti-inflammation drug (NSAIDs), salicylate has developed from natural substance salicylic acid to natrium salicylicum, to aspirin. Now, methyl salicylate glycoside, a new derivative of salicylic acid, is modified with a -COOH group integrated one methyl radical into formic ether, and a -OH linked with a monosaccharide, a disaccharide or a trisaccharide unit by glycosidic linkage. It has the similar pharmacological activities, anti-inflammatory, analgesic, antipyretic and antithrombotic as the previous salicylates' without resulting in serious side effects, particularly the gastrointestinal toxicity. Owing to the superiority of those significant bioactivities, methyl salicylate glycosides have became a hot research area in NSAIDs for several years. This paper compiles all 9 naturally occurring methyl salicylate glycosides, their distribution of the resource and pharmacological mechanism, which could contribute to the new drug discovery.

  6. Analysis of chemical signatures of alkaliphiles using fatty acid methyl ester analysis

    Directory of Open Access Journals (Sweden)

    Basha Sreenivasulu

    2017-01-01

    Full Text Available Background: Fatty acids occur in nearly all living organisms as the important predominant constituents of lipids. While all fatty acids have essentially the same chemical nature, they are an extremely diverse group of compounds. Materials and Methods: To test the hypothesis, fatty acids of alkaliphiles isolates, Bacillus subtilis SVUNM4, Bacillus licheniformis SVUNM8, Bacillus methylotrohicus SVUNM9, and Paenibacillus dendritiformis SVUNM11, were characterized compared using gas chromatography-mass spectrometry (GC-MS analysis. Results: The content of investigated ten fatty acids, 1, 2-benzenedicarboxylic acid butyl 2-methylpropyl ester, phthalic acid, isobutyl 2-pentyl ester, dibutyl phthalate, cyclotrisiloxane, hexamethyl, cyclotetrasiloxane, octamethyl, dodecamethyl, heptasiloxane 1,1,3,3,5,5,7,7,9,9,11,11,13,13-etradecamethyl, 7,15-dihydroxydehydroabietic acid, methyl ester, di (trimethylsilyl ether, hentriacontane, 2-thiopheneacetic acid, undec-2-enyl ester, obviously varied among four species, suggesting each species has its own fatty acid pattern. Conclusions: These findings demonstrated that GC-MS-based fatty acid profiling analysis provides the reliable platform to classify these four species, which is helpful for ensuring their biotechnological interest and novel chemotaxonomic.

  7. Acid-catalyzed rearrangements of flavans to novelbenzofuran derivatives

    Science.gov (United States)

    Richard W. Hemingway; Weiling Peng; Anthony H. Conner; Petrus J. Steynberg; Jan P. Steynberg

    1998-01-01

    The objective of this work was to define reactions that occur when proanthocyanidins and their derivatives are reacted in the presence of acid catalysts. Pure compounds (either as the free phenols, the methyl ether, or the methyl ether-acetate derivatives) were isolated by a variety of chromatographic methods. Proof of their structure was based mainly on 2D-NMR, as...

  8. Volumetric Behaviour of the Ternary System (Methyl Tert-butyl ether + Methylbenzene + Butan-1-ol) and Its Binary sub-System (Methyl Tert-Butyl Ether + Butan-1-ol) within the Temperature Range (298.15–328.15) K

    Czech Academy of Sciences Publication Activity Database

    Morávková, Lenka; Troncoso, J.; Škvorová, M.; Havlica, Jaromír; Petrus, P.; Sedláková, Zuzana

    2015-01-01

    Roč. 90, NOV 2015 (2015), s. 59-70 ISSN 0021-9614 R&D Projects: GA ČR(CZ) GAP105/12/0664; GA MŠk(CZ) LD14094 Grant - others:GNIL(IT) 408 REGALIs (CN2012/120) Institutional support: RVO:67985858 Keywords : methylbenzene * density * methyl-tert-butyl ether Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.196, year: 2015

  9. Gold-catalyzed alkylation of silyl enol ethers with ortho-alkynylbenzoic acid esters

    Directory of Open Access Journals (Sweden)

    Yoshinori Yamamoto

    2011-05-01

    Full Text Available Unprecedented alkylation of silyl enol ethers has been developed by the use of ortho-alkynylbenzoic acid alkyl esters as alkylating agents in the presence of a gold catalyst. The reaction probably proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack on the silyl enol ethers. The generated leaving compound abstracts a proton to regenerate the silyl enol ether structure.

  10. INTERACTION OF METHYL-TERT BUTYL ETHER AND WATER STRESS ON SEED GERMINATION AND SEEDLING GROWTH IN SOIL MICROCOSMS

    Science.gov (United States)

    Methyl tert-butyl ether (MTBE) is a widespread contaminant in surface and ground water in the United States. Frequently irrigation is used to water fields to germinate planted seeds and sustain plant growth. A likely possibility exists that water used may have some MTBE. Our s...

  11. 40 CFR 721.6980 - Dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols...

    Science.gov (United States)

    2010-07-01

    ... reporting. (1) The chemical substance dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl... glycol, bisphenol A-diglycidyl ether, and alky-lenepolyols polyglycidyl ethers (generic name). 721.6980... Substances § 721.6980 Dimer acids, polymer with polyalkylene glycol, bisphenol A-diglycidyl ether, and alky...

  12. Thermal stability of homo- and copolymers of vinyl fluoride

    International Nuclear Information System (INIS)

    Raucher, D.; Levy, M.

    1979-01-01

    The thermal stability of poly(vinyl fluoride)(PVF) was studied by thermal gravimetry and mass spectrometry (TGA and TGA-MS). In low-molecular-weight polymers a two-step decomposition pattern was observed. It consisted of the dehydrofluorination to a polyene chain followed by decomposition of the resulting polyene at higher temperatures. Copolymers of vinyl fluoride-vinyl acetate (VF-VAc) and vinyl fluoride-vinyl chloride (VF-VCl) showed a simultaneous evolution of hydrofluoric acid and acetic acid and hydrofluoric acid and hydrochloric acid, respectively. This suggests that after the elimination of the weakest link a spontaneous elimination of neighboring HF molecules takes place

  13. Proton-conducting membrane based on epoxy resin-poly(vinyl alcohol)-sulfosuccinic acid blend and its nanocomposite with sulfonated multiwall carbon nanotubes for fuel-cell application

    Science.gov (United States)

    Kakati, Nitul; Das, Gautam; Yoon, Young Soo

    2016-01-01

    A blend of poly(vinyl alcohol) (PVA) with diglycidyl ether of bisphenol-A (DGB) in the presence of sulfosuccinic acid (SSA) was investigated as hydrolytically-stable proton-conducting membrane. The PVA modification was carried out by varying the DGB:SSA ratio (20:20, 10:20, and 5:20). A nanocomposite of the blend (20:20) was prepared with sulfonated multiwall carbon nanotubes (viz., 1, 3 and 5 wt%). The water uptake behavior and the proton conductivity of the prepared membranes were evaluated. The ionic conductivity of the membranes and the water uptake behavior depended on the s-MWCNT and the DGB contents. The ionic conductivity showed an enhancement for the blend and for the nanocomposite membrane as compared to the pristine polymer.

  14. Novel sulfonated poly (ether ether keton)/polyetherimide acid-base blend membranes for vanadium redox flow battery applications

    International Nuclear Information System (INIS)

    Liu, Shuai; Wang, Lihua; Ding, Yue; Liu, Biqian; Han, Xutong; Song, Yanlin

    2014-01-01

    Highlights: • SPEEK/PEI acid-base blend membranes are prepared for VRB applications. • The acid-base blend membranes have much lower vanadium ion permeability. • The energy efficiency of SPEEK/PEI maintain around 86.9% after 50 cycles. - Abstract: Novel acid-base blend membranes composed of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared for vanadium redox flow battery (VRB). The blend membranes were characterized by Fourier transform infrared spectroscopy (FT-IR) and scanning electronic microscopy (SEM). The ion exchange capacity (IEC), proton conductivity, water uptake, vanadium ion permeability and mechanical properties were measured. As a result, the acid-base blend membranes exhibit higher water uptake, IEC and lower vanadium ion permeability compared to Nafion117 membranes and all these properties decrease with the increase of PEI. In VRB single cell test, the VRB with blend membranes shows lower charge capacity loss, higher coulombic efficiency (CE) and energy efficiency (EE) than Nafion117 membrane. Furthermore, the acid-base blend membranes present stable performance up to 50 cycles with no significant decline in CE and EE. All experimental results indicate that the SPEEK/PEI (S/P) acid-base blend membranes show promising prospects for VRB

  15. Overview of technologies for removal of methyl tert-butyl ether (MTBE) from water.

    Science.gov (United States)

    Levchuk, Irina; Bhatnagar, Amit; Sillanpää, Mika

    2014-04-01

    Wide use of methyl tert-butyl ether (MTBE) as fuel oxygenates leads to worldwide environment contamination with this compound basically due to fuel leaks from storage or pipelines. Presence of MTBE in drinking water is of high environmental and social concern. Existing methods for MTBE removal from water have a number of limitations which can be possibly overcome in the future with use of emerging technologies. This work aims to provide an updated overview of recent developments in technologies for MTBE removal from water. Copyright © 2014. Published by Elsevier B.V.

  16. DFT study on the adsorption of diethyl, ethyl methyl, and dimethyl ethers on the surface of gallium doped graphene

    Energy Technology Data Exchange (ETDEWEB)

    Shokuhi Rad, Ali, E-mail: a.shokuhi@gmail.com [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Sani, Emad; Binaeian, Ehsan [Department of Chemical Engineering, Qaemshahr Branch, Islamic Azad University, Qaemshahr (Iran, Islamic Republic of); Peyravi, Majid; Jahanshahi, Mohsen [Faculty of Chemical Engineering, Babol University of Technology, Babol (Iran, Islamic Republic of)

    2017-04-15

    Highlights: • Adsorption of three ether molecules on the surface of Ga-doped graphene has been investigated. • High degree of adsorption for all analytes is found. • Ga-doped graphene shows p-type semiconductor property upon adsorption of ether molecules. - Abstract: In this study, we used density functional theory (DFT) to search on the adsorption properties of three important compounds of ether family; diethyl ether (DEE), ethyl methyl ether (EME), and dimethyl ether (DME) on the surface of Gallium doped graphene (GaG). We used three functionals (B3LYP, wb97xd, and MPW1PW91) for optimization and calculation of adsorption energy. After fully optimization, we scrutinized on the charge allocations on the adsorbed ethers as well as GaG (at the area of interaction) based on natural bond orbitals (NBO). Besides, we have calculated the amount of charge transfer upon adsorption of each analyte. We revel that GaG is an ideal adsorbent for chemisorption of all above-mentioned ethers. There is a little difference between the values of adsorption; −123.5, −120, and −118.3 kJ/mol (based on wb97xd) for DEE, EME, and DME, respectively. We found significant changes in the electronic structure of both adsorbent and adsorbate upon adsorption. Moreover, results of charge analyses confirm GaG is a p-type semiconductor.

  17. DFT study on the adsorption of diethyl, ethyl methyl, and dimethyl ethers on the surface of gallium doped graphene

    International Nuclear Information System (INIS)

    Shokuhi Rad, Ali; Sani, Emad; Binaeian, Ehsan; Peyravi, Majid; Jahanshahi, Mohsen

    2017-01-01

    Highlights: • Adsorption of three ether molecules on the surface of Ga-doped graphene has been investigated. • High degree of adsorption for all analytes is found. • Ga-doped graphene shows p-type semiconductor property upon adsorption of ether molecules. - Abstract: In this study, we used density functional theory (DFT) to search on the adsorption properties of three important compounds of ether family; diethyl ether (DEE), ethyl methyl ether (EME), and dimethyl ether (DME) on the surface of Gallium doped graphene (GaG). We used three functionals (B3LYP, wb97xd, and MPW1PW91) for optimization and calculation of adsorption energy. After fully optimization, we scrutinized on the charge allocations on the adsorbed ethers as well as GaG (at the area of interaction) based on natural bond orbitals (NBO). Besides, we have calculated the amount of charge transfer upon adsorption of each analyte. We revel that GaG is an ideal adsorbent for chemisorption of all above-mentioned ethers. There is a little difference between the values of adsorption; −123.5, −120, and −118.3 kJ/mol (based on wb97xd) for DEE, EME, and DME, respectively. We found significant changes in the electronic structure of both adsorbent and adsorbate upon adsorption. Moreover, results of charge analyses confirm GaG is a p-type semiconductor.

  18. Post irradiation effects on the graft of poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) films

    International Nuclear Information System (INIS)

    Geraldes, Adriana N.; Zen, Heloisa A.; Ribeiro, Geise; Ferreira, Henrique P.; Souza, Camila P.; Parra, Duclerc F.; Lugao, Ademar B.

    2009-01-01

    Radiation induced grafting of monomers into fluorinated polymers was designed as an alternative route to polymer modification. In this work, grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) was studied. Radiation-induced grafting of styrene onto PFA films was investigated after simultaneous irradiation (in post-irradiation condition) using a 60 Co source. The films of PFA were irradiated at 20, 40, 80 and 100 kGy doses at room temperature and chemical changes were monitored after contact with styrene for grafting. The post-irradiation time was established between 7 and 28 days when films of PFA were maintained in styrene/toluene 1:1 v/v solution at room temperature. After these periods the grafting degrees were evaluated in the samples. The highest degree of grafting was achieved after 14 days. Chemical modifications were evaluated by infrared spectroscopic analysis (FTIR), thermogravimetry (TG), differential scanning calorimetry (DSC) and also by scanning electron microscopy (SEM). The degree of grafting (DOG) was determined gravimetrically. The results showed that irradiated PFA films at 100 kGy exhibited higher grafting degree. Surface analysis by SEM technique of irradiated, grafted and original films have presented an homogeneous surface. (author)

  19. Crosslinked poly(vinyl alcohol)/sulfonated poly(ether ether ketone) blend membranes for fuel cell applications - Surface energy characteristics and proton conductivity

    Energy Technology Data Exchange (ETDEWEB)

    Kanakasabai, P.; Vijay, P.; Deshpande, Abhijit P.; Varughese, Susy [Department of Chemical Engineering, Indian Institute of Technology Madras, Chennai 600 036 (India)

    2011-02-01

    Ionic polymers, their blends and composites are considered potential candidates for application as electrolytes in fuel cells. While developing new materials for membranes, it is important to understand the interactions of these electrolytic materials with electrodes/catalysts and with reactants/products. Some of these interactions can be understood by estimating the surface energy and wettability of the membrane materials. In this work, polyvinyl alcohol with varying degrees of sulfonation and its blend with sulfonated poly(ether ether ketone) are prepared and studied for their wettability characteristics using goniometry. The surface energy and its components are estimated using different approaches and compared. Properties such as the ion-exchange capacity, the proton conductivity and the water sorption/desorption behaviour are also investigated to understand the relationship with wettability and surface energy and its components. Among the different methods, the van Oss acid-base and the modified Berthelot approaches yield comparable estimates for the total surface energy. (author)

  20. Enhancement of methyl tert-butyl ether degradation by the addition of readily metabolizable organic substrates

    International Nuclear Information System (INIS)

    Chen Dongzhi; Chen Jianmeng; Zhong Weihong

    2009-01-01

    Supplements with readily metabolizable organic substrates were investigated to increase the biomass and enhance degradation of methyl tert-butyl ether (MTBE) due to the low biomass yield of MTBE which has been one of the factors for low-rate MTBE degradation. The influence of various organic substrates on the rate of aerobic degradation of methyl tert-butyl ether (MTBE) by Methylibium petroleiphilum PM1 was investigated, and only yeast extract (YE), beef extract and tryptone exhibited stimulatory effect. With the concentration of each substrate being 100 mg/L, the average MTBE removal rate could increase to 1.29, 1.20 and 1.04 mg/(L h), respectively, in comparison with 0.71 mg/(L h) when carried out in medium without addition. The stimulatory effects of YE addition, as well as induction period required by MTBE degradation, varied dramatically with the storage conditions, pre-culture medium and concentrations of the inoculums. The extent of stimulatory effects of YE might be closely related to the proportion of induction period in the total time of MTBE-degradation. The removal efficiency increased from about 50% to 90.5% with the addition of YE in a packed-bed reactor loaded with calcium alginate immobilized cells.

  1. Anaerobic degradation of veratrylglycerol-beta-guaiacyl ether and guaiacoxyacetic acid by mixed rumen bacteria.

    OpenAIRE

    Chen, W; Supanwong, K; Ohmiya, K; Shimizu, S; Kawakami, H

    1985-01-01

    Veratrylglycerol-beta-guaiacyl ether (0.2 g/liter), a lignin model compound, was found to be degraded by mixed rumen bacteria in a yeast extract medium under strictly anaerobic conditions to the extent of 19% within 24 h. Guaiacoxyacetic acid, 2-(o-methoxyphenoxy)ethanol, vanillic acid, and vanillin were detected as degradation products of veratrylglycerol-beta-guaiacyl ether by thin-layer chromatography, gas chromatography, and gas chromatography-mass spectrometry. Guaiacoxyacetic acid (0.25...

  2. Biodegradation of methyl tert-butyl ether by Kocuria sp.

    Directory of Open Access Journals (Sweden)

    Kiković Dragan D.

    2012-01-01

    Full Text Available Methyl tert-butyl ether (MTBE has been used to replace the toxic compounds from gasoline and to reduce emission of air pollutants. Due to its intensive use, MTBE has become one of the most important environment pollutants. The aim of this paper is isolation and identification of the bacteria from wastewater sample of “HIP Petrohemija” Pančevo (Serbia, capable of MTBE biodegradation. The results of the investigation showed that only the bacterial isolate 27/1 was capable of growth on MTBE. The result of sequence analyzes of 16S rDNA showed that this bacterial isolate belongs to the Kocuria sp. After the incubation period of 86 days, the degradation rates of initial MTBE concentration of 25 and 125 μg/ml were 55 and 36%, respectively. These results indicated that bacteria Kocuria sp. is successfully adapted on MTBE and can be potentially used in bioremediation of soils and waters contaminated with MTBE.

  3. Inactivation of γ-aminobutyric acid aminotransferase by γ-ethynyl- and γ-vinyl GABA

    International Nuclear Information System (INIS)

    Silverman, R.B.; Burke, J.R.; Nanavati, S.M.

    1989-01-01

    γ-Ethynyl- and γ-vinyl GABA (vigabatrin) are anticonvulsant agents that have been shown to be mechanism-based inactivators of γ-aminobutyric acid aminotransferase (GABA-T). The inactivation mechanisms of these compounds have been investigated. Inactivation of GABA-T by [ 3 H]γ-ethynyl GABA led to the incorporation of 1.0 equiv of 3 H into the enzyme which is not released by enzyme denaturation. Inactivation by γ-ethynyl GABA of GABA-T reconstituted with [ 3 H]PLP followed by denaturation resulted in release of 3 H as PLP. Eight different possible adducts are consistent with that result. Experiments have been carried out to differentiate these possibilities. Similar studies have been carried out with γ-vinyl GABA. Inactivation by [ 14 C]γ-vinyl GABA resulted in the incorporation of 1.0 equiv of 14 C per active site. Unlike the case with γ-ethynyl GABA, γ-vinyl GABA inactivation of GABA-T reconstituted with [ 3 H]PLP followed by denaturation resulted in release of 3 H as PMP

  4. Vapor phase carbonylation of dimethyl ether and methyl acetate with supported transition metal catalysts

    International Nuclear Information System (INIS)

    Shikada, T.; Fujimoto, K.; Tominaga, H.O.

    1986-01-01

    The synthesis of acetic acid (AcOH) from methanol (MeOH) and carbon monoxide has been performed industrially in the liquid phase using a rhodium complex catalyst and an iodide promoter. The selectivity to AcOH is more than 99% under mild conditions (175 0 C, 28 atm). The homogeneous rhodium catalyst has been also effective for the synthesis of acetic anhydride (Ac 2 O) by carbonylation of dimethyl ether (DME) or methyl acetate (AcOMe). However, rhodium is one of the most expensive metals and its proved reserves are quite limited. It is highly desired, therefore, to develop a new catalyst as a substitute for rhodium. The authors have already reported that nickel supported on active carbon exhibits an excellent activity for the vapor phase carbonylation of MeOh in the presence of iodide promoter and under moderately pressurized conditions. In addition, corrosive attack on reactors by iodide compounds is expected to be negligible in the vapor phase system. In the present work, vapor phase carbonylation of DME and AcOMe on nickel-active carbon (Ni/A.C.) and molybdenum-active carbon (Mo/A.C.) catalysts was studied

  5. DC conduction mechanism and dielectric properties of Poly (methyl methacrylate)/Poly (vinyl acetate) blends doped and undoped with malachite green

    International Nuclear Information System (INIS)

    Abd-El Kader, F.H.; Osman, W.H.; Hafez, R.S.

    2013-01-01

    Cast thin films of Poly (methyl methacrylate)/Poly (vinyl acetate) blends of different concentrations undoped and doped with malachite green have been prepared and subjected to both dc electrical conduction and dielectric spectroscopy measurements. The analysis of dc electrical conduction data showed that the space charge limited current mechanism has been dominant for Poly (vinyl acetate) while Schottky-Richardson conduction mechanism prevailed for the Poly (methyl methacrylate) and blended samples. The values of field lowering constant β and the thermal activation energy ΔE involved in the dc conduction were reported, which provide another support for the suggested Schottky-Richardson mechanism. The increase in current for the blend sample doped with malachite green has been attributed to the formation of charge transfer complexes inside the polyblend matrix. The dielectric constant as a function of temperature for all samples have been calculated which are affected by the composition ratio and the addition of dye. The relaxation peak that appeared in the dielectric loss curve at 347 K for the doped blend sample is related to local dipoles that are present in the dye material. The obtained relaxation process spectra present in the investigated samples were analyzed with the well-known model of Havriliak-Negami.

  6. Preparation of Macroporous Poly (vinyl alcohol-co-triallyl isocyanurate) Beads Bearing Aminocarboxylic Acid as Functional Groups by Suspension Polymerization

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Macroporous poly (vinyl acetate-co-triallyl isocyanurate) beads were prepared with suspension polymerization method. The copolymer beads were then transformed into poly (vinyl alcohol-co-triallyl isocyanurate) by ester exchange reaction. Aminocarboxylic acids were immobilized on the copolymer beads by the esterification of hydroxyl groups with diethyl-lenetriaminepentaacetic bisanhydride. The weak acid exchange capacities, specific surface areas and mean pore diameters of the resultant resin beads were measured.

  7. High performance oligomers: synthesis and photochemical properties of calix(n)arene containing various photoreactive groups

    International Nuclear Information System (INIS)

    Nishikubo, T.; Kameyama, A.

    1999-01-01

    Photoreactive calix(n)arenes containing radical polymerizable (meth)acrylate groups, and catatonically polymerizable vinyl ether, propargyl ether, oxirane and oxetane groups were synthesized by certain reactions of calix(n)arenes with the corresponding (meth)acrylic acid derivatives, vinyl ether compound, epibromohydrin and oxetane derivatives, respectively. The photochemical reaction of these calix(n)arene derivatives were also examined

  8. MILLIMETER WAVE SPECTRUM AND ASTRONOMICAL SEARCH FOR VINYL FORMATE

    Energy Technology Data Exchange (ETDEWEB)

    Alonso, E. R.; Kolesniková, L.; Cabezas, C.; Alonso, J. L. [Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Área de Química-Física, Laboratorios de Espectroscopia y Bioespectroscopia, Parque Científico UVa, Unidad Asociada CSIC, Universidad de Valladolid, E-47011 Valladolid (Spain); Tercero, B.; Cernicharo, J. [Grupo de Astrofísica Molecular, ICMM-CSIC, C/Sor Juana Inés de la Cruz 3, E-28049 Cantoblanco (Spain); Guillemin, J.-C. [Institut des Sciences Chimiques de Rennes, École Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, 11 Allée de Beaulieu, CS 50837, F-35708 Rennes Cedex 7 (France)

    2016-11-20

    Previous detections of methyl and ethyl formate make other small substituted formates potential candidates for observation in the interstellar medium. Among them, vinyl formate is one of the simplest unsaturated carboxylic ester. The aim of this work is to provide direct experimental frequencies of the ground vibrational state of vinyl formate in a large spectral range for astrophysical use. The room-temperature rotational spectrum of vinyl formate has been measured from 80 to 360 GHz and analyzed in terms of Watson’s semirigid rotor Hamiltonian. Two thousand six hundred transitions within J = 3–88 and K {sub a} = 0–28 were assigned to the most stable conformer of vinyl formate and a new set of spectroscopic constants was accurately determined. Spectral features of vinyl formate were then searched for in Orion KL, Sgr B2(N), B1-b, and TMC-1 molecular clouds. Upper limits to the column density of vinyl formate are provided.

  9. Graft copolymerization of vinyl monomers onto nylon 6 fibers by γ-ray pre-irradiation in air

    International Nuclear Information System (INIS)

    Iwasaki, Tatsuo; Ueda, Yoshitsugu

    1992-01-01

    Vinyl acetate, methyl methacrylate, alkyl acrylates, acrylonitrile, and acrylamide, were grafted onto nylon 6 fibers by the γ-ray pre-irradiation technique, and the effects of grafting on the microstructure and the mechanical properties of the graft copolymers were investigated. According to the analysis by wide-angle X-ray diffraction, the degree of crystallization decreased by increasing the percent graft of poly(vinyl acetate) in the grafted nylon 6 films. The mechanical parameters, such as the Young's modulus and the tensile strength at break, increased with increasing percent graft up to 50%. When percent grafting was smaller than 50%, rather homogeneous amorphous materials were obtained with vinyl acetate, while heterogeneous ones were obtained with other vinyl monomers. A poly(vinyl alcohol) grafted nylon 6 was obtained effectively by saponification of poly(vinyl acetate) grafted nylon 6, the former showing higher mechanical properties than the latter. Similar behavior was observed after saponification of the poly(methyl acrylate) grafted nylon 6. (author)

  10. Acute effects of sodium valproate and gamma-vinyl GABA on regional amino acid metabolism in the rat brain: incorporation of 2-[14C]glucose into amino acids.

    Science.gov (United States)

    Chapman, A G; Riley, K; Evans, M C; Meldrum, B S

    1982-09-01

    Amino acid concentrations have been determined in rat brain regions (cortex, striatum, cerebellum, and hippocampus) by HPLC after administration of acute anticonvulsant doses of sodium valproate (400 mg/kg, i.p.) and gamma-vinyl-GABA (1 g/kg, i.p.). After valproate administration the GABA level increases only in the cortex; aspartic acid concentration decreases in the cortex and hippocampus, and glutamic acid decreases in the hippocampus and striatum and increases in the cortex and cerebellum. There are no changes in the concentrations of glutamine, taurine, glycine, serine, and alanine following valproate administration. Only the GABA level increases in all the regions after gamma-vinyl-GABA administration. Cortical analyses 2, 4 and 10 minutes after pulse labeling with 2-[14C]glucose, i.v., show no change in the rate of cortical glucose utilization in the valproate treated group. The rate of labeling of glutamic acid is also unchanged, but the rate of labeling of GABA is reduced following valproate administration. After gamma-vinyl-GABA administration there is no change in the rate of labeling of GABA. These biochemical findings can be interpreted in terms of a primary anticonvulsant action of valproate on membrane receptors with secondary effects on the metabolism of amino acid neurotransmitters. This contrasts with the primary action of gamma-vinyl-GABA on GABA-transaminase activity.

  11. Chain-modified radioiodinated fatty acids

    International Nuclear Information System (INIS)

    Otto, C.A.

    1987-01-01

    Several carbon chain manipulations have been studied in terms of their effects on myocardial activity levels and residence time. The manipulations examined included: chain length, chain branching, chain unsaturation, and carbon-iodine bond stabilization. It was found that chain length affects myocardial activity levels for both straight-chain alkyl acids and branched chain alkyl and aryl acids. Similar results have been reported for the straight-chain aryl acids. Generally, the longer chain lengths correlated with higher myocardial activity levels and longer residence times. This behavior is attributed to storage as triglycerides. Branched chain acids are designed to be anti-metabolites but only the aryl β-methyl acids possessed the expected time course of constant or very slowly decreasing activity levels. The alkyl β-methyl acids underwent rapid deiodination - a process apparently independent of β-oxidation. Inhibition of β-oxidation by incorporation of carbon-carbon double and triple bonds was studied. Deiodination of ω-iodo alkyl fatty acids prevented an assessment of suicide inhibition using an unsaturated alkynoic acid. Stabilization of the carbon-iodine bond by attachment of iodine to a vinylic or aryl carbon was studied. The low myocardial values and high blood values observed for an eleven carbon ω-iodo vinylic fatty acid were not encouraging but ω-iodo aryl fatty acids appear to avoid the problems of rapid deiodination. (Auth.)

  12. Absolute photoionization cross-section of the methyl radical.

    Science.gov (United States)

    Taatjes, Craig A; Osborn, David L; Selby, Talitha M; Meloni, Giovanni; Fan, Haiyan; Pratt, Stephen T

    2008-10-02

    The absolute photoionization cross-section of the methyl radical has been measured using two completely independent methods. The CH3 photoionization cross-section was determined relative to that of acetone and methyl vinyl ketone at photon energies of 10.2 and 11.0 eV by using a pulsed laser-photolysis/time-resolved synchrotron photoionization mass spectrometry method. The time-resolved depletion of the acetone or methyl vinyl ketone precursor and the production of methyl radicals following 193 nm photolysis are monitored simultaneously by using time-resolved synchrotron photoionization mass spectrometry. Comparison of the initial methyl signal with the decrease in precursor signal, in combination with previously measured absolute photoionization cross-sections of the precursors, yields the absolute photoionization cross-section of the methyl radical; sigma(CH3)(10.2 eV) = (5.7 +/- 0.9) x 10(-18) cm(2) and sigma(CH3)(11.0 eV) = (6.0 +/- 2.0) x 10(-18) cm(2). The photoionization cross-section for vinyl radical determined by photolysis of methyl vinyl ketone is in good agreement with previous measurements. The methyl radical photoionization cross-section was also independently measured relative to that of the iodine atom by comparison of ionization signals from CH3 and I fragments following 266 nm photolysis of methyl iodide in a molecular-beam ion-imaging apparatus. These measurements gave a cross-section of (5.4 +/- 2.0) x 10(-18) cm(2) at 10.460 eV, (5.5 +/- 2.0) x 10(-18) cm(2) at 10.466 eV, and (4.9 +/- 2.0) x 10(-18) cm(2) at 10.471 eV. The measurements allow relative photoionization efficiency spectra of methyl radical to be placed on an absolute scale and will facilitate quantitative measurements of methyl concentrations by photoionization mass spectrometry.

  13. A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters

    KAUST Repository

    Urban, Jiří T.

    2011-09-26

    An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. © 2011 Wiley Periodicals, Inc.

  14. A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters

    KAUST Repository

    Urban, Jiří T.; Švec, František; Frechet, Jean

    2011-01-01

    An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. © 2011 Wiley Periodicals, Inc.

  15. A monolithic lipase reactor for biodiesel production by transesterification of triacylglycerides into fatty acid methyl esters.

    Science.gov (United States)

    Urban, Jiri; Svec, Frantisek; Fréchet, Jean M J

    2012-02-01

    An enzymatic reactor with lipase immobilized on a monolithic polymer support has been prepared and used to catalyze the transesterification of triacylglycerides into the fatty acid methyl esters commonly used for biodiesel. A design of experiments procedure was used to optimize the monolithic reactor with variables including control of the surface polarity of the monolith via variations in the length of the hydrocarbon chain in alkyl methacrylate monomer, time of grafting of 1-vinyl-4,4-dimethylazlactone used to activate the monolith, and time used for the immobilization of porcine lipase. Optimal conditions involved the use of a poly(stearyl methacrylate-co-ethylene dimethacrylate) monolith, grafted first with vinylazlactone, then treated with lipase for 2 h to carry out the immobilization of the enzyme. Best conditions for the transesterification of glyceryl tributyrate included a temperature of 37°C and a 10 min residence time of the substrate in the bioreactor. The reactor did not lose its activity even after pumping through it a solution of substrate equaling 1,000 reactor volumes. This enzymatic reactor was also used for the transesterification of triacylglycerides from soybean oil to fatty acid methyl esters thus demonstrating the ability of the reactor to produce biodiesel. Copyright © 2011 Wiley Periodicals, Inc.

  16. Poly(Poly(Ethylene Glycol Methyl Ether Methacrylate Grafted Chitosan for Dye Removal from Water

    Directory of Open Access Journals (Sweden)

    Bryan Tsai

    2017-03-01

    Full Text Available As the demand for textile products and synthetic dyes increases with the growing global population, textile dye wastewater is becoming one of the most significant water pollution contributors. Azo dyes represent 70% of dyes used worldwide, and are hence a significant contributor to textile waste. In this work, the removal of a reactive azo dye (Reactive Orange 16 from water by adsorption with chitosan grafted poly(poly(ethylene glycol methyl ether methacrylate (CTS-GMA-g-PPEGMA was investigated. The chitosan (CTS was first functionalized with glycidyl methacrylate and then grafted with poly(poly(ethylene glycol methyl ether methacrylate using a nitroxide-mediated polymerization grafting to approach. Equilibrium adsorption experiments were carried out at different initial dye concentrations and were successfully fitted to the Langmuir and Freundlich adsorption isotherm models. Adsorption isotherms showed maximum adsorption capacities of CTS-g-GMA-PPEGMA and chitosan of 200 mg/g and 150 mg/g, respectively, while the Langmuir equations estimated 232 mg/g and 194 mg/g, respectively. The fundamental assumptions underlying the Langmuir model may not be applicable for azo dye adsorption, which could explain the difference. The Freundlich isotherm parameters, n and K, were determined to be 2.18 and 17.7 for CTS-g-GMA-PPEGMA and 0.14 and 2.11 for chitosan, respectively. An “n” value between one and ten generally indicates favorable adsorption. The adsorption capacities of a chitosan-PPEGMA 50/50 physical mixture and pure PPEGMA were also investigated, and both exhibited significantly lower adsorption capacities than pure chitosan. In this work, CTS-g-GMA-PPEGMA proved to be more effective than its parent chitosan, with a 33% increase in adsorption capacity.

  17. Fracture behavior of highly toughened poly(lactic acid)/ethylene-co-vinyl acetate blends

    NARCIS (Netherlands)

    Zeng, Q.; Feng, Y.; Wang, R.; Ma, P.

    2018-01-01

    Poly(lactic acid) (PLA) is brittle which restricts the range of its applications. The toughness of PLA was effectively improved in this work by incorporation of rubber grade ethylene-co-vinyl acetate (EVM). For example, the elongation at break of PLA increased by about 50 times after the addition of

  18. Effect of gamma ray on poly(lactic acid)/poly(vinyl acetate-co-vinyl alcohol) blends as biodegradable food packaging films

    Science.gov (United States)

    Razavi, Seyed Mohammad; Dadbin, Susan; Frounchi, Masoud

    2014-03-01

    Poly(lactic acid) (PLA)/poly(vinyl acetate-co-vinyl alcohol) [P(VAc-co-VA)] blends as new transparent film packaging materials were prepared at various blend compositions and different vinyl alcohol contents. The blends and pure PLA were irradiated by gamma rays to investigate the extent of changes in the packaging material during gamma ray sterilization process. The miscibility of the blends was dependent on the blend composition and vinyl alcohol content; gamma irradiation had little effect on the extent of miscibility. The glass transition temperature of pure PLA and PLA/P(VAc-co-VA) miscible blends reduced after irradiation. On the other hand in PLA/P(VAc-co-VA) immiscible blends, while the glass transition temperature of the PLA phase decreased; that of the copolymer phase slightly increased. The reduction in the glass transition was about 10 percent for samples irradiated with 50 kGy indicating dominance of chain scission of PLA molecules at high irradiation dose. The latter was verified by drop in mechanical properties of pure PLA after exposing to gamma irradiation at 50 kGy. Blending of PLA with the copolymer P(VAc-co-VA) compensated greatly the adverse effects of irradiation on PLA. The oxygen-barrier property of the blend was superior to the neat PLA and remained almost intact with irradiation. The un-irradiated and irradiated blends had excellent transparency. Gamma ray doses used for sterilization purposes are usually less than 20 kGy. It was shown that gamma irradiation at 20 kGy had no or little adverse effects on PLA/P(VAc-co-VA) blends mechanical and gas barrier properties.

  19. Novel sulfonated poly (ether ether ketone)/phosphonic acid-functionalized titania nanohybrid membrane by an in situ method for direct methanol fuel cells

    Science.gov (United States)

    Wu, Hong; Cao, Ying; Li, Zhen; He, Guangwei; Jiang, Zhongyi

    2015-01-01

    Sulfonated poly (ether ether ketone)/phosphonic acid-functionalized titania nanohybrid membranes are prepared by an in situ method using titanium tetrachloride (TiCl4) as inorganic precursor and amino trimethylene phosphonic acid (ATMP) as modifier. Phosphonic acid-functionalized titania nanoparticles with a uniform particle size of ∼50 nm are formed and dispersed homogeneously in the SPEEK matrix with good interfacial compatibility. Accordingly, the nanohybrid membranes display remarkably enhanced proton conduction property due to the incorporation of additional sites for proton transport and the formation of well-connected channels by bridging the hydrophilic domains in SPEEK matrix. The nanohybrid membrane with 6 wt. % of phosphonic acid-functionalized titania nanoparticles exhibits the highest proton conductivity of 0.334 S cm-1 at 65 °C and 100% RH, which is 63.7% higher than that of pristine SPEEK membrane. Furthermore, the as-prepared nanohybrid membranes also show elevated thermal and mechanical stabilities as well as decreased methanol permeability.

  20. Journal of Chemical Sciences | Indian Academy of Sciences

    Indian Academy of Sciences (India)

    ) andMn(II) complexes of poly(methyl vinyl ether-alt-maleic anhydride). Synthesis, characterization and thermodynamic parameters. Hidayet Mazi Ali Gulpinar. Volume 126 Issue 1 January 2014 pp 239-245 ...

  1. Decrease of intracellular pH as possible mechanism of embryotoxicity of glycol ether alkoxyacetic acid metabolites

    International Nuclear Information System (INIS)

    Louisse, Jochem; Bai Yanqing; Verwei, Miriam; Sandt, Johannes J.M. van de; Blaauboer, Bas J.; Rietjens, Ivonne M.C.M.

    2010-01-01

    Embryotoxicity of glycol ethers is caused by their alkoxyacetic acid metabolites, but the mechanism underlying the embryotoxicity of these acid metabolites is so far not known. The present study investigates a possible mechanism underlying the embryotoxicity of glycol ether alkoxyacetic acid metabolites using the methoxyacetic acid (MAA) metabolite of ethylene glycol monomethyl ether as the model compound. The results obtained demonstrate an MAA-induced decrease of the intracellular pH (pH i ) of embryonic BALB/c-3T3 cells as well as of embryonic stem (ES)-D3 cells, at concentrations that affect ES-D3 cell differentiation. These results suggest a mechanism for MAA-mediated embryotoxicity similar to the mechanism of embryotoxicity of the drugs valproic acid and acetazolamide (ACZ), known to decrease the pH i in vivo, and therefore used as positive controls. The embryotoxic alkoxyacetic acid metabolites ethoxyacetic acid, butoxyacetic acid and phenoxyacetic acid also caused an intracellular acidification of BALB/c-3T3 cells at concentrations that are known to inhibit ES-D3 cell differentiation. Two other embryotoxic compounds, all-trans-retinoic acid and 5-fluorouracil, did not decrease the pH i of embryonic cells at concentrations that affect ES-D3 cell differentiation, pointing at a different mechanism of embryotoxicity of these compounds. MAA and ACZ induced a concentration-dependent inhibition of ES-D3 cell differentiation, which was enhanced by amiloride, an inhibitor of the Na + /H + -antiporter, corroborating an important role of the pH i in the embryotoxic mechanism of both compounds. Together, the results presented indicate that a decrease of the pH i may be the mechanism of embryotoxicity of the alkoxyacetic acid metabolites of the glycol ethers.

  2. Identification of a polyketide synthase required for alternariol (AOH and alternariol-9-methyl ether (AME formation in Alternaria alternata.

    Directory of Open Access Journals (Sweden)

    Debjani Saha

    Full Text Available Alternaria alternata produces more than 60 secondary metabolites, among which alternariol (AOH and alternariol-9-methyl ether (AME are important mycotoxins. Whereas the toxicology of these two polyketide-based compounds has been studied, nothing is known about the genetics of their biosynthesis. One of the postulated core enzymes in the biosynthesis of AOH and AME is polyketide synthase (PKS. In a draft genome sequence of A. alternata we identified 10 putative PKS-encoding genes. The timing of the expression of two PKS genes, pksJ and pksH, correlated with the production of AOH and AME. The PksJ and PksH proteins are predicted to be 2222 and 2821 amino acids in length, respectively. They are both iterative type I reducing polyketide synthases. PksJ harbors a peroxisomal targeting sequence at the C-terminus, suggesting that the biosynthesis occurs at least partly in these organelles. In the vicinity of pksJ we found a transcriptional regulator, altR, involved in pksJ induction and a putative methyl transferase, possibly responsible for AME formation. Downregulation of pksJ and altR caused a large decrease of alternariol formation, suggesting that PksJ is the polyketide synthase required for the postulated Claisen condensations during the biosynthesis. No other enzymes appeared to be required. PksH downregulation affected pksJ expression and thus caused an indirect effect on AOH production.

  3. Metabolism of methyl-branched iodo palmitic acids in cultured hepatocytes

    International Nuclear Information System (INIS)

    Thomas, G.; Pepin, D.; Loriette, C.; Chambaz, J.; Bereziat, G.; Vidal, M.; Apparu, M.; Coornaert, S.

    1989-01-01

    The metabolic fate of methyl-branched iodo fatty acids was studied in primary culture of rat hepatocytes. We compared 16-iodo-2-R,S-methyl palmitic acid (2-Me), which can be β oxidized, with 16-iodo-3-R,S-methyl palmitic acid (3-Me) which can be β oxidized only after an initial α oxydation and with 16-iodo-2,2-dimethyl palmitic acid (2,2-Me 2 ) and 16-iodo-3,3-dimethyl palmitic acid (3,3-Me 2 ) which cannot be β oxidized at all. The normal fate of natural fatty acids was given by comparative experiments with [1- 14 C] palmitic acid. Monomethyl-branched iodo fatty acids were taken up in the same range as palmitic acid but more than dimethyl-branched iodo fatty acids. After a 15-h incubation, acido-soluble products (ASP) accounted for 75% of the radioactivity taken up as 16-iodo-2-methyl palmitic acid, 50% as other methyl-branched iodo fatty acids and only 30% as palmitic acid. Cultured hepatocytes, labelled for 3 h with the various fatty acids and reincubated for 12 h without fatty acid, secreted large amounts of free dimethyl-branched iodo fatty acids as compared to the monomethyl ones and palmitic acid. Only hepatocytes prelabelled with 16-[ 125 I]iodo-2,2-dimethyl palmitic acid exhibited an appreciable secretion of labeled triglycerides, but at a lower rate than with [1- 14 C] palmitic acid. Conversely, the 16-iodo-monomethyl palmitic acids remained chiefly in hepatocyte triglycerides. Minute amounts of 16-iodo-methyl-branched palmitic acids were found in hepatocyte or secreted phospholipids as compared with palmitic acid. (orig.)

  4. Radiation chemistry of alternative fuel oxygenates - substituted ethers

    International Nuclear Information System (INIS)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-01-01

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

  5. The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate).

    Science.gov (United States)

    Arellanes-Lozada, Paulina; Olivares-Xometl, Octavio; Guzmán-Lucero, Diego; Likhanova, Natalya V; Domínguez-Aguilar, Marco A; Lijanova, Irina V; Arce-Estrada, Elsa

    2014-08-07

    Compounds of poly(ionic liquid)s (PILs), derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium) (PImC 12 ), poly(1-vinyl-3-octylimidazolium) (PImC₈) and poly(1-vinyl-3-butylimidazolium) (PImC₄) hexafluorophosphate) were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1-1 M H₂SO₄) by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir's isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC 12 > PImC₈ > PImC₄) to reach 61% for PImC 12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs' partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.

  6. 21 CFR 573.640 - Methyl esters of higher fatty acids.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Methyl esters of higher fatty acids. 573.640... ANIMALS Food Additive Listing § 573.640 Methyl esters of higher fatty acids. The food additive methyl esters of higher fatty acids may be safely used in animal feeds in accordance with the following...

  7. Mucoadhesive hydrogel microparticles based on poly (methacrylic acid-vinyl pyrrolidone)-chitosan for oral drug delivery.

    Science.gov (United States)

    Sajeesh, S; Sharma, Chandra P

    2011-05-01

    The study was aimed at the evaluation of N-vinyl pyrrolidone (NVP) incorporated polymethacrylic acid-chitosan microparticles for oral drug delivery applications. Poly (methacrylic acid)-chitosan (PMC) and poly(methacrylic acid-vinyl pyrrolidone)-chitosan (PMVC) microparticles were prepared by an ionic-gelation method. Mucoadhesion behaviour of these particles was evaluated by ex-vivo adhesion method using freshly excised rat intestinal tissue. Cytotoxicity and absorption enhancing property of PMC and PMVC particles were evaluated on Caco 2 cell monolayers. Protease enzyme inhibition capability and insulin loading/release properties of these hydrogel particles was evaluated under in vitro experimental conditions. Addition of NVP units enhanced the mucoadhesion behavior of PMC particles on isolated rat intestinal tissue. Both PMC and PMVC particles were found non-toxic on Caco 2 cell monolayers and PMC particles was more effective in improving paracellular transport of fluorescent dextran across Caco 2 cell monolayers as compared to PMVC particles. However, protease inhibition efficacy of PMC particles was not significantly affected with NVP addition. NVP incorporation improved the insulin release properties of PMC microparticles at acidic pH. Hydrophilic modification seems to be an interesting approach in improving mucoadhesion capability of PMC microparticles.

  8. DNA methylation of amino acid transporter genes in the human placenta.

    Science.gov (United States)

    Simner, C; Novakovic, B; Lillycrop, K A; Bell, C G; Harvey, N C; Cooper, C; Saffery, R; Lewis, R M; Cleal, J K

    2017-12-01

    Placental transfer of amino acids via amino acid transporters is essential for fetal growth. Little is known about the epigenetic regulation of amino acid transporters in placenta. This study investigates the DNA methylation status of amino acid transporters and their expression across gestation in human placenta. BeWo cells were treated with 5-aza-2'-deoxycytidine to inhibit methylation and assess the effects on amino acid transporter gene expression. The DNA methylation levels of amino acid transporter genes in human placenta were determined across gestation using DNA methylation array data. Placental amino acid transporter gene expression across gestation was also analysed using data from publically available Gene Expression Omnibus data sets. The expression levels of these transporters at term were established using RNA sequencing data. Inhibition of DNA methylation in BeWo cells demonstrated that expression of specific amino acid transporters can be inversely associated with DNA methylation. Amino acid transporters expressed in term placenta generally showed low levels of promoter DNA methylation. Transporters with little or no expression in term placenta tended to be more highly methylated at gene promoter regions. The transporter genes SLC1A2, SLC1A3, SLC1A4, SLC7A5, SLC7A11 and SLC7A10 had significant changes in enhancer DNA methylation across gestation, as well as gene expression changes across gestation. This study implicates DNA methylation in the regulation of amino acid transporter gene expression. However, in human placenta, DNA methylation of these genes remains low across gestation and does not always play an obvious role in regulating gene expression, despite clear evidence for differential expression as gestation proceeds. Copyright © 2017. Published by Elsevier Ltd.

  9. Detection and Quantification of Methyl tert-Butyl Ether-Degrading Strain PM1 by Real-Time TaqMan PCR

    OpenAIRE

    Hristova, Krassimira R.; Lutenegger, Christian M.; Scow, Kate M.

    2001-01-01

    The fuel oxygenate methyl tert-butyl ether (MTBE), a widely distributed groundwater contaminant, shows potential for treatment by in situ bioremediation. The bacterial strain PM1 rapidly mineralizes and grows on MTBE in laboratory cultures and can degrade the contaminant when inoculated into groundwater or soil microcosms. We applied the TaqMan quantitative PCR method to detect and quantify strain PM1 in laboratory and field samples. Specific primers and probes were designed for the 16S ribos...

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

    Science.gov (United States)

    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.

  11. Theoretical calculation on a compound formed by methyl alcohol and simmondsin

    Directory of Open Access Journals (Sweden)

    İzzet KARA

    2016-12-01

    Full Text Available Etheric oil results from the esterification reactions of oil acids with alcohols. In these reactions, one molecule water (H2O is composed of H× protons from oil acids and OH- groups which separated from alcohol. Etheric oil is commonly used in food industry, perfume industry and medicine. From this perspective, we need to know physical properties of etheric oil as well as chemical properties. In this study, the highest occupied molecular orbital (HOMO energies, the lowest unoccupied molecular orbital (LUMO energies, the electronic properties (total energy, electronegativity, chemical hardness and softness, NBO analysis and thermodynamic parameters of a compound formed by methyl alcohol and simmondsin have been performed by using Gaussian 09W program. The structural and spectroscopic data of the molecule in the ground state have been calculated by using density functional method (DFT/B3LYP with the 6-31++G(d,p basis set.

  12. Proton-conducting membranes based on benzimidazole-containing sulfonated poly(ether ether ketone) compared with their carboxyl acid form

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongtao; Wu, Jing; Zhao, Chengji; Zhang, Gang; Zhang, Yang; Shao, Ke; Xu, Dan; Lin, Haidan; Han, Miaomiao; Na, Hui [Alan G MacDiarmid Institute, College of Chemistry, Jilin University, Changchun 130012 (China)

    2009-10-15

    A series of sulfonated poly(ether ether ketone) containing pendant carboxyl (C-SPEEKs) have been synthesized using a nucleophilic polycondesation reaction. A condensation reaction between 1,2-diaminobenzene and carboxyl resulted in a new series of copolymers containing benzimidazole groups (SPEEK-BIms). The expected structures of the sulfonated copolymers are confirmed by {sup 1}H NMR. The dependence of ion exchange capacity, water uptake, proton conductivity and methanol diffusion coefficient of SPEEK-BIm membranes has been studied and compared with their carboxyl acid form. The results suggest that the introduction of benzimidazole groups may be responsible for many excellent properties of the membranes for fuel cell. It is noticeable that the markedly improved oxidative stability is benefit for the application of membrane. (author)

  13. Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via {gamma}-ray irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Chirachanchai, S.; Kumkrong, A. [The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok (Thailand); Ishida, Hatsuo [Department of Macromolecular Science, Case Western Reserve University, Cleveland, OH (United States)

    2000-03-01

    Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3{alpha}, 12{alpha} -dihydroxy-5{beta}-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by {gamma}-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

  14. Inclusion polymerization of vinyl chloride monomer in deoxycholic acid host via γ-ray irradiation

    International Nuclear Information System (INIS)

    Chirachanchai, S.; Kumkrong, A.; Ishida, Hatsuo

    2000-01-01

    Inclusion polymerization of vinyl chloride monomer (VCM) was studied in the system of 3α, 12α -dihydroxy-5β-cholan-24-oic acid (deoxycholic acid, DCA). DCA-VCM inclusion compound system was originally prepared by guest intercalation technique in DCA guest free crystal. The inclusion polymerization of DCA-VCM by γ-irradiation at total dose 2 Mrad, gives a syndiotactic rich polyvinyl chloride (PVC) as can be confirmed by FT-IR and FT-NMR. (author)

  15. One-Pot Catalytic Enantio- and Diastereoselective Syntheses of anti-, syn-cis-Disubstituted, and syn-Vinyl Cyclopropyl Alcohols

    Science.gov (United States)

    Kim, Hun Young; Salvi, Luca; Carroll, Patrick J.; Walsh, Patrick J.

    2009-01-01

    Highly enantio- and diastereoselective methods for the synthesis of a variety of cyclopropyl alcohols are reported. These methods represent the first one-pot approaches to syn-vinyl cyclopropyl alcohols, syn-cis-disubstituted cyclopropyl alcohols, and anti-cyclopropyl alcohols from achiral precursors. The methods begin with enantioselective C–C bond formations promoted by a MIB-based zinc catalyst to generate allylic alkoxide intermediates. The intermediates are then subjected to in situ alkoxide-directed cyclopropanation to provide cyclopropyl alcohols. In the synthesis of vinyl cyclopropyl alcohols, hydroboration of enynes is followed by transmetalation of the resulting dienylborane to zinc to provide dienylzinc reagents. Enantioselective addition to aldehydes generates the requisite dienyl zinc alkoxides, which are then subjected to in situ cyclopropanation to furnish vinyl cyclopropyl alcohols. Cyclopropanation occurs at the double bond allylic to the alkoxide. Using this method, syn-vinylcyclopropyl alcohols are obtained in 65–85% yield, 76–93% ee, and >19:1 dr. To prepare anti-cyclopropanols, enantioselective addition of alkylzinc reagents to conjugated enals provides allylic zinc alkoxides. Because direct cyclopropanation provides syn-cyclopropyl alcohols, the intermediate allylic alkoxides were treated with TMSCl/Et3N to generate intermediate silyl ethers. In situ cyclopropanation of the allylic silyl ether resulted in cyclopropanation to form the anti-cyclopropyl silyl ether. Workup with TBAF affords the anti-cyclopropyl alcohols in one-pot in 60–82% yield, 89–99% ee, and ≥10:1 dr. For the synthesis of cis-disubstituted cyclopropyl alcohols, in situ generated (Z)-vinyl zinc reagents were employed in asymmetric addition to aldehydes to generate (Z)-allylic zinc alkoxides. In situ cyclopropanation provides syn-cis-disubstituted cyclopropyl alcohols in 42–70% yield, 88–97% ee, and >19:1 dr. These one-pot procedures enable the synthesis of a

  16. Simultaneous Determination of Salicylic Acid, Jasmonic Acid, Methyl Salicylate, and Methyl Jasmonate from Ulmus pumila Leaves by GC-MS

    OpenAIRE

    Huang, Zhi-hong; Wang, Zhi-li; Shi, Bao-lin; Wei, Dong; Chen, Jian-xin; Wang, Su-li; Gao, Bao-jia

    2015-01-01

    Salicylic acid, jasmonic acid, methyl salicylate, and methyl jasmonate are important phytohormones and defensive signaling compounds, so it is of great importance to determine their levels rapidly and accurately. The study uses Ulmus pumila leaves infected by Tetraneura akinire Sasaki at different stages as materials; after extraction with 80% methanol and ethyl acetate and purification with primary secondary amine (PSA) and graphitized carbon blacks (GCB), the contents of signal compounds sa...

  17. Design and synthesis of aryl ether and sulfone hydroxamic acids as potent histone deacetylase (HDAC) inhibitors.

    Science.gov (United States)

    Pabba, Chittari; Gregg, Brian T; Kitchen, Douglas B; Chen, Zhen Jia; Judkins, Angela

    2011-01-01

    A series of novel hydroxamic acid based histone deacetylases (HDAC) inhibitors with aryl ether and aryl sulfone residues at the terminus of a substituted, unsaturated 5-carbon spacer moiety have been synthesized for the first time and evaluated. Compounds with meta- and para-substitution on the aryl ring of ether hydroxamic acids 19c, 20c, 19e, 19f and 19g are potent HDAC inhibitors with activities at low nanomolar levels. Copyright © 2010 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

    Moon, Young-E; Jung, Gowun; Yun, Jumi; Kim, Hyung-Il

    2013-01-01

    Graphical abstract: The photocatalytic removal of pollutants was improved by the two-step mechanism based on the adsorption of pollutants by hydrogel and the effective decomposition by combination of TiO 2 and graphene oxide. -- Highlights: • pH sensitive PVA/PAAc hydrogels were prepared by radical polymerization and condensation reaction. • PVA/PAAc/TiO 2 /graphene oxide nanocomposite hydrogels were used for treatment of basic waste water. • Photocatalytic acitivity of TiO 2 was improved by incorporation of graphene oxide. • Photocatalytic decomposition by nanocomposite hydrogel was improved by increasing pH. -- Abstract: Poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 nanocomposite hydrogels. Both TiO 2 and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO 2 and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water

  19. The Inhibition of Aluminum Corrosion in Sulfuric Acid by Poly(1-vinyl-3-alkyl-imidazolium Hexafluorophosphate

    Directory of Open Access Journals (Sweden)

    Paulina Arellanes-Lozada

    2014-08-01

    Full Text Available Compounds of poly(ionic liquids (PILs, derived from imidazole with different alkylic chain lengths located in the third position of the imidazolium ring (poly(1-vinyl-3-dodecyl-imidazolium (PImC12, poly(1-vinyl-3-octylimidazolium (PImC8 and poly(1-vinyl-3-butylimidazolium (PImC4 hexafluorophosphate were synthesized. These compounds were tested as corrosion inhibitors on aluminum alloy AA6061 in diluted sulfuric acid (0.1–1 M H2SO4 by weight loss tests, polarization resistance measurements and inductively coupled plasma optical emission spectroscopy. Langmuir’s isotherms suggested film formation on bare alloy while standard free energy indicated inhibition by a physisorption process. However, compound efficiencies as inhibitors ranked low (PImC12 > PImC8 > PImC4 to reach 61% for PImC12 in highly diluted acidic solution. Apparently, the high mobility of sulfates favored their adsorption in comparison to PILs. The surface film displayed general corrosion, and pitting occurred as a consequence of PILs’ partial inhibition along with a continuous dissolution of defective patchy film on formation. A slight improvement in efficiency was displayed by compounds having high molecular weight and a long alkyl chain, as a consequence of steric hindrance and PIL interactions.

  20. N-methyl-D-aspartic acid receptor agonists

    DEFF Research Database (Denmark)

    Madsen, U; Frydenvang, Karla Andrea; Ebert, B

    1996-01-01

    (R,S)-2-Amino-2-(3-hydroxy-5-methyl-4-isoxazolyl)acetic acid [(R,S)-AMAA, 4] is a potent and selective agonist at the N-methyl-D-aspartic acid (NMDA) subtype of excitatory amino acid receptors. Using the Ugi "four-component condensation" method, the two diastereomers (2R)- and (2S)-2-[3-(benzyloxy......) showed peak affinity for [3H]AMPA receptor sites (IC50 = 72 +/- 13 microM) and was shown to be a more potent inhibitor of [3H]CPP binding (IC50 = 3.7 +/- 1.5 microM) than (S)-AMAA (9) (IC50 = 61 +/- 6.4 microM). Neither enantiomer of AMAA affected [3H]kainic acid receptor binding significantly...

  1. Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, F

    2005-04-01

    Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

  2. Preparation of Citric Acid Crosslinked Chitosan/Poly(Vinyl Alcohol Blend Membranes for Creatinine Transport

    Directory of Open Access Journals (Sweden)

    Retno Ariadi Lusiana

    2016-08-01

    Full Text Available Preparation of membrane using crosslinking reaction between chitosan and citric acid showed that functional group modification increased the number of active carrier groups which lead to better transport capacity of the membrane. In addition, the substitution of the carboxyl group increased creatinine permeation of chitosan membrane. The transport capacity of citric acid crosslinked chitosan membrane for creatinine was found to be 6.3 mg/L. The presence of cyanocobalamin slightly hindered the transport of creatinine although compounds did not able to pass through citric acid crosslinked chitosan/poly(vinyl alcohol blend membrane, as compounds no found in the acceptor phase.

  3. Neural Tube Defects, Folic Acid and Methylation

    Science.gov (United States)

    Imbard, Apolline; Benoist, Jean-François; Blom, Henk J.

    2013-01-01

    Neural tube defects (NTDs) are common complex congenital malformations resulting from failure of the neural tube closure during embryogenesis. It is established that folic acid supplementation decreases the prevalence of NTDs, which has led to national public health policies regarding folic acid. To date, animal studies have not provided sufficient information to establish the metabolic and/or genomic mechanism(s) underlying human folic acid responsiveness in NTDs. However, several lines of evidence suggest that not only folates but also choline, B12 and methylation metabolisms are involved in NTDs. Decreased B12 vitamin and increased total choline or homocysteine in maternal blood have been shown to be associated with increased NTDs risk. Several polymorphisms of genes involved in these pathways have also been implicated in risk of development of NTDs. This raises the question whether supplementation with B12 vitamin, betaine or other methylation donors in addition to folic acid periconceptional supplementation will further reduce NTD risk. The objective of this article is to review the role of methylation metabolism in the onset of neural tube defects. PMID:24048206

  4. Chronic Carcinogenicity Study of Gasoline Vapor Condensate (GVC) and GVC Containing Methyl Tertiary-Butyl Ether in F344 Rats

    OpenAIRE

    Benson, Janet M.; Gigliotti, Andrew P.; March, Thomas H.; Barr, Edward B.; Tibbetts, Brad M.; Skipper, Betty J.; Clark, Charles R.; Twerdok, Lorraine

    2011-01-01

    Chronic inhalation studies were conducted to compare the toxicity and potential carcinogenicity of evaporative emissions from unleaded gasoline (GVC) and gasoline containing the oxygenate methyl tertiary-butyl ether (MTBE; GMVC). The test materials were manufactured to mimic vapors people would be exposed to during refueling at gas stations. Fifty F344 rats per gender per exposure level per test article were exposed 6 h/d, 5 d/wk for 104 wk in whole body chambers. Target total vapor concentra...

  5. Radiation curing of mixtures of diallylphthalate prepolymer and vinyl monomer, 9

    International Nuclear Information System (INIS)

    Gotoda, Masao; Kitada, Yoshinori.

    1975-01-01

    Radiation curing, mainly by electron beams was studied with mixtures of low molecular weight diallylphthalate prepolymer (DAPsub(p).L) and vinyl monomers with special reference to their workability. Among the vinyl monomers, acrylonitrile gave a solution of low viscosity and methyl acrylate gave a solution of low dose curing. Radiation curing of DAPsub(p).L/vinyl monomer mixtures impregnated in wood was also tried. To obtain uniform wood-polymer composites, γ-irradiation after impregnation at 10 kg/cm 2 was found to be required for thick plate (110 mm), while electron beam irradiation after impregnation at normal pressure was sufficient for thin plate. (author)

  6. Copolymers of Vinyl-Containing Benzoxazine with Vinyl Monomers as Precursors for High Performance Thermosets

    Directory of Open Access Journals (Sweden)

    Tsutomu Takeichi

    2015-04-01

    Full Text Available A benzoxazine containing a vinyl group (P-4va was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA, and n-butyl acrylate (BuA was examined. The chemical structure of the copolymers was confirmed by FT-IR and 1H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900–51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229–250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA.

  7. Biodegradability of fuel-ethers in environment; Biodegradabilite des ethers-carburants dans l'environnement

    Energy Technology Data Exchange (ETDEWEB)

    Fayolle-Guichard, F.

    2005-04-01

    Fuel ethers (methyl tert-butyl ether or MTBE, ethyl tert-butyl ether or ETBE and tert-amyl methyl ether or TAME have been used as gasoline additives since about twenty years in order to meet the requirements for the octane index and to limit the polluting emission in exhaust pipe gas (unburnt hydrocarbons and carbon monoxide). The high water solubility and the poor biodegradability of these compounds make them pollutants frequently encountered in aquifers. The present manuscript summarizes the knowledge concerning the biodegradability of fuel ethers obtained both at IFP and during collaborations with the Pasteur Institute (Paris), the Biotechnology Research Institute (Montreal, Canada) and the Center for Environmental Biotechnology (University of Tennessee, USA). Rhodococcus ruber IFP 2001 and Mycobacterium austroafricanum IFP 2012, two microorganisms isolated at IFP for their ability to grow, respectively, on ETBE and MTBE, were studied in order to determine the intermediates produced during MTBE and ETBE biodegradation and the enzymes required for each biodegradation step, thus allowing us to propose MTBE and ETBE catabolic pathways. A proteomic approach, from the protein induced during the degradation of ETBE or MTBE to the genes encoding these different enzymes, was carried out. The isolation of such genes is required:1) to use them for help in determining the bio-remediation capacities in polluted aquifers (DNA micro-arrays), 2) to monitor the microorganisms isolated for their degradative capacities during bio-remediation processes (fluorescent in situ hybridization or FISH) and 3) to create new tools for the detection and the quantification of ETBE or MTBE in contaminated aquifers (bio-sensor). The manuscript also describes the different ways for the adaptation of microorganisms to the presence of a xenobiotic compound. (author)

  8. 40 CFR 721.6181 - Fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acid, reaction product with... Specific Chemical Substances § 721.6181 Fatty acid, reaction product with substituted oxirane, formaldehyde... as fatty acid, reaction product with substituted oxirane, formaldehyde-phenol polymer glycidyl ether...

  9. α-Diazo oxime ethers for N-heterocycle synthesis.

    Science.gov (United States)

    Choi, Subin; Ha, Sujin; Park, Cheol-Min

    2017-06-01

    This Feature Article introduces the preparation and synthetic utility of α-diazo oxime ethers. α-Oximino carbenes are useful synthons for N-heterocycles, and can be easily prepared from α-diazo oxime ethers as precursors. We begin with the preparation of α-diazo oxime ethers and their application in [3+2] cycloaddition. It turns out that the nature of metals bound to carbenes plays a crucial role in modulating the reactivity of α-oximino carbenes, in which copper carbenes smoothly react with enamines, whereas the less reactive enol ethers and nitriles require gold carbenes. In Section 3.2, a discussion on N-O and C-H bond activation is presented. Carbenes derived from diazo oxime ethers show unique reactivity towards N-O and C-H bond activation, in which the proximity of the two functionalities, carbene and oxime ether, dictates the preferred reaction pathways toward pyridines, pyrroles, and 2H-azirines. In Section 3.3, the development of tandem reactions based on α-diazo oxime ethers is discussed. The nature of carbenes in which whether free carbenes or metal complexes are involved dissects the pathway and forms different types of 2H-azirines. The 2H-azirine formation turned out to be an excellent platform for the tandem synthesis of N-heterocycles including pyrroles and pyridines. In the last section, we describe the electrophilic activation of 2H-azirines with vinyl carbenes and oximino carbenes. The resulting azirinium species undergo rapid ring expansion rearrangements to form pyridines and pyrazines.

  10. Terpenoid biotransformation in mammals. IV Biotransformation of (+)-longifolene, (-)-caryophyllene, (-)-caryophyllene oxide, (-)-cyclocolorenone, (+)-nootkatone, (-)-elemol, (-)-abietic acid and (+)-dehydroabietic acid in rabbits.

    Science.gov (United States)

    Asakawa, Y; Ishida, T; Toyota, M; Takemoto, T

    1986-08-01

    The metabolism of (+)-longifolene, (-)-caryophyllene, (-)-caryophyllene oxide, (-)-cyclocolorenone, (+)-nootkatone, (-)-elemol, (-)-abietic acid and (+)-dehydroabietic acid was studied in rabbits. Each of these sesquiterpenoids was converted to primary, secondary or tertiary alcohols, among which the primary alcohol was predominant. A vinylic methyl group and an exomethylene group were easily hydroxylated and converted to a glycol via an epoxide in many cases. Eight new metabolites were determined by chemical and spectroscopic methods.

  11. Alternative Production of Fatty Acid Methyl Esters from Triglycerides ...

    African Journals Online (AJOL)

    The catalysts activity was tested in thermocatalytic cracking of triglyceride; a direct conversion process for fatty acid methyl esters (biodiesel). The SZ1 not only exhibited higher conversion of triglycerides but higher fatty acid methyl esters (FAMEs) yields of approximately 59% after 3h as compared to SZ2 (32%). In addition ...

  12. The polymerisation of oligo(ethylene glycol methyl ether) methacrylate from a multifunctional poly(ethylene imine) derived amide : a stabiliser for the synthesis and dispersion of magnetite nanoparticles

    NARCIS (Netherlands)

    Kleine, A.; Altan, C.L.; Yarar, U.E.; Sommerdijk, N.A.J.M.; Bucak, S.; Holder, S.J.

    2014-01-01

    A facile synthetic route to poly(ethylene imine)-graft-poly(oligo(ethylene glycol methyl ether)) (PEI-graft-POEGMA) functionalised superparamagnetic magnetite nanoparticles is described. The polymerisation of OEGMA from a model molecular amide demonstrated the feasibility of POEGMA synthesis under

  13. Preparation and characterization of proton exchange poly (ether sulfone)s membranes grafted propane sulfonic acid on pendant phenyl groups

    International Nuclear Information System (INIS)

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

    2014-01-01

    Poly(ether sulfone)s containing hexaphenyl (PHP) was prepared by 1,2-bis(4-hydroxyphenyl)-3,4,5,6-tetraphenylbenzene, 4,4-hydroxyphenylsulfone, and 4,4-fluorophenylsulfone, followed bromination on phenyl groups to produce brominated PHP (Br-PHP). Grafted sulfonated poly(ether sulfone)s containing hexaphenyl (GSPHP) were prepared from Br-PHP and 3-bromopropane sulfonic acid with potassium salt and copper powder. The salt form was converted to free acid using 1 M sulfuric acid solution. All these membranes were cast from dimethylacetamide (DMAc). The structural properties of the synthesized polymers were investigated by 1 H-NMR spectroscopy. The membranes were studied with regard to ion exchange capacity (IEC), water uptake, Fenton test, and proton conductivity. These grafted polymer membranes were compared with normal sulfonated poly(ether sulfone)s and Nafion

  14. Vapour pressures for 1-(butoxymethoxy)butane (dibutoxymethane) and 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane (methyl nonafluorobutyl ether) over the pressure range of (15–80) kPa

    International Nuclear Information System (INIS)

    Gárate, María P.; Bejarano, Arturo; Fuente, Juan C. de la

    2016-01-01

    Highlights: • Vapour pressures of two pure potential dry-cleaning solvent were measured. • Measurements were made over the temperature range of (294.6–442.7) K. • Three commonly used vapour pressure equations were fitted to the experimental data. • The parameters of Antoine and Wagner type equations were estimated. • The relative deviations (rmsd) from the three vapour-pressure equations were <0.6%. - Abstract: Saturated pressures of 1-(butoxymethoxy)butane (dibutoxymethane) and 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane (methyl nonafluorobutyl ether), new potential solvents for dry-cleaning processes, were measured with a dynamic recirculation apparatus at a pressure range of (15–80) kPa, at temperatures of (390.4–442.7) K for dibutoxymethane and (294.6–322.4) K for methyl nonafluorobutyl ether. The vapour pressures were represented using the correlations of Antoine, extended Antoine and Wagner with relative root mean square deviations of, 1%, 6% and 0.6% for dibutoxymethane, and, 1%, 2% and 0.6% for methyl nonafluorobutyl ether, respectively. The experimental data of dibutoxymethane was compared with those available in literature, the result showed consistency between both data sets.

  15. Miscibility and specific interactions in blends of poly(n-vinyl-2-pyrrolidone) and acid functional polyester resins.

    NARCIS (Netherlands)

    Senatore, D.; Berix, M.J.A.; Laven, J.; Benthem, van R.A.T.M.; With, de G.; Mezari, B.; Magusin, P.C.M.M.

    2008-01-01

    Miscibility and intermol. interactions of novel blends of poly(N-vinyl-2-pyrrolidone) (PVP) and acid functional polyester resins (APE) were studied by use of Differential Scanning Calorimetry (DSC), Attenuated Total Reflectance Fourier Transform IR (ATR-FTIR), Cross-Polarization Magic Angle Spinning

  16. A novel sulfonated poly(ether ether ketone) and cross-linked membranes for fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hongtao; Zhang, Gang; Wu, Jing; Zhao, Chengji; Zhang, Yang; Shao, Ke; Han, Miaomiao; Lin, Haidan; Zhu, Jing; Na, Hui [Alan G MacDiarmid Institute, College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, Jilin (China)

    2010-10-01

    A novel poly(ether ether ketone) (PEEK) containing pendant carboxyl groups has been synthesized by a nucleophilic polycondensation reaction. Sulfonated polymers (SPEEKs) with different ion exchange capacity are then obtained by post-sulfonation process. The structures of PEEK and SPEEKs are characterized by both FT-IR and {sup 1}H NMR. The properties of SPEEKs as candidates for proton exchange membranes are studied. The cross-linking reaction is performed at 140 C using poly(vinyl alcohol) (PVA) as the cross-linker. In comparison with the non-cross-linked membranes, some properties of the cross-linked membranes are significantly improved, such as water uptake, methanol resistance, mechanical and oxidative stabilities, while the proton conductivity decreases. The effect of PVA content on proton conductivity, water uptake, swelling ratio, and methanol permeability is also investigated. Among all the membranes, SPEEK-C-8 shows the highest selectivity of 50.5 x 10{sup 4} S s cm{sup -3}, which indicates that it is a suitable candidate for applications in direct methanol fuel cells. (author)

  17. UV-A photooxidation of β-carotene in Triton X-100 micelles by nitrodiphenyl ether herbicides

    International Nuclear Information System (INIS)

    Orr, G.L.; Hogan, M.E.

    1985-01-01

    Photooxidation of β-carotene in Triton X-100 micelles was stimulated by lipophilic nitrodiphenyl ether herbicides at concentrations as low as 5 μM after 15 min in UV radiation (UV-A between 315 and 400 nm). Bleaching of β-carotene by acifluorfen-methyl [methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate] was proportional to UV-A intensity and independent of pH. White light (400-700 nm) alone was without effect. At pH 6.5, 100 μM acifluorfen [sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate], a water-soluble nitrodiphenyl ether, stimulated photooxidation of β-carotene after 15 min in UV-A radiation. Activity of 200 μM acifluorfen was enhanced at pHs between 3.5 and 6.5. The chlorodiphenyl ether analogue of acifluorfen-methyl, methyl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-chlorobenzoate, exhibited little activity at 200 μM and 200 μM phenyl ether was without effect. Activation energy for acifluorfen-methyl stimulated β-carotene photooxidation near 20 and 30 0 C was 40.3 and 5.6 kJ mol -1 , respectively. Subsequent to UV-A exposure and placement into darkness no further bleaching of β-carotene was detected, indicating that reactive species were generated only in light and consumed quickly in darkness

  18. The failure of poly (ether ether ketone) in high speed contacts

    Science.gov (United States)

    Briscoe, B. J.; Stuart, B. H.; Sebastian, S.; Tweedale, P. J.

    1993-04-01

    The paper describes an experimental study, with an associated analysis incorporating supplementary data, of the anti-boundary lubricating action of an alkane-aliphatic carboxylic acid lubricant system in a poly (ether ether ketone)-mild steel contact. The experiments involve progressively increasing the load in a contact formed between a polymer plate and a rotating steel shaft and estimating the frictional work dissipated. Scuffing is identified when a rapid increase in frictional work is noted at a characteristic normal load. It is shown that the additive induces premature scuffing. Subsidiary data is provided using Raman spectroscopy and hardness probes, and confirms that certain additives such as decanoic acid and dodecylamine will induce surface plasticization in poly (ether ether ketone). The trends in the frictional data have been interpreted using the adhesive model of friction in conjunction with temperature-dependent interfacial theology and bulk mechanical property data. It is proposed that the scuffing process is induced prematurely as a consequence of excessive additive-induced subsurface plasticization. Restricted surface plasticization in this system provides an enhanced self-lubricating capacity.

  19. Fatty acid methyl esters production: chemical process variables

    Directory of Open Access Journals (Sweden)

    Paulo César Narváez Rincón

    2004-05-01

    Full Text Available The advantages of fatty acid methyl esters as basic oleochemicals over fatty acids, the seventies world energy crisis and the use of those oleochemicals as fuels, have increased research interest on fats and oils trans-esterification. In this document, a review about basic aspects, uses, process variables and problems associated to the production process of fatty acid methyl esters is presented. A global view of recent researches, most of them focused in finding a new catalyst with same activity as the alcohol-soluble hydroxides (NaOH, KOH, and suitable to be used in transforming fats and oils with high levels of free fatty acids and water avoiding separation problems and reducing process costs, is also discussed.

  20. Pervaporation of alcohol-toluene mixtures through polymer blend membranes of poly(acrylic acid) and poly(vinyl alcohol)

    NARCIS (Netherlands)

    Park, H.C.; Park, H.; Meertens, R.M.; Meertens, R.M.; Mulder, M.H.V.; Smolders, C.A.; Smolders, C.A.

    1994-01-01

    Homogeneous membranes were prepared by blending poly(acrylic acid) with poly(vinyl alcohol). These blend membranes were evaluated for the selective separation of alcohols from toluene by pervaporation. The flux and selectivity of the membranes were determined both as a function of the blend

  1. Mechanical, relaxation behavior and thermal degradation of UV irradiated poly(vinyl acetate)/poly( methyl methacrylate) blends

    International Nuclear Information System (INIS)

    Mansour, S.A.; Hafez, M.; Hussien, K.A.

    2005-01-01

    The effect of different doses of UV- irradiation on the mechanical and relaxation properties of poly(vinyl acetate)/poly(methyl methacrylate) blends were studied. Films of PVAc/PMMA blend with different contents were prepared using the casting technique. Also, PMMA could be blended with PVAc to improve its impact strength. Moreover UV-irradiation causes degradation of PVAc and formation of ketonic and aldehyde carbonyl groups according to a suggested scheme. Irradiation of PvAc/ PMMA blends causes a higher degree of degradation as compared to the PVAc alone although the PMMA is more susceptible than PVAc to the influence of radiation. Recognizable differences are observed for all parameters between the unirradiated and irradiated samples. Existence of a relaxation mechanism within the first 200s is reported. The shear modulus for all samples is also obtained and discussed. These data are used to calculate the strain energy density using the equation proposed by Blatzetal(1974 trans. Soc.Rheol. 18 145-61), based on the n-measure of Sethe

  2. Chemoselective Deprotection of Triethylsilyl Ethers

    Science.gov (United States)

    Chandra, Tilak; Broderick, William E.; Broderick, Joan B.

    2009-01-01

    An efficient and selective method was developed for the deprotection of triethylsilyl (TES) ethers using formic acid in methanol (5–10%) or in methylene chloride 2–5%) with excellent yields. TES ethers are selectively deprotected to the corresponding alcohols in high yields using formic acid in methanol under mild reaction conditions. Other hydroxyl protecting groups like t-butyldimethylsilyl (TBDMS) remain unaffected. PMID:20183570

  3. Composite electrolytes composed of Cs-substituted phosphotungstic acid and sulfonated poly(ether-ether ketone) for fuel cell systems

    Energy Technology Data Exchange (ETDEWEB)

    Oh, Song-Yul, E-mail: ms089203@tutms.tut.ac.jp [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Yoshida, Toshihiro; Kawamura, Go [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Muto, Hiroyuki [Department of Materials Science and Engineering, Kurume National College of Technology, 1-1-1 Komorino, Kurume, Fukuoka 830-8555 (Japan); Sakai, Mototsugu [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Matsuda, Atsunori, E-mail: matsuda@tutms.tut.ac.jp [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan)

    2010-10-15

    Composite electrolytes composed of cesium hydrogen sulfate containing phosphotungstic acids (CsHSO{sub 4}-H{sub 3}PW{sub 12}O{sub 40}) and sulfonated poly(ether-ether ketone) (SPEEK) were prepared by casting the corresponding precursor for application in fuel cells. Partially Cs-substituted phosphotungstic acids (Cs{sub x}H{sub 3-x}PW{sub 12}O{sub 40}) were formed in the CsHSO{sub 4}-H{sub 3}PW{sub 12}O{sub 40} system by mechanochemical treatment. SPEEK was prepared from PEEK by sulfonation using concentrated sulfuric acid. Flexible composite electrolytes were obtained and their electrochemical properties were markedly improved with the addition of Cs{sub x}H{sub 3-x}PW{sub 12}O{sub 40}, into the SPEEK matrix. A maximum power density of 213 mW cm{sup -2} was obtained from the single cell test for 50H{sub 3}PW{sub 12}O{sub 40}-50CsHSO{sub 4} in SPEEK (1/5 by weight) composite electrolyte at 80 deg. C and at 80 RH%. Electrochemical properties and transmission electron microscopy (TEM) results suggest that three-dimensional cluster particles were formed and homogeneously distributed in the SPEEK matrix. The mechanochemically synthesized Cs{sub x}H{sub 3-x}PW{sub 12}O{sub 40} incorporated into the SPEEK matrix increased the number of protonate sites in the electrolyte. The composite electrolytes were successfully formed with Cs{sub x}H{sub 3-x}PW{sub 12}O{sub 40}, which consist of hydrogen bonding between surface of inorganic solid acids and not only -HSO{sub 4}{sup -} dissociated from CsHSO{sub 4} but also -SO{sub 3}H groups in the SPEEK.

  4. Self-supported poly(methyl methacrylate-acrylonitrile-vinyl acetate)-based gel electrolyte for lithium ion battery

    Energy Technology Data Exchange (ETDEWEB)

    Liao, Y.H.; Zhou, D.Y.; Rao, M.M.; Cai, Z.P.; Liang, Y. [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Li, W.S.; Tan, C.L. [School of Chemistry and Environment, South China Normal University, Guangzhou 510006 (China); Key Lab of Electrochemical Technology on Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006 (China)

    2009-04-01

    Self-supported gel polymer electrolyte (GPE) was prepared based on copolymer, poly(methyl methacrylate-acrylonitrile-vinyl acetate) (P(MMA-AN-VAc)). The copolymer P(MMA-AN-VAc) was synthesized by emulsion polymerization and the copolymer membrane was prepared through phase inversion. The structure and the performance of the copolymer, the membrane and the GPE were characterized by FTIR, NMR, SEM, XRD, DSC/TG, LSV, CA, and EIS. It is found that the copolymer was formed through the breaking of double bond C=C in each monomer. The membrane has low crystallinity and has low glass transition temperature, 39.1 C, its thermal stability is as high as 310 C, and its mechanical strength is improved compared with P(MMA-AN). The GPE is electrochemically stable up to 5.6 V (vs. Li/Li{sup +}) and its conductivity is 3.48 x 10{sup -3} S cm{sup -1} at ambient temperature. The lithium ion transference number in the GPE is 0.51 and the conductivity model of the GPE is found to obey the Vogel-Tamman-Fulcher (VTF) equation. (author)

  5. The analysis of methyl salicylate and salicylic acid from Chinese herbal medicine ingestion.

    Science.gov (United States)

    Parker, Dawn; Martinez, Christina; Stanley, Christina; Simmons, Jerry; McIntyre, Iain M

    2004-04-01

    This paper presents a multi-drug fatality in which methyl salicylate was ingested. It is presented to inform the toxicological community that a particularly expeditious method of detection for methyl salicylate exists. Previously published methods for the analysis of methyl salicylate include a gas chromatographic-mass spectrometric method and an alkaline/acidic extraction followed by high-performance liquid chromatographic (HPLC) analysis. This article describes a method for analyzing methyl salicylate using HPLC, in which a simple, rapid extraction procedure is used. Using a previously published HPLC method, methyl salicylate and salicylic acid were easily identified in biological specimens. Methyl salicylate and salicylic acid were detected using an extraction solution of acetonitrile coupled with internal standard and then analyzed by HPLC-diode-array detection. Because of its concentrated liquid form, methyl salicylate ingestion can cause rapid onset salicylate toxicity. As the potentially fatal methyl salicylate forms are readily available and easily found on drugstore shelves, the need to rapidly detect and quantitate salicylic acid concentrations that are due to methyl salicylate ingestion may arise. In the case presented, the peripheral blood concentration of salicylic acid from methyl salicylate ingestion was 320 mg/L, and the concentration in gastric contents was 820 mg. It alone was not the cause of death, however. The discovery of the ability to detect and quantitate methyl salicylate was due to its suspected ingestion.

  6. Studies on the Simultaneous Formation of Aroma-Active and Toxicologically Relevant Vinyl Aromatics from Free Phenolic Acids during Wheat Beer Brewing.

    Science.gov (United States)

    Langos, Daniel; Granvogl, Michael

    2016-03-23

    During the brewing process of wheat beer, the desired aroma-active vinyl aromatics 2-methoxy-4-vinylphenol and 4-vinylphenol as well as the undesired and toxicologically relevant styrene are formed from their respective precursors, free ferulic acid, p-coumaric acid, and cinnamic acid, deriving from the malts. Analysis of eight commercial wheat beers revealed high concentrations of 2-methoxy-4-vinylphenol and 4-vinylphenol always in parallel with high concentrations of styrene or low concentrations of the odorants in parallel with low styrene concentrations, suggesting a similar pathway. To better understand the formation of these vinyl aromatics, each process step of wheat beer brewing and the use of different strains of Saccharomyces cerevisiae were evaluated. During wort boiling, only a moderate decarboxylation of free phenolic acids and formation of desired and undesired vinyl aromatics were monitored due to the thermal treatment. In contrast, this reaction mainly occurred enzymatically catalyzed during fermentation with S. cerevisiae strain W68 with normal Pof(+) activity (phenolic off-flavor) resulting in a wheat beer eliciting the typical aroma requested by consumers due to high concentrations of 2-methoxy-4-vinylphenol (1790 μg/L) and 4-vinylphenol (937 μg/L). Unfortunately, also a high concentration of undesired styrene (28.3 μg/L) was observed. Using a special S. cerevisiae strain without Pof(+) activity resulted in a significant styrene reduction (beer aroma.

  7. Influence of the structure of bile acids on their partition coefficient in dibutyl ether and chloroform

    Directory of Open Access Journals (Sweden)

    Sebenji Ana S.

    2015-01-01

    Full Text Available Bile acids are well known natural surfactants able to modify the per­meability of biological membranes. The logarithm of partition coefficient between, tradi­tionally used, n-octanol and water is a measure of lipophilicity as a predictor of solute membrane partitioning. The aim of this work was to determine partition coefficients of bile acids in a mixture of water and chloroform and dibutyl ether at different pH values and with addition of different concentrations of sodium ions, and to examine the influence of the structure of bile acid nucleus on measured partition coefficients. Partition coefficients of three bile acid salts were determined using shake-flask method and the concentration of bile acids was determined after twelve hours of shaking at the room temperature in aqueous and organic layer using reversed phase HPLC with DAD detector on 210 nm. For all three analysed bile acid salts values of logP are lower in dibutyl ether than in chloroform. At certain pH values, curves representing the dependence of partition coeffi­cient on pH value intersect, and these are the pH values for which partition coefficients are the same for both solvents. Increasing the solution ionic strength, this intersection is shifted toward lower pH values. It is found that, for both organic solvents, after the addition of hy­droxyl group in the steroid nucleus (i.e. if the bile acid is less hydrophobic the value of logP falls, especially if more hydroxyl groups are present. With chloroform as a solvent, system quickly comes to excess with electrolyte ions than with dibutyl ether. [Projekat Ministarstva nauke Republike Srbije, br. 172021

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

    Energy Technology Data Exchange (ETDEWEB)

    Oh, S.Y.; Yoshida, T.; Kawamura, G.; Sakai, M.; Matsuda, A. [Department of Materials Science, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi, Aichi 441-8580 (Japan); Muto, H. [Department of Materials Science and Engineering, Kurume National College of Technology, 1-1-1 Komorino, Kurume, Fukuoka 830-8555 (Japan)

    2010-09-15

    Inorganic-organic composite electrolytes were fabricated from partially Cs{sup +}-substituted heteropoly acids (Cs-HPAs) and sulfonated poly(ether-ether ketone) (SPEEK) for application in fuel cells. Heteropoly acids, such as phosphotungstic acid (H{sub 3}PW{sub 12}O{sub 40}:WPA), and silicotungstic acid (H{sub 4}SiW{sub 12}O{sub 40}:WSiA), were mechanochemically treated with cesium hydrogen sulfate (CsHSO{sub 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{sup +} 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{sup -2} were obtained for 50WPA.50CsHSO{sub 4} and 50WSiA.50CsHSO{sub 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{sub 4}{sup -}, dissociated from CsHSO{sub 4}, are promising materials as inorganic fillers in inorganic-organic composite. (author)

  9. 21 CFR 177.1360 - Ethylene-vinyl acetate-vinyl alcohol copolymers.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate-vinyl alcohol copolymers... for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1360 Ethylene-vinyl acetate-vinyl alcohol copolymers. Ethylene-vinyl acetate-vinyl alcohol copolymers (CAS Reg. No. 26221-27-2...

  10. Regio and stereoselectivity in ionic cycloadditions

    Indian Academy of Sciences (India)

    WINTEC

    Though the reactions have both electrostatic control and frontier orbital control the former dominates in the initial stages of the reaction. Keywords. Stereoselectivity; ionic cycloaddition; density functional theory; acridizinium ion; methyl vinyl ether; 2,3-dimethylisoquinolinium ion. 1. Introduction. In polar or ionic cycloadditions ...

  11. Copolymerization of poly (ethylene oxide) and poly (methyl methacrylate) initiated by ceric ammonium nitrate

    International Nuclear Information System (INIS)

    Gomes, A.S.; Ferreira, A.A.; Coutinho, F.M.B.; Marinho, J.R.D.

    1984-01-01

    Cerium (IV) salts such as the ceric ammonium nitrate and ceric ammonium sulfate in aqueous acid solution with reducing agents such as alcohols, thiols, glycols, aldehydes and amines are well known initiators of vinyl polymerization. In this work, the polymerization of methyl methacrylate initiated by ceric ammonium nitrate/HNO 3 -poly(ethylene oxide) with hydroxyl end group system was studied in aqueous solution at 25 0 C to obtain block copolymers. (Author) [pt

  12. Preparation and Characterization of Sulfonated Poly (ether ether ...

    African Journals Online (AJOL)

    NJD

    2007-08-10

    Aug 10, 2007 ... Preparation and Characterization of Sulfonated Poly (ether ... Currently perfluori- ... with phosphoric acid solution according to the method described earlier.11,12 ... where A is the membrane area available for diffusion; CA is.

  13. Convenient synthesis of 6-nor-9,10-dihydrolysergic acid methyl ester.

    Science.gov (United States)

    Crider, A M; Grubb, R; Bachmann, K A; Rawat, A K

    1981-12-01

    6-Nor-9,10-dihydrolysergic acid methyl ester (IV) was prepared by demethylation of 9,10-dihydrolysergic acid methyl ester (II) with 2,2,2-trichloroethyl chloroformate, followed by reduction of the intermediate carbamate (III) with zinc in acetic acid. The 6-ethyl-V and 6-n-propyl-VI derivatives were prepared by alkylation of IV with the appropriate halide. All of the ergoline derivatives were evaluated for stereotyped behavior in rats, with 6-nor-6-ethyl-9,10-dihydrolysergic acid methyl ester (V) being active but much less potent than apomorphine. Compound VI was evaluated for its effect on blood pressure; at a dose of 30 mg/kg ip, it significantly lowered, diastolic pressure in normotensive rats.

  14. Effect of methyl jasmonate application to grapevine leaves on grape amino acid content.

    Science.gov (United States)

    Garde-Cerdán, Teresa; Portu, Javier; López, Rosa; Santamaría, Pilar

    2016-07-15

    Over the last few years, considerable attention has been paid to the application of elicitors to vineyard. However, research about the effect of elicitors on grape amino acid content is scarce. Therefore, the aim of this study was to evaluate the influence of foliar application of methyl jasmonate on must amino acid content. Results revealed that total amino acid content was not modified by the application of methyl jasmonate. However, the individual content of certain amino acids was increased as consequence of methyl jasmonate foliar application, i.e., histidine, serine, tryptophan, phenylalanine, tyrosine, asparagine, methionine, and lysine. Among them, phenylalanine content was considerably increased; this amino acid is precursor of phenolic and aromatic compounds. In conclusion, foliar application of methyl jasmonate improved must nitrogen composition. This finding suggests that methyl jasmonate treatment might be conducive to obtain wines of higher quality since must amino acid composition could affect the wine volatile composition and the fermentation kinetics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Thermally reversible cross-linked poly(ether-urethanes

    Directory of Open Access Journals (Sweden)

    V. Gaina

    2013-07-01

    Full Text Available Cross-linked poly(ether-urethanes were prepared by Diels-Alder (DA reaction of the furan-containing poly(ether-urethane to bismaleimides and showed thermal reversibility evidenced by differential scanning calorimetry and attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR-FTIR. The furan-containing poly(ether-urethanes were synthesized by the polyaddition reaction of 1,6-hexamethylene diisocyanate (HMDI or 4,4'- dibenzyl diisocyanate (DBDI to poly(tetramethylene ether glycol (PTMEG having Mn = 250, 650, 1000, 1500 and 2000 and 2-[N,N-bis(2-methyl-2-hydroxyethylamino]furfuryl as chain extender by the solution prepolymer method. The molar ratio of isocyanate: PTMEG:chain extender varied from 2:1:1 to 4:1:3, which produces a molar concentration of furyl group ranging between 3.65•10–4 and 1.25•10–3 mol/g.

  16. Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Tang, G.H. [Xian Medical Univ. (China); Shen, Y.; Shen, H.M. [National Univ. of Singapore (Singapore)] [and others

    1996-12-31

    Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

  17. Activity relationships for aromatic crown ethers

    International Nuclear Information System (INIS)

    Wilson, Mark James

    1998-01-01

    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities from molecular modelling and this rational has been applied to the study of proton ionisable and lariating crown ethers. The incorporation of crown ethers into polyamic acid and polyimide frameworks has also been investigated, where the resulting materials have been found to exhibit unusual cation binding and uptake properties. These results imply that the combination of the crown ethers' macrocycle and adjacent carboxylic acid residues, from the polyamic acids, are conducive to effective cationic binding. NMR measurements, in conjunction with molecular modelling, have been used to explore the geometry changes encountered as the crown ether goes from it's uncomplexed to its complexed state. The energy requirement for these geometry changes has subsequently been used to examine the cation selectivity of these materials. The electronic charge changes associated with the complexation have also been investigated and correlated with the theoretical results. (author)

  18. Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

    Science.gov (United States)

    Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

    2018-04-11

    Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

  19. Direct Vinylation of Alcohols or Aldehydes Employing Alkynes as Vinyl Donors: A Ruthenium Catalyzed C-C Bond Forming Transfer Hydrogenation

    Science.gov (United States)

    Patman, Ryan L.; Chaulagain, Mani Raj; Williams, Vanessa M.; Krische, Michael J.

    2011-01-01

    Under the conditions of ruthenium catalyzed transfer hydrogenation, 2-butyne couples to benzylic and aliphatic alcohols 1a–1i to furnish allylic alcohols 2a–2i, constituting a direct C-H vinylation of alcohols employing alkynes as vinyl donors. Under related transfer hydrogenation conditions employing formic acid as terminal reductant, 2-butyne couples to aldehydes 4a, 4b, and 4e to furnish identical products of carbonyl vinylation 2a, 2b, and 2e. Thus, carbonyl vinylation is achieved from the alcohol or the aldehyde oxidation level in the absence of any stoichiometric metallic reagents. Nonsymmetric alkynes 6a–6c couple efficiently to aldehyde 4b to provide allylic alcohols 2m–2o as single regioisomers. Acetylenic aldehyde 7a engages in efficient intramolecular coupling to deliver cyclic allylic alcohol 8a. PMID:19173651

  20. Direct methylation procedure for converting fatty amides to fatty acid methyl esters in feed and digesta samples.

    Science.gov (United States)

    Jenkins, T C; Thies, E J; Mosley, E E

    2001-05-01

    Two direct methylation procedures often used for the analysis of total fatty acids in biological samples were evaluated for their application to samples containing fatty amides. Methylation of 5 mg of oleamide (cis-9-octadecenamide) in a one-step (methanolic HCl for 2 h at 70 degrees C) or a two-step (sodium methoxide for 10 min at 50 degrees C followed by methanolic HCl for 10 min at 80 degrees C) procedure gave 59 and 16% conversions of oleamide to oleic acid, respectively. Oleic acid recovery from oleamide was increased to 100% when the incubation in methanolic HCl was lengthened to 16 h and increased to 103% when the incubation in methoxide was modified to 24 h at 100 degrees C. However, conversion of oleamide to oleic acid in an animal feed sample was incomplete for the modified (24 h) two-step procedure but complete for the modified (16 h) one-step procedure. Unsaturated fatty amides in feed and digesta samples can be converted to fatty acid methyl esters by incubation in methanolic HCl if the time of exposure to the acid catalyst is extended from 2 to 16 h.

  1. Critical properties of some aliphatic symmetrical ethers

    International Nuclear Information System (INIS)

    Nikitin, Eugene D.; Popov, Alexander P.; Bogatishcheva, Nataliya S.

    2014-01-01

    Highlights: • Critical properties of simple aliphatic ethers were measured. • The ethers decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. -- Abstract: The critical temperatures T c and the critical pressures p c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T c = (665 ± 7) K, p c = (1.44 ± 0.04) MPa for dihexyl ether, T c = (723 ± 7) K, p c = (1.19 ± 0.04) MPa for dioctyl ether, and T c = (768 ± 8) K, p c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson

  2. Lifetime Analysis of Rubber Gasket Composed of Methyl Vinyl Silicone Rubber with Low-Temperature Resistance

    Directory of Open Access Journals (Sweden)

    Young-Doo Kwon

    2015-01-01

    Full Text Available Most machines and instruments constantly require elastomeric materials like rubber for the purposes of shock absorption, noise attenuation, and sealing. The material properties and accurate lifetime prediction of rubber are closely related to the quality of machines, especially their durability and reliability. The properties of rubber-like elastomers are influenced by ambient conditions, such as temperature, environment, and mechanical load. Moreover, the initial properties of rubber gaskets must be sustained under working conditions to satisfy their required function. Because of its technical merits, as well as its low cost, the highly accelerated life test (HALT is used by many researchers to predict the long-term lifetime of rubber materials. Methyl vinyl silicone rubber (VMQ has recently been adopted to improve the lifetime of automobile radiator gaskets. A four-parameter method of determining the recovery ability of the gaskets was recently published, and two revised methods of obtaining the recovery were proposed for polyacrylate (ACM rubber. The recovery rate curves for VMQ were acquired using the successive zooming genetic algorithm (SZGA. The gasket lifetime for the target recovery (60% of a compressed gasket was computed somewhat differently depending on the selected regression model.

  3. Palladium-Catalyzed Decarboxylative γ-Olefination of 2,5-Cyclohexadiene-1-carboxylic Acid Derivatives with Vinyl Halides.

    Science.gov (United States)

    Chang, Chi-Hao; Chou, Chih-Ming

    2018-04-06

    This study explores a Pd-catalyzed decarboxylative Heck-type Csp 3 -Csp 2 coupling reaction of 2,5-cyclohexadiene-1-carboxylic acid derivatives with vinyl halides to provide γ-olefination products. The olefinated 1,3-cyclohexadienes can be further oxidized to produce meta-alkylated stilbene derivatives. Additionally, the conjugated diene products can also undergo a Diels-Alder reaction to produce a bicyclo[2.2.2]octadiene framework.

  4. Preparation of robust braid-reinforced poly(vinyl chloride) ultrafiltration hollow fiber membrane with antifouling surface and application to filtration of activated sludge solution.

    Science.gov (United States)

    Zhou, Zhuang; Rajabzadeh, Saeid; Fang, Lifeng; Miyoshi, Taro; Kakihana, Yuriko; Matsuyama, Hideto

    2017-08-01

    Braid-reinforced hollow fiber membranes with high mechanical properties and considerable antifouling surface were prepared by blending poly(vinyl chloride) (PVC) with poly(vinyl chloride-co-poly(ethylene glycol) methyl ether methacrylate) (poly(VC-co-PEGMA)) copolymer via non-solvent induced phase separation (NIPS). The tensile strength of the braid-reinforced PVC hollow fiber membranes were significantly larger than those of previously reported various types of PVC hollow fiber membranes. The high interfacial bonding strength indicated the good compatibility between the coating materials and the surface of polyethylene terephthalate (PET)-braid. Owing to the surface segregation phenomena, the membrane surface PEGMA coverage increased upon increasing the poly(VC-co-PEGMA)/PVC blending ratio, resulting in higher hydrophilicities and bovine serum albumin (BSA) repulsion. To compare the fouling properties, membranes with similar PWPs were prepared by adjusting the dope solution composition to eliminate the effect of hydrodynamic conditions on the membrane fouling performance. The blend membranes surface exhibited considerable fouling resistance to the molecular adsorption from both BSA solution and activated sludge solution. In both cases, the flux recovered to almost 80% of the initial flux using only water backflush. Considering their great mechanical properties and antifouling resistance to activated sludge solution, these novel membranes show good potential for application in wastewater treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Tailoring the morphology and properties of poly(lactic acid)/poly(ethylene-co-vinyl acetate)/starch blends via reactive compatibilization

    NARCIS (Netherlands)

    Ma, P.; Hristova - Bogaerds, D.G.; Schmit, P.; Goossens, J.G.P.; Lemstra, P.J.

    2012-01-01

    Poly(lactic acid)/poly(ethylene-co-vinyl acetate)/starch (PLA/EVA/starch) ternary blends were prepared by multi-step melt processing (reactive extrusion) in the presence of maleic anhydride (MA), benzoyl peroxide and glycerol. The effects of MA and glycerol concentration on the morphology and

  6. Thermoset coatings from epoxidized sucrose soyate and blocked, bio-based dicarboxylic acids.

    Science.gov (United States)

    Kovash, Curtiss S; Pavlacky, Erin; Selvakumar, Sermadurai; Sibi, Mukund P; Webster, Dean C

    2014-08-01

    A new 100% bio-based thermosetting coating system was developed from epoxidized sucrose soyate crosslinked with blocked bio-based dicarboxylic acids. A solvent-free, green method was used to block the carboxylic acid groups and render the acids miscible with the epoxy resin. The thermal reversibility of this blocking allowed for the formulation of epoxy-acid thermoset coatings that are 100% bio-based. This was possible due to the volatility of the vinyl ethers under curing conditions. These systems have good adhesion to metal substrates and perform well under chemical and physical stress. Additionally, the hardness of the coating system is dependent on the chain length of the diacid used, making it tunable. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. DNA methyltransferase homologue TRDMT1 in Plasmodium falciparum specifically methylates endogenous aspartic acid tRNA.

    Science.gov (United States)

    Govindaraju, Gayathri; Jabeena, C A; Sethumadhavan, Devadathan Valiyamangalath; Rajaram, Nivethika; Rajavelu, Arumugam

    2017-10-01

    In eukaryotes, cytosine methylation regulates diverse biological processes such as gene expression, development and maintenance of genomic integrity. However, cytosine methylation and its functions in pathogenic apicomplexan protozoans remain enigmatic. To address this, here we investigated the presence of cytosine methylation in the nucleic acids of the protozoan Plasmodium falciparum. Interestingly, P. falciparum has TRDMT1, a conserved homologue of DNA methyltransferase DNMT2. However, we found that TRDMT1 did not methylate DNA, in vitro. We demonstrate that TRDMT1 methylates cytosine in the endogenous aspartic acid tRNA of P. falciparum. Through RNA bisulfite sequencing, we mapped the position of 5-methyl cytosine in aspartic acid tRNA and found methylation only at C38 position. P. falciparum proteome has significantly higher aspartic acid content and a higher proportion of proteins with poly aspartic acid repeats than other apicomplexan pathogenic protozoans. Proteins with such repeats are functionally important, with significant roles in host-pathogen interactions. Therefore, TRDMT1 mediated C38 methylation of aspartic acid tRNA might play a critical role by translational regulation of important proteins and modulate the pathogenicity of the malarial parasite. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. 46 CFR 151.50-34 - Vinyl chloride (vinyl chloride monomer).

    Science.gov (United States)

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Vinyl chloride (vinyl chloride monomer). 151.50-34... chloride (vinyl chloride monomer). (a) Copper, aluminum, magnesium, mercury, silver, and their alloys shall... equipment that may come in contact with vinyl chloride liquid or vapor. (b) Valves, flanges, and pipe...

  9. Observation of the side chain O-methylation of glutamic acid or aspartic acid containing model peptides by electrospray ionization-mass spectrometry.

    Science.gov (United States)

    Atik, A Emin; Guray, Melda Z; Yalcin, Talat

    2017-03-15

    O-methylation of the side chains of glutamic acid (E) and aspartic acid (D) residues is generally observed modification when an acidified methanol/water (MeOH/dH 2 O) mixture is used as a solvent system during sample preparation for proteomic research. This chemical modification may result misidentification with endogenous protein methylation; therefore, a special care should be taken during sample handling prior to mass spectrometric analysis. In the current study, we systematically examined the extent of E/D methylation and C-terminus carboxyl group of synthetic model peptides in terms of different incubation temperatures, storage times, and added acid types as well as its percentages. To monitor these effects, C-terminus amidated and free acid forms of synthetic model peptides comprised of E or D residue(s) have been analyzed by electrospray ionization-mass spectrometry (ESI-MS). Additionally, LC-MS/MS experiments were performed to confirm the formation of methylated peptide product. The results showed that the rate of methylation was increased as the temperature increases along with prolong incubation times. Moreover, the extent of methylation was remarkably high when formic acid (FA) used as a protonation agent instead of acetic acid (AA). In addition, it was found that the degree of methylation was significantly decreased by lowering acid percentages in ESI solution. More than one acidic residue containing model peptides have been also used to explore the extent of multiple methylation reaction. Lastly, the ethanol (EtOH) and isopropanol (iPrOH) have been substituted separately with MeOH in sample preparation step to investigate the extent of esterification reaction under the same experimental conditions. However, in the positive perspective of view, this method can be used as a simple, rapid and cheap method for methylation of acidic residues under normal laboratory conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Directory of Open Access Journals (Sweden)

    Marcia E. Richard

    2013-10-01

    Full Text Available A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

  11. The 11C-radioisotopic study of methanol conversion on V-MCM-41; the influence of methyl iodide on the transformation

    International Nuclear Information System (INIS)

    Sarkadi-Priboczki, E.; Szelecsenyi, F.; Kovacs, Z.; Solmaz, A.; Balci, S.; Dogu, T.

    2007-01-01

    Complete text of publication follows. The MCM-41 mesoporous material has Lewis and even Bronsted acid sites to produce dimethyl ether with some hydrocarbons, while over metal modified MCM-41 mostly formaldehyde and dimethoxy methane (i.e. methylal) or methyl formate are produced. In present experiments V incorporated basically mild acid sites of MCM-41 was prepared by low temperature direct synthesis. The V-MCM-41 has enough main active Lewis sites (by V-) to form formaldehyde and also light Bronsted acid sites to let the adsorbed formaldehyde eliminate and afterwards, with methanol, to form dimethoxy methane in nonoxidative environment. This V-MCM-41 has been tested by ethanol conversion in non-oxidative environments too and diethoxy methane as main product was detected. In present work the methanol conversion, as well as the methanol co-reaction with methyl iodide are studied from the same V-MCM-41 sample using 11 C-technique. The 11 C-labelled radioactive methanol has been already applied for determination of methanol conversion rates on Cu-modified MCM-41. The V-MCM-41 was prepared by direct hydrothermal synthesis method. The adsorption rate of 11 C-methanol and, after the reaction, the desorption rate of the remaining 11 C-derivatives on catalyst were continuously detected by gamma detectors. The derivatives were analyzed by radio-gas chromatography (gas chromatograph with FID coupled on-line with a radioactivity detector). Both dimethyl ether and hydrocarbon formation are also in slight degrees according to weak Lewis and Bronsted acidities. Since the conversion was carried out without added oxygen gas, only the frame oxygen can take part into catalysis. In presence of non-radioactive methyl iodide, the radioactive methanol is converted to radioactive methyl iodide on V-MCM-41. The radio-GC analysis confirmed that the iodide induced change of the reaction performance was reversible i.e. the radioactive methyl iodide was regenerated to non-radioactive methyl

  12. Model-based analysis of CO2 revalorization for di-methyl ether synthesis driven by solar catalytic reforming

    International Nuclear Information System (INIS)

    Luu, Minh Tri; Milani, Dia; Sharma, Manish; Zeaiter, Joseph; Abbas, Ali

    2016-01-01

    Highlights: • Solar energy applied for synthesis of di-methyl ether via dry methane reforming. • Concentrated solar energy at receiver reaction zone for syngas generation. • H 2 /CO molar ratio of ‘1’ is maintained via two alternative processing routes. • Assessed three days of operation under different insolation levels. • Improvements of 18.7%, 32.2% and 20% for methane, energy and CO 2 emission intensities. - Abstract: The application of solar energy is investigated for the synthesis of di-methyl ether (DME) in a solar irradiated dry methane reformer (DMR). Solar radiations are concentrated onto a receiver and distributed to the reaction zone to provide necessary energy for syngas (CO and H 2 ) generation. In order to maintain a H 2 /CO molar ratio of ‘1’, as required in DME synthesis, the produced syngas is processed via two alternative routes: solar reformer coupled in parallel with a non-solar reformer (SoR-NSoR) and solar reformer integrated with a water-gas shift reactor (SoR-WGS). It is found that steam methane reforming (SMR) is the most suitable methodology when coupled with a solar reformer due to high H 2 content in the SMR syngas. Further performance analysis is conducted by simulating three days of operation under different insolation levels (high, medium and low irradiations). The simulation results showed that the SoR-WGS configuration produces the highest improvements of 18.7%, 32.2% and 20% in terms of methane, energy and CO 2 emission intensity respectively. This enhanced process performance originates from the exothermic nature of the WGS process which helps in controlling the overall syngas composition, whereas the SoR-NSoR requires fossil based thermal energy to drive the NSoR process to similar control targets. This promising improvement of all metrics in SoR-WGS may stimulate in-depth techno-economic feasibility of this unique solar integration for DME and other synthetic fuels production.

  13. Ester Sensing with Poly (Aniline-co-m-aminobenzoic Acid Deposited on Poly (Vinyl Alcohol

    Directory of Open Access Journals (Sweden)

    S. ADHIKARI

    2011-02-01

    Full Text Available Poly (aniline-co-m-aminobenzoic acid was deposited on poly (vinyl alcohol film by in situ oxidative polymerization of the monomers aniline and m-aminobenzoic acid. Sensing experiments were performed on the composite film with the injection of various concentrations of hexenyl acetate and hexenyl butyrate at room temperature. The sensor responded rapidly and reversibly in the presence of hexenyl acetate and hexenyl butyrate vapors which was detected by resistance change of the composite film upon exposure to the vapor. Selectivity tests revealed that the sensor selectively responded to hexenyl butyrate compared to hexenyl acetate. The sensing response has been explained on the basis of FT-IR spectroscopic analysis of the polymer film before and after exposure to the ester vapor.

  14. Determining the fatty acid composition in plasma and tissues as fatty acid methyl esters using gas chromatography – a comparison of different derivatization and extraction procedures.

    Science.gov (United States)

    Ostermann, Annika I; Müller, Maike; Willenberg, Ina; Schebb, Nils Helge

    2014-12-01

    Analysis of the fatty acid (FA) composition in biological samples is commonly carried out using gas liquid chromatography (GC) after transesterification to volatile FA methyl esters (FAME). We compared the efficacy of six frequently used protocols for derivatization of different lipid classes as well as for plasma and tissue samples. Transesterification with trimethylsulfonium hydroxide (TMSH) led to insufficient derivatization efficacies for polyunsaturated FAs (PUFA, ester (CE) as well as triacylglycerols (TGs). In contrast, methanolic hydrochloric acid (HCl) as well as a combination of BF3 with methanolic sodium hydroxide (NaOH+BF3) were suitable for the derivatization of FFAs, polar lipids, TGs, and CEs (derivatization rate >80% for all tested lipids). Regarding plasma samples, all methods led to an overall similar relative FA pattern. However, significant differences were observed, for example, for the relative amount of EPA+DHA (n3-index). Absolute FA plasma concentrations differed considerably among the methods, with low yields for KOH and BF3. We also demonstrate that lipid extraction with tert-butyl methyl ether/methanol (MTBE/MeOH) is as efficient as the classical method according to Bligh and Dyer, making it possible to replace (environmentally) toxic chloroform.We conclude that HCl-catalyzed derivatization in combination with MeOH/MTBE extraction is the most appropriate among the methods tested for the analysis of FA concentrations and FA pattern in small biological samples. A detailed protocol for the analysis of plasma and tissues is included in this article.

  15. Carcinogenicity of methyl-tertiary butyl ether in gasoline.

    Science.gov (United States)

    Mehlman, Myron A

    2002-12-01

    Methyl tertiary butyl ether (MTBE) was added to gasoline on a nationwide scale in 1992 without prior testing of adverse, toxic, or carcinogenic effects. Since that time, numerous reports have appeared describing adverse health effects of individuals exposed to MTBE, both from inhalation of fumes in the workplace and while pumping gasoline. Leakage of MTBE, a highly water-soluble compound, from underground storage tanks has led to contamination of the water supply in many areas of the United States. Legislation has been passed by many states to prohibit the addition of MTBE to gasoline. The addition of MTBE to gasoline has not accomplished its stated goal of decreasing air pollution, and it has posed serious health risks to a large portion of the population, particularly the elderly and those with respiratory problems, asthma, and skin sensitivity. Reports of animal studies of carcinogenicity of MTBE began to appear in the 1990s, prior to the widespread introduction of MTBE into gasoline. These reports were largely ignored. In ensuing years, further studies have shown that MTBE causes various types of malignant tumors in mice and rats. The National Toxicology Program (NTP) Board of Scientific Counselors' Report on Carcinogens Subcommittee met in December 1998 to consider listing MTBE as "reasonably anticipated to be a human carcinogen." In spite of recommendations from Dr. Bailer, the primary reviewer, and other scientists on the committee, the motion to list MTBE in the report was defeated by a six to five vote, with one abstention. On the basis of animal studies, it is widely accepted that if a chemical is carcinogenic in appropriate laboratory animal test systems, it must be treated as though it were carcinogenic in humans. In the face of compelling evidence, NTP Committee members who voted not to list MTBE as "reasonably anticipated to be a human carcinogen" did a disservice to the general public; this action may cause needless exposure of many to health risks

  16. Microwave-assisted pyrolysis of methyl ricinoleate for continuous production of undecylenic acid methyl ester (UAME).

    Science.gov (United States)

    Nie, Yong; Duan, Ying; Gong, Ruchao; Yu, Shangzhi; Lu, Meizhen; Yu, Fengwen; Ji, Jianbing

    2015-06-01

    Undecylenic acid methyl ester (UAME) was continuously produced from methyl ricinoleate using a microwave-assisted pyrolysis system with atomization feeding. The UAME yield of 77 wt.% was obtained at 500°C using SiC as the microwave absorbent and heating medium. The methyl ricinoleate conversion and UAME yield from microwave-assisted pyrolysis process were higher than those from conventional pyrolysis. The effect of temperature on the pyrolysis process was also investigated. The methyl ricinoleate conversion increased but the cracking liquid yield decreased when the temperature increased from 460°C to 560°C. The maximum UAME yield was obtained at the temperature of 500°C. Copyright © 2015 Elsevier Ltd. All rights reserved.

  17. Degradation of methyl tert-butyl ether by gel immobilized Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Chen, Dongzhi; Chen, Jianmeng; Zhong, Weihong; Cheng, Zhuowei

    2008-07-01

    Cells of Methylibium petroleiphilum PM1 were immobilized in gel beads to degrade methyl tert-butyl ether (MTBE). Calcium alginate, agar, polyacrylamide and polyvinvyl alcohol were screened as suitable immobilization matrices, with calcium alginate demonstrating the fastest MTBE-degradation rate. The rate was accelerated by 1.8-fold when the beads had been treated in physiological saline for 24h at 28 degrees C. MTBE degradation in mineral salts medium (MSM) was accompanied by the increase of biomass. The half-life of MTBE-degradation activity for the encapsulated cells stored at 28 degrees C was about 120 h, which was obviously longer than that of free cells (approximately 36 h). Efficient reusability of the beads up to 30 batches was achieved in poor nutrition solution as compared to only 6 batches in MSM. The immobilized cells could be operated in a packed-bed reactor for degradation of 10 mg L(-1) MTBE in groundwater with more than 99% removal efficiency at hydraulic retention time of 20 min. These results suggested that immobilized cells of PM1 in bioreactor might be applicable to a groundwater treatment system for the removal of MTBE.

  18. Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Lopes Ferreira, N

    2005-11-15

    Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

  19. Catabolism of methyl ter-butyl ether (MTBE): characterization of the enzymes of Mycobacterium austroafricanum IFP 2012 involved in MTBE degradation; Catabolisme du methyl tert-butyl ether (MTBE): caracterisation des enzymes impliquees dans la degradation du MTBE chez Mycobacterium austroafricanum IFP 2012

    Energy Technology Data Exchange (ETDEWEB)

    Lopes Ferreira, N.

    2005-11-15

    Methyl tert-butyl ether (MTBE) is added to gasoline to meet the octane index requirement. its solubility in water and its poor biodegradability made the use of MTBE a great environmental concern, particularly regarding aquifers. We previously isolated M austroafricanum IFP 2012 able to use MTBE as a sole source of carbon and energy and the MTBE pathway was partially characterized. In the present study, which aimed at isolating the genes involved in MTBE biodegradation in order to use them for estimation of MTBE biodegradation capacities in contaminated environment, we isolated a new M. austroafricanum strain, IFP 2015. A new degradation intermediate, the 2-methyl 1,2-propane-diol (2-M1,2-PD), the product of tert-butanol (TBA) oxidation, was identified. We also determined the enzymes induced during growth of M. austroafricanum IFP 2012 on MTBF. Then, using the tools of protein analysis and of molecular biology, we isolated and cloned the mpd genes cluster in the plasmid pCL4D. Heterologous expression of the recombinant plasmid in M smegmatis tmc2 155, showed the involvement of an 2-M1,2-PD dehydrogenase (MpdB) and a hydroxy-iso-butyr-aldehyde dehydrogenase (MpdC), encoded by mpdB and mpdC, respectively. Both enzymes were responsible for the conversion of 2-M 1,2-PD to hydroxy-isobutyric acid (HIBA). A further survey of different M austroafricanum strains, including IFP 2012, IFP 2015 and JOBS (ex-M vaccae) showed the link between the ability to grow on C{sub 2} to C{sub 16} n-alkanes and the MTBE and TBA degradation capacities. The alkB gene was partially sequenced in all these strains. Expression of alkB was demonstrated in M. austroafricanum IFP 2012 after growth on propane, hexane, hexadecane and TBA. Finally, we identified 2-propanol as the intermediate of HIBA degradation. The gene encoding the 2-propanol:p-N,N'-dimethyl-4-nitroso-aniline (NDMA) oxidoreductase was detected M austroafricanum IFP 2012. (author)

  20. Kinetic Isotope Effects in the Reduction of Methyl Iodide

    DEFF Research Database (Denmark)

    Holm, Torkil

    1999-01-01

    a Grignard reagent to methyl iodide, and for reduction of methyl iodide with tributyltin hydride or with gaseous hydrogen iodide. Very small KIE's were found for electron transfer to methyl iodide from magnesium in ether or from sodium in ammonia. The reason may be that these reactions are transport...

  1. Evaluation of various Crown ethers for the supercritical fluid extraction of uranium from nitric acid medium

    International Nuclear Information System (INIS)

    Kumar, Pradeep; Rao, Ankita; Ramakumar, K.L.

    2009-01-01

    Various crowns have been evaluated for supercritical fluid extraction of uranium from nitric acid medium employing HPFOA as counter ion. Uranium extraction efficiency was found to be influenced by cavity size of crown ether and nature of substituents. Complexation tendency of UO 2 2+ increases with increasing cavity size of crown ether. Electron withdrawing substituents decreased the extraction efficiency which could be attributed to decrease in the basicity of four oxygen atoms and hence their bonding ability. Whereas electron donating substituents increased the efficiency due to increases in basicity of oxygen atoms and hence in increase in bonding ability. (author)

  2. Synthesis and characterization of copolymers from hindered amines and vinyl monomers

    Directory of Open Access Journals (Sweden)

    Marcelo Aparecido Chinelatto

    2014-01-01

    Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

  3. Effects of altered maternal folic acid, vitamin B12 and docosahexaenoic acid on placental global DNA methylation patterns in Wistar rats.

    Directory of Open Access Journals (Sweden)

    Asmita Kulkarni

    Full Text Available Potential adverse effects of excess maternal folic acid supplementation on a vegetarian population deficient in vitamin B(12 are poorly understood. We have previously shown in a rat model that maternal folic acid supplementation at marginal protein levels reduces brain omega-3 fatty acid levels in the adult offspring. We have also reported that reduced docosahexaenoic acid (DHA levels may result in diversion of methyl groups towards DNA in the one carbon metabolic pathway ultimately resulting in DNA methylation. This study was designed to examine the effect of normal and excess folic acid in the absence and presence of vitamin B(12 deficiency on global methylation patterns in the placenta. Further, the effect of maternal omega 3 fatty acid supplementation on the above vitamin B(12 deficient diets was also examined. Our results suggest maternal folic acid supplementation in the absence of vitamin B(12 lowers plasma and placental DHA levels (p<0.05 and reduces global DNA methylation levels (p<0.05. When this group was supplemented with omega 3 fatty acids there was an increase in placental DHA levels and subsequently DNA methylation levels revert back to the levels of the control group. Our results suggest for the first time that DHA plays an important role in one carbon metabolism thereby influencing global DNA methylation in the placenta.

  4. Pulse radiolysis study of reactions of alkyl and alkylperoxy radicals originating from methyl tert-butyl ether in the gas phase

    DEFF Research Database (Denmark)

    Langer, S.; Ljungström, E.; Ellermann, T.

    1995-01-01

    UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm, sigma(R) = (2.6 +/- 0.4) X...... and the alkylperoxy radicals with NO and NO2 are (9.1 +/- 1.5) X 10(-13), (4.3 +/- 1.6) X 10(-12) and (1.2 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1), respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule....

  5. Elution behavior of poly(ethylene glycol) through poly(vinyl alcohol) gel column using several solvents as eluents

    International Nuclear Information System (INIS)

    Hirayama, Chuichi; Motozato, Yoshiaki; Matsumoto, Kazuaki.

    1983-01-01

    γ-Irradiated poly(vinyl alcohol) beads, which were sufficiently allowed to swell in water, were washed with methanol, and then were packed into column. Gel chromatography was performed using methanol, benzene, esters and ketones as eluents and poly(ethylene glycol) as a sample. When the elution was carried out using methanol and benzene as eluents, elution behavior of samples was ordinary. When ethyl formate, methyl acetate and ethyl propionate were used as eluents, samples were slightly adsorbed and the elution was delayed. In the case the elution was carried out using ethyl acetate, propyl acetate, butyl acetate and ethyl methyl ketone as eluents, samples were adsorbed strongly on the bed material, and the adsorption curve was analogous to the calibration curve using methanol as an eluent. Dried poly(vinyl alcohol) gel as a packing material, showed ordinary elution behaviors for the samples. The adsorption of poly(ethylene glycol) on the present bed material was attributed to the existence of hydrated water on poly(vinyl alcohol) gel matrix. (author)

  6. Synthesis of Fischer carbene complexes of iridium by C-H bond activation of methyl and cyclic ethers: Evidence for reversible {alpha}-hydrogen migration

    Energy Technology Data Exchange (ETDEWEB)

    Luecke, H.F.; Arndtsen, B.A.; Burger, P.; Bergman, R.G. [Lawrence Berkeley Lab., CA (United States)]|[Univ. of California, Berkeley, CA (United States)

    1996-03-13

    We report here a mild and versatile route to Fischer carbene complexes of iridium via the activation of C-H bonds of methyl and cyclic ethers, along with our preliminary studies of this rare family of carbene complexes. Theoretical studies suggest that {alpha}-hydrogen migrations can be kinetically favorable if a coordinatively unsaturated species can be accessed. Thus, the lability of the triflate ligand presumably facilitates this process. Further evidence for the rapidity, as well as reversibility, of this rearrangement was obtained by NMR analysis. 20 refs.

  7. Acid-degradable and bioerodible modified polyhydroxylated materials

    Energy Technology Data Exchange (ETDEWEB)

    Frechet, Jean M. J.; Bachelder, Eric M.; Beaudette, Tristan T.; Broaders, Kyle E.

    2017-05-09

    Compositions and methods of making a modified polyhydroxylated polymer comprising a polyhydroxylated polymer having reversibly modified hydroxyl groups, whereby the hydroxyl groups are modified by an acid-catalyzed reaction between a polydroxylated polymer and a reagent such as acetals, aldehydes, vinyl ethers and ketones such that the modified polyhydroxylated polymers become insoluble in water but freely soluble in common organic solvents allowing for the facile preparation of acid-sensitive materials. Materials made from these polymers can be made to degrade in a pH-dependent manner. Both hydrophobic and hydrophilic cargoes were successfully loaded into particles made from the present polymers using single and double emulsion techniques, respectively. Due to its ease of preparation, processability, pH-sensitivity, and biocompatibility, of the present modified polyhydroxylated polymers should find use in numerous drug delivery applications.

  8. Theoretical study of the regioselectivity of the interaction of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone with Lewis acids.

    Science.gov (United States)

    Kasende, Okuma Emile; Muya, Jules Tshishimbi; Broeckaert, Lies; Maes, Guido; Geerlings, Paul

    2012-08-23

    A density functional theory (DFT) study is performed to determine the stability of the complexes formed between either the N or O site of 3-methyl-4-pyrimidone and 1-methyl-2-pyrimidone molecules and different ligands. The studied ligands are boron and alkali Lewis acids, namely, B(CH(3))(3), HB(CH(3))(2), H(2)B(CH(3)), BH(3), H(2)BF, HBF(2), BF(3), Li(+), Na(+), and K(+). The acids are divided into two groups according to their hardness. The reactivity predictions, according to the molecular electrostatic potential (MEP) map and the natural bond orbital (NBO) analysis, are in agreement with the calculated relative stabilities. Our findings reveal a strong regioselectivity with borane and its derivatives preferring the nitrogen site in both pyrimidone isomers, while a preference for oxygen is observed for the alkali acids in the 3-methyl-4-pyrimidone molecule. The complexation of 1-methyl-2-pyrimidone with these hard alkali acids does not show any discrimination between the two sites due to the presence of a continuous delocalized density region between the nitrogen and the oxygen atoms. The preference of boron Lewis acids toward the N site is due to the stronger B-N bond as compared to the B-O bond. The influence of fluorine or methyl substitution on the boron atom is discussed through natural orbital analysis (NBO) concentrating on the overlap of the boron empty p-orbital with the F lone pairs and methyl hyperconjugation, respectively. The electrophilicity of the boron acids gives a good overall picture of the interaction capabilities with the Lewis base.

  9. 21 CFR 172.872 - Methyl ethyl cellulose.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Methyl ethyl cellulose. 172.872 Section 172.872... CONSUMPTION Multipurpose Additives § 172.872 Methyl ethyl cellulose. The food additive methyl ethyl cellulose... a cellulose ether having the general formula [C6H(10 -x-y)O5(CH3)x(C2H5)y]n, where x is the number...

  10. CFD simulation of fatty acid methyl ester production in bubble column reactor

    Science.gov (United States)

    Salleh, N. S. Mohd; Nasir, N. F.

    2017-09-01

    Non-catalytic transesterification is one of the method that was used to produce the fatty acid methyl ester (FAME) by blowing superheated methanol bubbles continuously into the vegetable oil without using any catalyst. This research aimed to simulate the production of FAME from palm oil in a bubble column reactor. Computational Fluid Dynamic (CFD) simulation was used to predict the distribution of fatty acid methyl ester and other product in the reactor. The fluid flow and component of concentration along the reaction time was investigated and the effects of reaction temperature (523 K and 563 K) on the non-catalytic transesterification process has been examined. The study was carried out using ANSYS CFX 17.1. The finding from the study shows that increasing the temperature leads to higher amount of fatty acid methyl ester can be produced in shorter time. On the other hand, concentration of the component such as triglyceride (TG), glycerol (GL) and fatty acid methyl ester (FAME) can be known when reaching the optimum condition.

  11. Effect of organoelemental compounds of group 3 elements on radical polymerization of vinyl monomers

    International Nuclear Information System (INIS)

    Grishin, D.F.; Mojkin, A.A.

    1996-01-01

    When alkyl, alkyl alkoxy, and alkyl halide derivatives of boron and aluminium are introduced into the system in amounts that are comparable to the concentration of initiator, they coordinate to the growing macroradicals, thus changing their reactivity, and exert regulating effect on the rate of polymerization of vinyl monomers and the molecular mass of the resulting polymers. The said organoelemental compounds accelerate the polymerization of butyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate, and vinylidene chloride, reduce the molecular mass of acrylic polymers, and virtually do not affect the polymerization of styrene. The specific features of vinyl polymerization are associated with participation of organoelemental additives at the stages of chain growth and chain termination and can be explained within the framework of the mechanism of radical-coordination polymerization. 32 refs., 3 tabs

  12. Two-year drinking water carcinogenicity study of methyl tertiary-butyl ether (MTBE) in Wistar rats.

    Science.gov (United States)

    Dodd, Darol; Willson, Gabrielle; Parkinson, Horace; Bermudez, Edilberto

    2013-07-01

    Methyl tertiary-butyl ether (MTBE) has been used as a gasoline additive to reduce tailpipe emissions and its use has been discontinued. There remains a concern that drinking water sources have been contaminated with MTBE. A two-year drinking water carcinogenicity study of MTBE was conducted in Wistar rats (males, 0, 0.5, 3, 7.5 mg ml(-1); and females, 0, 0.5, 3, and 15 mg ml(-1)). Body weights were unaffected and water consumption was reduced in MTBE-exposed males and females. Wet weights of male kidneys were increased at the end of two years of exposure to 7.5 mg ml(-1) MTBE. Chronic progressive nephropathy was observed in males and females, was more severe in males, and was exacerbated in the high MTBE exposure groups. Brain was the only tissue with a statistically significant finding of neoplasms. One astrocytoma (1/50) was found in a female rat (15 mg ml(-1)). The incidence of brain astrocytomas in male rats was 1/50, 1/50, 1/50 and 4/50 for the 0, 0.5, 3 and 7.5 mg ml(-1) exposure groups, respectively. This was a marginally significant statistical trend, but not statistically significant when pairwise comparisons were made or when multiple comparisons were taken into account. The incidence of astrocytoma fell within historical control ranges for Wistar rats, and the brain has not been identified as a target organ following chronic administration of MTBE, ethyl tert-butyl ether, or tertiary butyl alcohol (in drinking water) to mice and rats. We conclude that the astrocytomas observed in this study are not associated with exposure to MTBE. Copyright © 2011 John Wiley & Sons, Ltd.

  13. Determination of alcohols, ethers and organic acids in irradiated sweet potato wine by capillary gas chromatography

    International Nuclear Information System (INIS)

    Zhou Yingcai; Yuan Bihuai; Xu Peishu; Wang Xiuying

    1986-01-01

    Alcohols, ethers and organic acids in irradiated sweet potato wine have been determined with capillary GC. The results show that the contents of some components have changed after irradiation, but no new species are formed. The G values of the changed components have been calculated

  14. Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

    Directory of Open Access Journals (Sweden)

    Kenji Michiue

    2015-11-01

    Full Text Available In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’2]ZrCl2 (Indenyl’ = generic substituted indenyl, after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenylzirconium dichloride (1, rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl] zirconium dichloride (2, rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl]zirconium dichloride (3, rac-dimethy1si1y1- bis(2-ethyl-4-phenylindenyl zirconium dichloride (4, rac-dimethylsilyl-bis[l-(2-n-propyl -4-(1-naphthylindenyl]zirconium dichloride (5, rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenylindenyl][1-(2-n-propyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenylindenyl]zirconium dichloride (6, rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthrylindenyl]zirconium dichloride (7, and rac-dimethylsilyl-bis[l-(2-n-propyl-4-(9-phenanthrylindenyl]zirconium dichloride (8. We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 > 7 > 6 > 5 > 4 > 3 > 2 > 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.

  15. Site selectivity in the addition of ketoximes to activated allenes and alkynes; N- versus O-alkylation

    OpenAIRE

    Heaney, Frances; Kelly, Bronwyn M.; Bourke, Sharon; Rooney, Oliver; Cunningham, Desmond; McArdle, Patrick

    1999-01-01

    Reaction of ketoximes with methyl propiolate afforded geometrical isomers of the methyl 3-(hydroxyimino)propanoates 4 and of the O-vinyl oximes 5 as well as the 2-isoxazoline 6. With dimethyl penta-2,3-diendioate 8c reaction progressed via an O-alkylation to give the O-oxime ethers 9, only in the case of cyclopentanone oxime was the spirocyclic dihydroazepinol 11 also obtained, its identity has been confirmed by an X-ray structure determination.

  16. Kinetics of Vinyl Polymerization of Methyl Methacrylate Initiated by Ce(IV-Vanillin Redox System

    Directory of Open Access Journals (Sweden)

    M. Palanivelu

    2012-01-01

    Full Text Available The kinetics of polymerization of methyl methacrylate initiated by Ce(IV-Vanillin redox system was studied in aqueous solution of sulfuric acid at 40°C. The rate of polymerization (Rp and the reaction orders with respect to monomer, initiator and ligand have been determined and found to be 1.5, 0.5 and 0.5 respectively. The effect of concentration of sulfuric acid on the polymerization was also studied. The rate of polymerization was found to increase with increasing temperature 30–60°C and decreases at higher temperature (>60°C. The overall activation energy (Ea was found to be 36.7 kJ/mol. A suitable kinetic scheme has been proposed.

  17. ON THE PECULIARITIES OF THE RING CONTRACTION REACTIONS OF HOMODRIMANES VIA ACID MEDIATED EPOXIDE REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Veaceslav Kulciţki

    2011-06-01

    Full Text Available A selective rearrangement of a epoxy-homodrimanic substrate is described. Using fluorosulfonic acid at low temperature leads by ring contraction to a perhydrindanic structure. On the contrary, using boron trifluoride-diethyl ether at r.t. selectively brings about angular methyl migration.

  18. Permeability of solutes through cellophanes grafted with vinyl monomers. I. Diffusion of potassium chloride, urea, and uric acid

    International Nuclear Information System (INIS)

    Takigami, S.; Maeda, Y.; Nakamura, Y.

    1979-01-01

    The diffusive permeability of potassium chloride, urea, and uric acid through cellophanes grafted with acrylamide, acrylic acid, styrene, and N-vinyl-2-pyrrolidone by γ-ray irradiation was studied. The diffusive permeability coefficients of the permeants through the grafted cellophanes were increased with increase in hydration of the grafted membranes, except for the permeation of potassium chloride through cellophanes grafted with acrylic acid. The permeation of potassium chloride, urea, and uric acid through the various grafted cellophanes is explained by the free volume concept of homogeneously water-swollen membranes. However, the behavior of the permeation of potassium chloride through cellophane grafted with acrylic acid deviated from that of nonionic membranes because of the contribution of the electrical interaction between electrolyte and charge of the membrane. 4 figures, 3 tables

  19. Separation of gases through gas enrichment membrane composites

    Science.gov (United States)

    Swedo, Raymond J.; Kurek, Paul R.

    1988-01-01

    Thin film composite membranes having as a permselective layer a film of a homopolymer of certain vinyl alkyl ethers are useful in the separation of various gases. Such homopolymers have a molecular weight of greater than 30,000 and the alkyl group of the vinyl alkyl monomer has from 4 to 20 carbon atoms with branching within the alkyl moiety at least at the carbon atom bonded to the ether oxygen or at the next adjacent carbon atom. These membranes show excellent hydrolytic stability, especially in the presence of acidic or basic gaseous components.

  20. Microalgal fatty acid methyl ester a new source of bioactive compounds with antimicrobial activity

    Directory of Open Access Journals (Sweden)

    Arumugham Suresh

    2014-09-01

    Full Text Available Objective: To evaluate fatty acid composition and the antimicrobial activity of the major fraction of fatty acid methyl ester (FAME extracts from three microalgae collected from freshwater lakes in Theni District, Tamil Nadu, India. Methods: Antimicrobial study was carried out by well diffusion method against bacterial as well as fungal pathogens such as Escherichia coli, Staphylococcus aureus, Enterobacter sp., Klebsiella sp., Salmonella typhi, Fusarium sp., Cryptococcus sp., Candida sp., and Aspergillus niger and Aspergillus flavus. The FAME profiles were determined through gas chromatography with a flame ionization detector. Results: The FAME was found to be radial effective in inhibiting the radial growth of both bacterial and fungal pathogens. The FAME extracts exhibited the antibacterial activity against three clinical pathogens, namely, Escherichia coli, Salmonella typhi and Enterobacter sp. with the maximum zone of inhibition of 12.0 mm, 12.0 mm and 11.0 mm, respectively. The FAME showed moderate antifungal activity against Cryptococcus sp. (11.8 mm, Aspergillus niger (10.5 mm, Candida sp. (11.8 mm and Fusarium sp. (10.4 mm. Gas chromatography-flame ionization detector analysis revealed about 30 different FAMEs. Conclusions: We assume that the observed antimicrobial potency may be due to the abundance of erucic acid methyl ester (C22:0, arachidic acid methyl ester (C20:0, palmitic acid methyl ester (C16:0, cis-11-eicosenoicmethyl ester (C20:1, cis-11, 14-eicosadienoic acid methyl ester (C20:2 and linolenic acid methyl ester (C18:3 in FAMEs which appears to be promising to treat microbial diseases.

  1. Incineration of oxygenated volatile organic compounds. Experimental study and kinetic modeling of the oxidation of methyl ethyl ketone, ethyl acetate and butan-2-ol in methane flames; Incineration de composes organiques volatils oxygenes. Etude experimentale et modelisation cinetique de l'oxydation de la methyl ethyl cetone, de l'acetate d'ethyle et du butan-2-ol dans des flammes de methane

    Energy Technology Data Exchange (ETDEWEB)

    Decottignies, V

    2000-12-01

    This work deals with the low pressure (0.05 atm) degradation of three volatile organic compounds (VOCs): methyl-ethyl-ketone, ethyl acetate and butan-2-ol, in premixed stoichiometric laminar methane flames seeded with 1 to 3% of each VOC. Molar fraction profiles of species have been obtained using microprobe sampling coupled with a gas chromatography and a mass spectroscopy analysis. Temperature profiles have been obtained using the covered thermocouple technique in the presence of the microprobe. The addition of a VOC in the initial reagents mixture leads to an increase of the quantity of intermediate hydrocarbon compounds and in particular of some soot precursor species. The degradation of VOCs leads to the formation of oxygenated intermediates like methanol, dimethyl-ether, acetaldehyde, propanal, acetone and vinyl acetate, the type of VOC having an effect on the quantities produced. The degradation of a VOC can lead to the formation of more toxic or polluting compounds (methyl vinyl ketone, acetic acid and acrolein) than the VOC itself. In the conditions of the study, the intermediate compounds are totally destructed inside the reactional area of the flame front and are no more present in the burnt gases. Sub-mechanisms of VOC oxidation have been developed using experimental observations and the most recent recommendations of the literature. These sub-mechanisms comprise 49 species involved in 241 elementary reactions. Their validation has been performed by comparing the experiment with the kinetic modeling on the molar fraction profiles of the detected species. Experimental data are well reproduced by the model for most species. The addition of a VOC inside the initial reagents mixture creates an important reactivity increase, in particular in the case of butan-2-ol seeded flames. The analysis of reactional ways has permitted to draw out the main reactions responsible for the degradation of the 3 VOCs and the ways of formation and consumption of the

  2. Adverse eff ects of polymeric nanoparticle poly(ethylene glycol- block-polylactide methyl ether (PEG-b-PLA on steroid hormone secretion by porcine granulosa cells

    Directory of Open Access Journals (Sweden)

    Scsukova Sona

    2017-04-01

    Full Text Available Objectives. 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.

  3. Optimization of reactive simulated moving bed systems with modulation of feed concentration for production of glycol ether ester.

    Science.gov (United States)

    Agrawal, Gaurav; Oh, Jungmin; Sreedhar, Balamurali; Tie, Shan; Donaldson, Megan E; Frank, Timothy C; Schultz, Alfred K; Bommarius, Andreas S; Kawajiri, Yoshiaki

    2014-09-19

    In this article, we extend the simulated moving bed reactor (SMBR) mode of operation to the production of propylene glycol methyl ether acetate (DOWANOL™ PMA glycol ether) through the esterification of 1-methoxy-2-propanol (DOWANOL™ PM glycol ether) and acetic acid using AMBERLYST™ 15 as a catalyst and adsorbent. In addition, for the first time, we integrate the concept of modulation of the feed concentration (ModiCon) to SMBR operation. The performance of the conventional (constant feed) and ModiCon operation modes of SMBR are analyzed and compared. The SMBR processes are designed using a model based on a multi-objective optimization approach, where a transport dispersive model with a linear driving force for the adsorption rate has been used for modeling the SMBR system. The adsorption equilibrium and kinetics parameters are estimated from the batch and single column injection experiments by the inverse method. The multiple objectives are to maximize the production rate of DOWANOL™ PMA glycol ether, maximize the conversion of the esterification reaction and minimize the consumption of DOWANOL™ PM glycol ether which also acts as the desorbent in the chromatographic separation. It is shown that ModiCon achieves a higher productivity by 12-36% over the conventional operation with higher product purity and recovery. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Gas-Phase Infrared Spectra of Vinyl Selenol and Vinyl Tellurol

    Science.gov (United States)

    Benidar, Abdessamad; Khater, Brahim; Guillemin, Jean-Claude; Gámez, José A.; Yáñez, Manuel

    2009-10-01

    The infrared spectra (3500-500 cm-1) of gaseous vinyl selenol and vinyl tellurol have been recorded at 0.1 cm-1 resolution. For the latter the spectra were obtained at room temperature, but for the former a temperature of -40 °C was required because of the chemical instability of vinyl selenol at room temperature. To compensate the very weak vapor pressure of vinyl tellurol at room temperature, a long optical path up to 136 m was necessary to record its spectrum. B3LYP density functional theory (DFT) calculations have been performed to assign the different absorption bands. Since an unambiguous assignment of the absorption bands requires a precise knowledge on the relative abundance of the syn and gauche rotamers of these compounds, their relative energies and their anharmonic vibrational frequencies were obtained using a very extended Def2-QZVP basis set. Two rotamers, the syn, which is planar, and a nonplanar gauche, were found to be local minima for both compounds. The gauche rotamer presents two degenerate conformers, which differ by the position of the SeH (TeH) hydrogen atom above or below the molecular plane. Our theoretical results are in good agreement with the main features of the experimental spectra. Fundamental bands and some combination bands of vinyl selenol and vinyl tellurol were assigned and compared with those of vinyl alcohol and vinyl thiol, whose spectra had been reported previously in the literature.

  5. Rapid anion exchange separation of fermium with mineral acid-methyl alcohol mixed media

    International Nuclear Information System (INIS)

    Usuda, S.; Shinohara, N.; Ichikawa, S.; Suzuki, T.

    1987-01-01

    Anion exchange separation of 250 Fm (30 m) synthesized by the 12 C+ 242 Pu and 16 O+ 238 U reactions was investigated with mineral acid-methyl alcohol mixed media at elevated temperature. Fermium was chromatographically separated from the other transplutonium elements, the target materials and an Al catcher foil by anion exchange with mixtures of nitric acid and methyl alcohol. By use of the mixed media of hydrochloric acid and methyl alcohol, Fm together with Cf was separated from Al, Am, Cm, Pu, U and from major fission products. The separation systems are suitable for rapid separation and immediate alpha-counting source preparation of Fm. (author) 22 refs.; 4 figs

  6. 40 CFR 116.4 - Designation of hazardous substances.

    Science.gov (United States)

    2010-07-01

    ... acetic acid, vinegar acid Acetic anhydride 108247 Acetic oxide, acetyl oxide Acetone cyanohydrin 75865 2... Allyl alcohol 107186 2-propen-1-ol, 1-propenol-3, vinyl carbinol Allyl chloride 107051 3-chloropropene..., mercaptomethane, methyl sulfhydrate, thiomethyl alcohol Methyl methacrylate 80626 Methacrylic acid methyl ester...

  7. Effects of secretagogues on ATP levels and protein carboxyl methylation in rat brain synaptosomes

    International Nuclear Information System (INIS)

    Bjorndahl, J.M.; Rutledge, C.O.

    1986-01-01

    The influence of various substances which are known to alter free intracellular calcium concentrations on protein carboxyl methyltransferase (PCM) activity was investigated in rat brain synaptosomes. The synaptosomes were labeled with L-[ 3 H]methionine and the 3 H-methyl esters of proteins were formed from the methyl donor S-[ 3 H]adenosyl-L-methionine ([ 3 H]AdoMet). The calcium ionophore A23187 and ouabain decreased PCM activity and the decrease produced by A23187 was antagonized by ethylene glycol bis(beta-aminoethyl ether)-N,N'-tetraacetic acid and MnCl 2 . On the other hand, ruthenium red, an inhibitor of calcium uptake, stimulated PCM activity. These data suggest that PCM activity is inversely related to the free cytoplasmic calcium concentration. Veratridine, A23187 and elevated potassium ions decreased the levels of ATP and [ 3 H]AdoMet. The A23187-mediated decrease in ATP levels and the reduced [ 3 H]AdoMet formation was antagonized by ethylene glycol bis(beta-aminoethyl ether)-N,N'-tetraacetic acid and MnCl 2 . Inhibition of metabolic activity of the synaptosomes by NaCN led to: decreased ATP levels; inhibition of [3H]AdoMet formation; and inhibition of PCM activity. These data suggest that the decrease in protein methylation produced by secretagogues is associated with an increase in the concentration of free intracellular calcium which results in a decrease in the metabolically active pool of ATP. This leads to a decreased rate of AdoMet formation, a cosubstrate for PCM and a resultant decrease in PCM activity

  8. Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly(arylene ether sulfone)s

    Science.gov (United States)

    Kwon, Sohyun; Rao, Anil H. N.; Kim, Tae-Hyun

    2018-01-01

    Azide-assisted terminal crosslinking of methyl morpholinium-functionalized poly(arylene ether sulfone) block copolymers yields products (xMM-PESs) suitable for use as anion exchange membranes. By combining the advantages of bulky morpholinium conductors and our unique polymer network crosslinked only at the termini of the polymer chains, we can produce AEMs that after the crosslinking show minimal loss in conductivity, yet with dramatically reduced water uptake. Terminal crosslinking also significantly increases the thermal, mechanical and chemical stability levels of the membranes. A high ion conductivity of 73.4 mS cm-1 and low water uptake of 26.1% at 80 °C are obtained for the crosslinked membrane with higher amount of hydrophilic composition, denoted as xMM-PES-1.5-1. In addition, the conductivity of the crosslinked xMM-PES-1.5-1 membrane exceeds that of its non-crosslinked counterpart (denoted as MM-PES-1.5-1) above 60 °C at 95% relative humidity because of its enhanced water retention capacity caused by the terminally-crosslinked structure.

  9. Effects on temperature and acidic pre-treatment on Fenton-driven oxidation of MTBE-spent granular activated carbon

    Science.gov (United States)

    Temperature-dependent mechanisms in the Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was investigated. Prior to iron (Fe) amendment to the GAC, acid-treatment altered the surface chemistry of the GAC and lowered the p...

  10. Artificial Neural Network Approach to Predict Biodiesel Production in Supercritical tert-Butyl Methyl Ether

    Directory of Open Access Journals (Sweden)

    Obie Farobie

    2016-05-01

    Full Text Available In this study, for the first time artificial neural network was used to predict biodiesel yield in supercritical tert-butyl methyl ether (MTBE. The experimental data of biodiesel yield conducted by varying four input factors (i.e. temperature, pressure, oil-to-MTBE molar ratio, and reaction time were used to elucidate artificial neural network model in order to predict biodiesel yield. The main goal of this study was to assess how accurately this artificial neural network model to predict biodiesel yield conducted under supercritical MTBE condition. The result shows that artificial neural network is a powerful tool for modeling and predicting biodiesel yield conducted under supercritical MTBE condition that was proven by a high value of coefficient of determination (R of 0.9969, 0.9899, and 0.9658 for training, validation, and testing, respectively. Using this approach, the highest biodiesel yield was determined of 0.93 mol/mol (corresponding to the actual biodiesel yield of 0.94 mol/mol that was achieved at 400 °C, under the reactor pressure of 10 MPa, oil-to-MTBE molar ratio of 1:40 within 15 min of reaction time.

  11. Biodegradation of Methyl tert-Butyl Ether by Co-Metabolism with a Pseudomonas sp. Strain

    Directory of Open Access Journals (Sweden)

    Shanshan Li

    2016-09-01

    Full Text Available Co-metabolic bioremediation is supposed to be an impressive and promising approach in the elimination technology of methyl tert-butyl ether (MTBE, which was found to be a common pollutant worldwide in the ground or underground water in recent years. In this paper, bacterial strain DZ13 (which can co-metabolically degrade MTBE was isolated and named as Pseudomonas sp. DZ13 based on the result of 16S rRNA gene sequencing analysis. Strain DZ13 could grow on n-alkanes (C5-C8, accompanied with the co-metabolic degradation of MTBE. Diverse n-alkanes with different carbon number showed a significant influence on the degradation rate of MTBE and accumulation of tert-butyl alcohol (TBA. When Pseudomonas sp. DZ13 co-metabolically degraded MTBE with n-pentane as the growth substrate, a higher MTBE-degrading rate (Vmax = 38.1 nmol/min/mgprotein, Ks = 6.8 mmol/L and lower TBA-accumulation was observed. In the continuous degradation experiment, the removal efficiency of MTBE by Pseudomonas sp. Strain DZ13 did not show an obvious decrease after five times of continuous addition.

  12. Molecular modeling of interactions in electronic nose sensors for environmental monitoring

    Science.gov (United States)

    Shevade, A. V.; Ryan, M. A.; Homer, M. L.; Manfreda, A. M.; Yen, S. -P. S.; Zhou, H.; Manatt, K.

    2002-01-01

    We report a study aimed at understanding analyte interactions with sensors made from polymer-carbon black composite films. The sensors are used in an Electronic Nose (ENose) which is used for monitoring the breathing air quality in human habitats. The model mimics the experimental conditions of the composite film deposition and formation and was developed using molecular modeling and simulation tools. The Dreiding 2.21 Force Field was used for the polymer and analyte molecules while graphite parameters were assigned to the carbon black atoms. The polymer considered for this work is methyl vinyl ether / maleic acid copolymer. The target analytes include both inorganic (NH3) and organic (methanol) types of compound. Results indicate different composite-analyte interaction behavior.

  13. Gas chromatography-vacuum ultraviolet spectroscopy for analysis of fatty acid methyl esters.

    Science.gov (United States)

    Fan, Hui; Smuts, Jonathan; Bai, Ling; Walsh, Phillip; Armstrong, Daniel W; Schug, Kevin A

    2016-03-01

    A new vacuum ultraviolet (VUV) detector for gas chromatography was recently developed and applied to fatty acid methyl ester (FAME) analysis. VUV detection features full spectral acquisition in a wavelength range of 115-240nm, where virtually all chemical species absorb. VUV absorption spectra of 37 FAMEs, including saturated, monounsaturated, and polyunsaturated types were recorded. Unsaturated FAMEs show significantly different gas phase absorption profiles than saturated ones, and these classes can be easily distinguished with the VUV detector. Another advantage includes differentiating cis/trans-isomeric FAMEs (e.g. oleic acid methyl ester and linoleic acid methyl ester isomers) and the ability to use VUV data analysis software for deconvolution of co-eluting signals. As a universal detector, VUV also provides high specificity, sensitivity, and a fast data acquisition rate, making it a powerful tool for fatty acid screening when combined with gas chromatography. The fatty acid profile of several food oil samples (olive, canola, vegetable, corn, sunflower and peanut oils) were analyzed in this study to demonstrate applicability to real world samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Rearrangements of Cycloalkenyl Aryl Ethers

    Directory of Open Access Journals (Sweden)

    Mercedesz Törincsi

    2016-04-01

    Full Text Available Rearrangement reactions of cycloalkenyl phenol and naphthyl ethers and the acid-catalyzed cyclization of the resulting product were investigated. Claisen rearrangement afforded 2-substituted phenol and naphthol derivatives. Combined Claisen and Cope rearrangement resulted in the formation of 4-substituted phenol and naphthol derivatives. In the case of cycloocthylphenyl ether the consecutive Claisen and Cope rearrangements were followed by an alkyl migration. The mechanism of this novel rearrangement reaction is also discussed.

  15. Modeling of the oxidation of methyl esters—Validation for methyl hexanoate, methyl heptanoate, and methyl decanoate in a jet-stirred reactor

    Science.gov (United States)

    Glaude, Pierre Alexandre; Herbinet, Olivier; Bax, Sarah; Biet, Joffrey; Warth, Valérie; Battin-Leclerc, Frédérique

    2013-01-01

    The modeling of the oxidation of methyl esters was investigated and the specific chemistry, which is due to the presence of the ester group in this class of molecules, is described. New reactions and rate parameters were defined and included in the software EXGAS for the automatic generation of kinetic mechanisms. Models generated with EXGAS were successfully validated against data from the literature (oxidation of methyl hexanoate and methyl heptanoate in a jet-stirred reactor) and a new set of experimental results for methyl decanoate. The oxidation of this last species was investigated in a jet-stirred reactor at temperatures from 500 to 1100 K, including the negative temperature coefficient region, under stoichiometric conditions, at a pressure of 1.06 bar and for a residence time of 1.5 s: more than 30 reaction products, including olefins, unsaturated esters, and cyclic ethers, were quantified and successfully simulated. Flow rate analysis showed that reactions pathways for the oxidation of methyl esters in the low-temperature range are similar to that of alkanes. PMID:23710076

  16. Modeling of the oxidation of methyl esters-Validation for methyl hexanoate, methyl heptanoate, and methyl decanoate in a jet-stirred reactor.

    Science.gov (United States)

    Glaude, Pierre Alexandre; Herbinet, Olivier; Bax, Sarah; Biet, Joffrey; Warth, Valérie; Battin-Leclerc, Frédérique

    2010-11-01

    The modeling of the oxidation of methyl esters was investigated and the specific chemistry, which is due to the presence of the ester group in this class of molecules, is described. New reactions and rate parameters were defined and included in the software EXGAS for the automatic generation of kinetic mechanisms. Models generated with EXGAS were successfully validated against data from the literature (oxidation of methyl hexanoate and methyl heptanoate in a jet-stirred reactor) and a new set of experimental results for methyl decanoate. The oxidation of this last species was investigated in a jet-stirred reactor at temperatures from 500 to 1100 K, including the negative temperature coefficient region, under stoichiometric conditions, at a pressure of 1.06 bar and for a residence time of 1.5 s: more than 30 reaction products, including olefins, unsaturated esters, and cyclic ethers, were quantified and successfully simulated. Flow rate analysis showed that reactions pathways for the oxidation of methyl esters in the low-temperature range are similar to that of alkanes.

  17. Novel fatty acid methyl esters from the actinomycete Micromonospora aurantiaca

    Science.gov (United States)

    Bruns, Hilke; Riclea, Ramona

    2011-01-01

    Summary The volatiles released by Micromonospora aurantiaca were collected by means of a closed-loop stripping apparatus (CLSA) and analysed by GC–MS. The headspace extracts contained more than 90 compounds from different classes. Fatty acid methyl esters (FAMEs) comprised the major compound class including saturated unbranched, monomethyl and dimethyl branched FAMEs in diverse structural variants: Unbranched, α-branched, γ-branched, (ω−1)-branched, (ω−2)-branched, α- and (ω−1)-branched, γ- and (ω−1)-branched, γ- and (ω−2)-branched, and γ- and (ω−3)-branched FAMEs. FAMEs of the last three types have not been described from natural sources before. The structures for all FAMEs have been suggested based on their mass spectra and on a retention index increment system and verified by the synthesis of key reference compounds. In addition, the structures of two FAMEs, methyl 4,8-dimethyldodecanoate and the ethyl-branched compound methyl 8-ethyl-4-methyldodecanoate were deduced from their mass spectra. Feeding experiments with isotopically labelled [2H10]leucine, [2H10]isoleucine, [2H8]valine, [2H5]sodium propionate, and [methyl-2H3]methionine demonstrated that the responsible fatty acid synthase (FAS) can use different branched and unbranched starter units and is able to incorporate methylmalonyl-CoA elongation units for internal methyl branches in various chain positions, while the methyl ester function is derived from S-adenosyl methionine (SAM). PMID:22238549

  18. Incineration of oxygenated volatile organic compounds. Experimental study and kinetic modeling of the oxidation of methyl ethyl ketone, ethyl acetate and butan-2-ol in methane flames; Incineration de composes organiques volatils oxygenes. Etude experimentale et modelisation cinetique de l'oxydation de la methyl ethyl cetone, de l'acetate d'ethyle et du butan-2-ol dans des flammes de methane

    Energy Technology Data Exchange (ETDEWEB)

    Decottignies, V.

    2000-12-01

    This work deals with the low pressure (0.05 atm) degradation of three volatile organic compounds (VOCs): methyl-ethyl-ketone, ethyl acetate and butan-2-ol, in premixed stoichiometric laminar methane flames seeded with 1 to 3% of each VOC. Molar fraction profiles of species have been obtained using microprobe sampling coupled with a gas chromatography and a mass spectroscopy analysis. Temperature profiles have been obtained using the covered thermocouple technique in the presence of the microprobe. The addition of a VOC in the initial reagents mixture leads to an increase of the quantity of intermediate hydrocarbon compounds and in particular of some soot precursor species. The degradation of VOCs leads to the formation of oxygenated intermediates like methanol, dimethyl-ether, acetaldehyde, propanal, acetone and vinyl acetate, the type of VOC having an effect on the quantities produced. The degradation of a VOC can lead to the formation of more toxic or polluting compounds (methyl vinyl ketone, acetic acid and acrolein) than the VOC itself. In the conditions of the study, the intermediate compounds are totally destructed inside the reactional area of the flame front and are no more present in the burnt gases. Sub-mechanisms of VOC oxidation have been developed using experimental observations and the most recent recommendations of the literature. These sub-mechanisms comprise 49 species involved in 241 elementary reactions. Their validation has been performed by comparing the experiment with the kinetic modeling on the molar fraction profiles of the detected species. Experimental data are well reproduced by the model for most species. The addition of a VOC inside the initial reagents mixture creates an important reactivity increase, in particular in the case of butan-2-ol seeded flames. The analysis of reactional ways has permitted to draw out the main reactions responsible for the degradation of the 3 VOCs and the ways of formation and consumption of the

  19. He-Ne laser protection barrier by means of poly (Tetrafluoroethylene-Perfluoro vinyl Ether) grafted by acrylic acid complexed with Cu(II)

    International Nuclear Information System (INIS)

    El-Ahdal, M.A.; Fayek, S.A.; El-Sawy, N.M.

    2006-01-01

    Appropriate eye and skin protection is a prerequisite for the safe operation of He-Ne laser in industrial and laboratory environments. In the present paper, measurement of the optical parameters of poly (tetrafluoroethylene-perfluorovinyl ether) grafted by acrylic acid and complexed with Cu(II) are reported. He-Ne laser beam radiation on wavelength of 632.8 nm and power 12.5mW was used. Transmittance and reflectance spectra and refractive index dispersion are presented. The study showed that the material has a protective level 4. Environmental conditions like thermal and fading processes were tested. This suggested that the material preserves its protective features as a protective eye and skin barriers of protective level 4. This was applied for occupational working time up to 8 h, temperature up to 50 degree C and for a time equal 74 days after laser irradiation. Radiation protection from laser sources has attracted a great deal of attention for long time because of their importance for human body. Intensive progress in lasers, optical communications, and data storage has challenged scientists to achieve perfection in optical components. These challenges have resulted in an active development of a wide variety of unconventional optical elements (Hariharan, 1996 and Efimov et al., 2002). Alexandrite solid state lasers with a wavelength of about 755 nm are frequently used in the field of medicine (Schirmarcher and Sutter, 2001). For removing tattoos, the Q-switched versions with impulse widths of several ten nanoseconds are an ideal instrument to keep the thermal stress of the patient's skin at low level. He-Ne laser is one of the most commonly used visible light lasers

  20. Effects of Temperature and Acidic Pre-Treatment on Fenton-Driven Oxidation of MTBE-Spent Granular Activated Carbon

    Science.gov (United States)

    Temperature-dependent mechanisms in the Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was investigated. Prior to iron (Fe) amendment to the GAC, acid-treatment altered the surface chemistry of the GAC and lowered the pH ...

  1. Solubility of nicotinic acid in water, ethanol, acetone, diethyl ether, acetonitrile, and dimethyl sulfoxide

    International Nuclear Information System (INIS)

    Gonçalves, Elsa M.; Minas da Piedade, Manuel E.

    2012-01-01

    Highlights: ► We determined the solubility of nicotinic acid in six solvents by the gravimetric method. ► We found that, regardless of the solvent, the same monoclinic solid phase was in equilibrium with the solution. ► We determined the activity coefficients of nicotinic acid in the six solvents. ► We found that the solubility trends seem to be determined by the polarity and polarizability of the solvent. - Abstract: The mole fraction equilibrium solubility of nicotinic acid in six solvents (water, ethanol, dimethyl sulfoxide, acetone, acetonitrile and diethyl ether) differing in polarity, polarizability, and hydrogen-bonding ability, was determined over the temperature range (283 to 333) K, using the gravimetric method. The results obtained led to the solubility order dimethyl sulfoxide (DMSO) ≫ ethanol > water > acetone > diethyl ether > acetonitrile. An analysis based on various solvent descriptors, indicated that this trend seems to be mainly determined by the polarity and polarizability of the solvent. The activity coefficients of nicotinic acid in the different solvents, under saturation conditions, were determined as a function of the temperature and it was found that DMSO exhibits enhanced solubility relative to an ideal solution while the opposite is observed for all other solvents. Both the solvent and the fact that nicotinic acid is primarily zwitterionic in aqueous solution and non-zwitterionic in non-aqueous media, did not affect the nature of the solid phases in equilibrium with the different solutions. Indeed, X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and differential scanning calorimetry analysis indicated that, despite some differences in particle size and morphology, the starting material and the solid products obtained at the end of the solubility studies in the six solvents used in this work were all crystalline and corresponded to the same monoclinic phase.

  2. Molecular structure impacts on secondary organic aerosol formation from glycol ethers

    Science.gov (United States)

    Li, Lijie; Cocker, David R.

    2018-05-01

    Glycol ethers, a class of widely used solvents in consumer products, are often considered exempt as volatile organic compounds based on their vapor pressure or boiling points by regulatory agencies. However, recent studies found that glycol ethers volatilize at ambient conditions nearly as rapidly as the traditional high-volatility solvents indicating the potential of glycol ethers to form secondary organic aerosol (SOA). This is the first work on SOA formation from glycol ethers. The impact of molecular structure, specifically -OH, on SOA formation from glycol ethers and related ethers are investigated in the work. Ethers with and without -OH, with methyl group hindrance on -OH and with -OH at different location are studied in the presence of NOX and under "NOX free" conditions. Photooxidation experiments under different oxidation conditions confirm that the processing of ethers is a combination of carbonyl formation, cyclization and fragmentation. Bulk SOA chemical composition analysis and oxidation products identified in both gas and particle phase suggests that the presence and location of -OH in the carbon bond of ethers determine the occurrence of cyclization mechanism during ether oxidation. The cyclization is proposed as a critical SOA formation mechanism to prevent the formation of volatile compounds from fragmentation during the oxidation of ethers. Glycol ethers with -CH2-O-CH2CH2OH structure is found to readily form cyclization products, especially with the presence of NOx, which is more relevant to urban atmospheric conditions than without NOx. Glycol ethers are evaluated as dominating SOA precursors among all ethers studied. It is estimated that the contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources. The contribution of glycol ethers to anthropogenic SOA is roughly 1% of the current organic aerosol from mobile sources and will play a more important role in future anthropogenic SOA

  3. Stable carbon and hydrogen isotope analysis of methyl tert-butyl ether and tert-amyl methyl ether by purge and trap-gas chromatography-isotope ratio mass spectrometry: method evaluation and application.

    Science.gov (United States)

    Kujawinski, Dorothea M; Stephan, Manuel; Jochmann, Maik A; Krajenke, Karen; Haas, Joe; Schmidt, Torsten C

    2010-01-01

    In order to monitor the behaviour of contaminants in the aqueous environment effective enrichment techniques often have to be employed due to their low concentrations. In this work a robust and sensitive purge and trap-gas chromatography-isotope ratio mass spectrometry method for carbon and hydrogen isotope analysis of fuel oxygenates in water is presented. The method evaluation included the determination of method detection limits, accuracy and reproducibility of deltaD and delta(13)C values. Lowest concentrations at which reliable delta(13)C values could be determined were 5 microg L(-1) and 28 microg L(-1) for TAME and MTBE, respectively. Stable deltaD values for MTBE and TAME could be achieved for concentrations as low as 25 and 50 microg L(-1). Good long-term reproducibility of delta(13)C and deltaD values was obtained for all target compounds. But deltaD values varying more than 5 per thousand were observed using different thermal conversion tubes. Thus, a correction of deltaD values in the analysis of groundwater samples was necessary to guarantee comparability of the results. The applicability of this method was shown by the analysis of groundwater samples from a gasoline contaminated site. By two dimensional isotope analysis two locations within this site were identified at which anaerobic and aerobic degradation of methyl tert-butyl ether occurred.

  4. 6-Methyl-1,2,4-benzenetriol, a new intermediate in penicillic acid biosynthesis in Penicillium cyclopium

    International Nuclear Information System (INIS)

    Sekiguchi, J.; Katayama, S.; Yamada, Y.

    1987-01-01

    Penicillic acid-negative mutants were obtained from a color mutant derived from Penicillium cyclopium NRRL 1888 through N-methyl-N'-nitro-N-nitrosoguanidine treatment. One mutant (SK2N6) accumulated 6-methyl-1,2,4-benzenetriol, which was not previously known to be a metabolite of P. cyclopium, in addition to orsellinic acid and orcinol. The radioactivity of [1- 14 C]acetic acid was rapidly incorporated into 6-methyl-1,2,4-benzenetriol in a culture of P. cyclopium SK2N6. Moreover, the radioactivity of [ 14 C]6-methyl-1,2,4-benzenetriol was efficiently incorporated into penicillic acid in a culture of P. cyclopium NRRL 1888. These data indicate that 6-methyl-1,2,4-benzenetriol is a precursor for penicillic acid biosynthesis. The results on the addition of 1,4-dihydroxy-6-methoxy-2-methylbenzene, 6-methoxy-2-methylbenzoquinone (1,4), and 1-O-methylorcinol to a culture of P. cyclopium SK2N6 indicated that only the former two compounds are converted to penicillic acid. Thus, a new portion of the penicillic acid biosynthetic pathway is proposed

  5. Temperature-Induced Desorption of Methyl tert-Butyl Ether Confined on ZSM-5: An In Situ Synchrotron XRD Powder Diffraction Study

    Directory of Open Access Journals (Sweden)

    Elisa Rodeghero

    2017-02-01

    Full Text Available The temperature-induced desorption of methyl tert-butyl ether (MTBE from aqueous solutions onto hydrophobic ZSM-5 was studied by in situ synchrotron powder diffraction and chromatographic techniques. This kind of information is crucial for designing and optimizing the regeneration treatment of such zeolite. The evolution of the structural features monitored by full profile Rietveld refinements revealed that a monoclinic (P21/n to orthorhombic (Pnma phase transition occurred at about 100 °C. The MTBE desorption process caused a remarkable change in the unit-cell parameters. Complete MTBE desorption was achieved upon heating at about 250 °C. Rietveld analysis demonstrated that the desorption process occurred without any significant zeolite crystallinity loss, but with slight deformations in the channel apertures.

  6. Vinyl Record

    DEFF Research Database (Denmark)

    Bartmanski, Dominik; Woodward, Ian

    2018-01-01

    . This relational process means that both the material affordances and entanglements of vinyl allow us to feel, handle, experience, project, and share its iconicity. The materially mediated meanings of vinyl enabled it to retain currency in independent and collector’s markets and thus resist the planned......In this paper, we use the case of the vinyl record to show that iconic objects become meaningful via a dual process. First, they offer immersive engagements which structure user interpretations through various material experiences of handling, use, and extension. Second, they always work via...

  7. Characterization of Functionalized Acrylic acid /4- Vinyl Pyridine Graft Copolymers

    International Nuclear Information System (INIS)

    Kamal, H.; Mahmoud, Gh.A.; Hegazy, D.E.

    2009-01-01

    Properties and characterization of the membranes prepared by radiation grafting of acrylic acid (AAc) or/ and 4-vinyl pyridine (4VP) onto low density polyethylene (LDPE) and polypropylene (PP) films were carried out. The FTIR spectra for the grafted membranes were studied to evaluate the structure change as a result of grafting. The swelling behaviour of the graft copolymer in methanol was studied. It was found that the grafting of AAc and/ or 4- VP onto LDPE and PP resulted in introducing good hydrophilic properties to such polymer substrates. The hydrophilic properties were directly proportional to the amount of functional groups. The mechanical properties (Young's modulus, elongation percent and tensile strength) of the grafted membranes also, have been investigated. As the grafting degree increases, the modulus also increases. Increasing the hydrophilicity of the membranes by chemical treatment enhances its mechanical properties. The thermal parameters of the grafted membranes such as δH m1 . δH m2 , and T rc have been also studied by using DSC

  8. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Norton, C.J.; Falk, D.O.

    1973-12-18

    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  9. Chemically imaging the effects of the addition of nanofibrillated cellulose on the distribution of poly(acrylic acid) in poly(vinyl alcohol)

    Science.gov (United States)

    Craig Clemons; Julia Sedlmair; Barbara Illman; Rebecca Ibach; Carol Hirschmugl

    2013-01-01

    The distribution of poly(acrylic acid) (PAA) in model laminates of nanocellulose and poly(vinyl alcohol) (PVOH) was investigated by FTIR chemical imaging. The method was effective in spatially discerning the three components of the composite. PAA can potentially improve the performance of nanocellulose reinforced PVOH by not only crosslinking the PVOH matrix but also...

  10. Properties and synthesis of D2EHPA and of alkylphosphoric acid

    International Nuclear Information System (INIS)

    Elias, Abdelhamid

    1996-07-01

    A great interest has been devoted to alkylphosphates which are used in various field of chemical industry as: agents for extracting metals (uranium, actinides and lanthanides), flame-retardant solid plasticizers for cellulose acetate,cellulose ethers and vinyls,ignition control agents for gasoline, lubricant additive,antifoam agents for water-based paints and in inks and paper manufacture. In this context, the present work is achieved in order to supply a selected bibliography and the main theoretical aspects concerning physical and chemical properties, analysis techniques, synthesis and purification processes and some applications of D2EHPA (di(2-ethylhexyl)phosphoric acid or di(2-ethylhexyl)phosphate) and of alkylphosphates in general

  11. Flavonoids and triterpenes from the nest of the stingless bee Trigona spinipes

    International Nuclear Information System (INIS)

    Freitas, Marinalva O.; Ponte, Flavio A.F.; Lima, Mary Anne S.; Silveira, Edilberto R.

    2008-01-01

    In the Northeast of Brazil the stingless bee Trigona spinipes Fabricius injures the tree bark of cultivated Eucalyptus citriodora specimens in order to make them exudate. The chemical investigation of the ethanol extract of an entire nest of T. spinipes allowed the isolation of the cycloartane triterpene magniferolic acid and 3β-hydroxy-24-methylenecicloartan-26-oic acid, besides the flavonoids 3'-methyl quercetin, sakuranetin, kaempferol 7-methyl ether, tricetin and aromadendrin 7-methyl ether as the main compounds. The isolation of sakuranetin, kaempferol 7-methyl ether, and aromadendrin 7-methyl ether from both Trigonas spinipes' nest and the exudate from Eucalyptus, may suggest this species as a botanical origin of the nest constituents of these stingless bee in the Northeast of Brazil. The structural characterization of the isolated compounds was accomplished by spectrometric means and comparison with the literature data. (author)

  12. 21 CFR 181.30 - Substances used in the manufacture of paper and paperboard products used in food packaging.

    Science.gov (United States)

    2010-04-01

    ... cyanodithioimidocarbamate with ethylene diamine and potassium N-methyl dithiocarbamate and/or sodium 2-mercaptobenzothiazole (slimicides).* Ethyl acrylate and methyl methacrylate copolymers of itaconic acid or methacrylic acid for use... acid (polymerized). Melamine formaldehyde polymer. Methyl acrylate (polymerized). Methyl ethers of mono...

  13. The fatty acid composition of a Vibrio alginolyticus associated with the alga Cladophora coelothrix. Identification of the novel 9-methyl-10-hexadecenoic acid.

    Science.gov (United States)

    Carballeira, N M; Sostre, A; Stefanov, K; Popov, S; Kujumgiev, A; Dimitrova-Konaklieva, S; Tosteson, C G; Tosteson, T R

    1997-12-01

    The fatty acid composition of a new strain of Vibrio alginolyticus, found in the alga Cladophora coelothrix, was studied. Among 38 different fatty acids, a new fatty acid, 9-methyl-10-hexadecenoic acid and the unusual 11-methyl-12-octadecenoic acid, were identified. Linear alkylbenzene fatty acids, such as 10-phenyldecanoic acid, 12-phenyldodecanoic acid and 14-phenyltetradecanoic acid, were also found in V. alginolyticus. The alga contained 43% saturated fatty acids, and 28% C16-C20 polyunsaturated fatty acids of the n-3 and n-6 families.

  14. In situ polymerization of vinyl monomers in polyester yarns

    International Nuclear Information System (INIS)

    Avny, Y.; Rebenfeld, L.; Weigmann, H.D.

    1978-01-01

    The effects of a pretreatment of polyester (PET) yarns with a strongly interacting solvent such as dimethylformamide (DMF) on vinyl monomer incorporation were investigated. When the DMF pretreatment is carried out at high temperatures (above 120 0 C), the swollen PET structure is stabilized by solvent-induced secondary crystallization. This substrate is highly suitable for the incorporation of vinyl monomers. In situ polymerization of vinyl monomers in DMF-treated PET was investigated using chemical and γ-irradiation polymerization techniques, both in the presence and in the absence of excess monomer outside the PET fibers. When polymerization was carried out in a system in which a constant supply of free radicals was available from the outside of the PET fibers, lower initiator concentrations and smaller γ-irradiation doses were necessary. These results are attributed to a low efficiency of the initiator inside the PET fiber due to mobility restrictions. Water uptake and moisture regain of PET yarns containing poly(hydroxyethyl methacrylate) and poly(acrylic acid) were also investigated. When most of the vinyl polymer was inside the PET fiber, water absorption was limited. The changes in mechanical properties of the PET yarns resulting from the DMF pretreatment were partially reversed by in situ polymerization of vinyl monomers

  15. The rapid detection of methyl tert-butyl ether (MtBE) in water using a prototype gas sensor system.

    Science.gov (United States)

    de Lacy Costello, B P J; Sivanand, P S; Ratcliffe, N M; Reynolds, D M

    2005-01-01

    The gasoline additive Methyl-tertiary-Butyl Ether (MtBE) is the second most common contaminant of groundwater in the USA and represents an important soil contaminant. This compound has been detected in the groundwater in at least 27 states as a result of leaking underground storage facilities (gasoline storage tanks and pipelines). Since the health effects of MtBE are unclear the potential threat to drinking water supplies is serious. Therefore, the ability to detect MtBE at low levels (ppb) and on-line at high-risk groundwater sites would be highly desirable. This paper reports the use of 'commercial' and metal oxide sensor arrays for the detection of MtBE in drinking and surface waters at low ppb level (microg.L(-1) range). The output responses from some of the sensors were found to correlate well with MtBE concentrations under laboratory conditions.

  16. Synthesis of 1-Methyl-3-oxo-7-oxabicyclo[2.2.1]hept-5-ene-2-carboxylic Acid Methyl Ester

    Directory of Open Access Journals (Sweden)

    Gil Valdo José da Silva

    2005-11-01

    Full Text Available A simple and efficient method for the preparation of 1-methyl-3-oxo-7- oxabicyclo[2.2.1]hept-5-en-2-carboxylic acid methyl ester (1 is described. The first step is a highly regioselective Diels-Alder reaction between 2-methylfuran and methyl-3-bromo- propiolate. A remarkably difficult ketal hydrolysis reaction was effected by treatment with HCl, a simple reagent that was shown to be more efficient, in this case, than commonly used more elaborate methods.

  17. Concentration determination of methyl magnesium chloride and other Grignard reagents by potentiometric titration with in-line characterization of reaction species by FTIR spectroscopy.

    Science.gov (United States)

    Chen, Yadan; Wang, Tao; Helmy, Roy; Zhou, George X; LoBrutto, Rosario

    2002-07-01

    A potentiometric titration method for methyl magnesium chloride and other Grignard reagents based on the reaction with 2-butanol in THF has been developed and validated. The method employs a commercially available platinum electrode, using an electrolyte compatible with non-aqueous solvents. Well-defined titration curves were obtained, along with excellent method precision. The endpoint was precisely determined based on the first derivative of the titration curve. Different solvents such as THF, diethyl ether and methylene chloride provided similar results with regard to sharpness of the endpoint and method precision. The method was applied to a wide array of Grignard reagents including methyl magnesium bromide, ethyl magnesium chloride, propyl magnesium chloride, vinyl magnesium chloride, phenyl magnesium chloride, and benzyl magnesium chloride with similar precision and accuracy. Application of in-line FTIR was demonstrated for in situ monitoring of the titration reaction, allowing characterization of the reaction species. An authentic spectrum of the MeMgCl-THF complex was obtained using spectral subtraction and the vibrational absorbance bands were identified. FTIR also provided an alternative for detecting the titration endpoint, and the titration results so obtained, provided a cross-validation of the accuracy of the potentiometric titration.

  18. γ-aminobutyric acidA (GABAA) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of Methyl Tert-Butyl Ether (MTBE)-induced impairment of spatial memory

    International Nuclear Information System (INIS)

    Zheng Gang; Zhang Wenbin; Zhang Yun; Chen Yaoming; Liu Mingchao; Yao Ting; Yang Yanxia; Zhao Fang; Li Jingxia; Huang Chuanshu; Luo Wenjing; Chen Jingyuan

    2009-01-01

    Experimental and occupational exposure to Methyl Tert-Butyl Ether (MTBE) has been reported to induce neurotoxicological and neurobehavioral effects, such as headache, nausea, dizziness, and disorientation, etc. However, the molecular mechanisms involved in MTBE-induced neurotoxicity are still not well understood. In the present study, we investigated the effects of MTBE on spatial memory and the expression and function of GABA A receptor in the hippocampus. Our results demonstrated that intraventricular injection of MTBE impaired the performance of the rats in a Morris water maze task, and significantly increased the expression of GABA A receptor α1 subunit in the hippocampus. The phosphorylation of ERK1/2 decreased after the MTBE injection. Furthermore, the decreased ability of learning and the reduction of phosphorylated ERK1/2 level of the MTBE-treated rats was partly reversed by bicuculline injected 30 min before the training. These results suggested that MTBE exposure could result in impaired spatial memory. GABA A receptor may play an important role in the MTBE-induced impairment of learning and memory by regulating the phosphorylation of ERK in the hippocampus.

  19. meta-PBI/methylated PBI-OO blend membranes for acid doped HT PEMFC

    DEFF Research Database (Denmark)

    Cho, Hyeongrae; Hur, Eun; Henkensmeier, Dirk

    2014-01-01

    Methylation of polybenzimidazole leads to positively charged polymer backbones, and moveable anions. Ion exchange of methylated PBI-OO in phosphoric acid (PA) shows that the resulting polymers dissolve. meta-PBI, however, absorbs about 400wt% PA while remaining a self supported membrane. We inves...

  20. Protective effects of folic acid on DNA damage and DNA methylation levels induced by N-methyl- N'-nitro- N-nitrosoguanidine in Kazakh esophageal epithelial cells.

    Science.gov (United States)

    Chen, Y; Feng, H; Chen, D; Abuduwaili, K; Li, X; Zhang, H

    2018-01-01

    The protective effects of folic acid on DNA damage and DNA methylation induced by N-methyl- N'-nitro- N-nitrosoguanidine (MNNG) in Kazakh esophageal epithelial cells were investigated using a 3 × 3 factorial design trial. The cells were cultured in vitro and exposed to media containing different concentrations of folic acid and MNNG, after which growth indices were detected. DNA damage levels were measured using comet assays, and genome-wide DNA methylation levels (MLs) were measured using high-performance liquid chromatography. The DNA methylation of methylenetetrahydrofolate reductase (MTHFR) and folate receptor- α (FR α) genes was detected by bisulfite sequencing polymerase chain reaction (PCR). The results showed significant increases in tail DNA concentration, tail length, and Olive tail moment ( p methylation frequencies of MTHFR and FR α genes. In particular, significant differences were observed in the promoter regions of both genes ( p methylation in Kazakh esophageal epithelial cells upon MNNG exposure. Thus, sufficient folic acid levels could play a protective role against the damage induced by this compound.

  1. Fatty acid and sterol contents during tulip leaf senescence induced by methyl jasmonate

    Directory of Open Access Journals (Sweden)

    Marian Saniewski

    2013-12-01

    Full Text Available It has been shown previously that methyl jasmonate (JA-Me applied in lanolin paste on the bottom surface of intact tulip leaves causes a rapid and intense its senescence. The aim of this work was to study the effect of JA-Me on free and bound fatty acid and sterol contents during tulip leaf senescence. The main free and bound fatty acids of tulip leaf, in decreasing order of their abundance, were linolenic, linoleic, palmitic, oleic, stearic and myristic acids. Only the content of free linolenic acid decreased after treatment with JA-Me during visible stage of senescence. ß-Sitosterol (highest concentration, campesterol, stigmasterol and cholesterol were identified in tulip leaf. Methyl jasmonate evidently increased the level of ß-sitosterol, campesterol and stigmasterol during induced senescence. It is suggested that the increase in sterol concentrations under the influence of methyl jasmonate induced changes in membrane fluidity and permeability, which may be responsible for senescence.

  2. Methyl vinyl ketone, a toxic ingredient in cigarette smoke extract, modifies glutathione in mouse melanoma cells.

    Science.gov (United States)

    Horiyama, Shizuyo; Takahashi, Yuta; Hatai, Mayuko; Honda, Chie; Suwa, Kiyoko; Ichikawa, Atsushi; Yoshikawa, Noriko; Nakamura, Kazuki; Kunitomo, Masaru; Date, Sachiko; Masujima, Tsutomu; Takayama, Mitsuo

    2014-01-01

    Cigarette smoke contains many harmful chemicals, which contribute to the pathogenesis of smoking-related diseases such as chronic obstructive pulmonary disease, cancer and cardiovascular disease. The cytotoxicity of cigarette smoke is well documented, but the definitive mechanism behind its toxicity remains unknown. Ingredients in cigarette smoke are known to deplete intracellular glutathione (GSH), the most abundant cellular thiol antioxidant, and to cause oxidative stress. In the present study, we investigated the mechanism of cigarette smoke extract (CSE)-induced cytotoxicity in B16-BL6 mouse melanoma (B16-BL6) cells using liquid chromatography-tandem mass spectrometry. CSE and ingredients in cigarette smoke, methyl vinyl ketone (MVK) and crotonaldehyde (CA), reduced cell viability in a concentration-dependent manner. Also, CSE and the ingredients (m/z 70, each) irreversibly reacted with GSH (m/z 308) to form GSH adducts (m/z 378) in cells and considerably decreased cellular GSH levels at concentrations that do not cause cell death. Mass spectral data showed that the major product formed in cells exposed to CSE was the GSH-MVK adduct via Michael-addition and was not the GSH-CA adduct. These results indicate that MVK included in CSE reacts with GSH in cells to form the GSH-MVK adduct, and thus a possible reason for CSE-induced cytotoxicity is a decrease in intracellular GSH levels.

  3. Poly(vinyl acetate-Based Block Copolymer/Clay Nanocomposites Prepared by In Situ Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    M.A. Semsarzadeh

    2009-12-01

    Full Text Available Atom transfer radical polymerization of styrene (St and methyl methacrylate (MMA was performed at 90oC in the absence and presence of nanoclay (Cloisite 30B. Trichloromethyl-terminated poly(vinyl acetate telomerand CuCl/ PMDETA were used as a macroinitiator and catalyst system, respectively. The experimental results showed that the atom transfer radical polymerization of St and MMA in the absence or presence of nanoclay proceeds via a controlled/living mode. It was observed that nanoclay significantly enhances the homopolymerization rate of MMA, which was attributed to the activated conjugated C=C bond of MMA monomer via interaction between the carbonyl group of MMA monomer and the hydroxyl moiety (Al-O-H of nanoclay as well as the effect of nanoclay on the dynamic equilibrium between the active (macro radicals and dormant species.Homopolymerization rate of St (a non-coordinative monomer with nanoclay decreased slightly in the presence of nanoclay. This could be explained by insertion of a portion of macroinitiator into the clay galleries, where no sufficient St monomer exists due to the low compatibility or interaction of St monomer with nanoclay to react with the macroinitiator. The results obtained from XRD, TEM and TGA analyses were fully in agreement with the kinetic data. Structure of the poly(vinyl acetate-bpolystyrene nanocomposite was found to be a combination of stacking layers and exfoliated structures while poly(vinyl acetate-b-poly(methyl methacryale nanocomposite had an exfoliated structure. This difference in the structure of nanocomposites was attributed to the different capability of the monomers (styrene and methyl methacrylate to react with the hydroxyl moiety (Al-O-H of nanoclay.

  4. Gasoline ether oxygenate occurrence in Europe, and a review of their fate and transport characteristics in the environment

    Energy Technology Data Exchange (ETDEWEB)

    Stupp, D.; Gass, M.; Leiteritz, H. [Dr. Stupp Consulting DSC, Tauw, Bergisch Gladbach (Germany); Pijls, C. [TAUW, Apeldoorn (Netherlands); Thornton, S. [University of Sheffield, Sheffield (United Kingdom); Smith, J.; Dunk, M.; Grosjean, T.; Den Haan, K. [CONCAWE, Brussels (Belgium)

    2012-06-15

    Ether oxygenates are added to certain gasoline (petrol) formulations to improve combustion efficiency and to increase the octane rating. In this report the term gasoline ether oxygenates (GEO) refers collectively to methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), diisopropyl ether (DIPE), tertiary amyl ethyl ether (TAEE), tertiary hexyl methyl ether (THxME), and tertiary hexyl ethyl ether (THxEE), as well as the associated tertiary butyl alcohol (TBA). This report presents newly collated data on the production capacities and use of MTBE, ETBE, TAME, DIPE and TBA in 30 countries (27 EU countries and Croatia, Norway and Switzerland) to inform continued and effective environmental management practices for GEO by CONCAWE members. The report comprises data on gasoline use in Europe that were provided by CONCAWE and obtained from the European Commission. Furthermore Societe Generale de Surveillance (SGS) provided detailed analytical data (more than 1,200 sampling campaigns) on the GEO composition of gasoline in European countries in the period 2000-2010. Another major aspect of this report is the investigation of GEO distribution in groundwater, drinking water, surface water, runoff water, precipitation (rain/snow) and air in the European environment. Apart from the general sources of literature for the study, local environmental authorities and institutes in the 30 European countries have been contacted for additional information. Finally, a review of the international literature on GEO natural attenuation processes was undertaken with a focus on international reports and peer-reviewed scientific publications to give an overview on the known fate, transport and degradation mechanisms of GEO in the subsurface, to inform risk-management strategies that may rely on natural attenuation processes. The literature reveals that all GEO compounds used in fuels are highly water soluble and weakly retarded by aquifer

  5. The antimicrobial efficacy and structure activity relationship of novel carbohydrate fatty acid derivatives against Listeria spp. and food spoilage microorganisms.

    Science.gov (United States)

    Nobmann, Patricia; Smith, Aoife; Dunne, Julie; Henehan, Gary; Bourke, Paula

    2009-01-15

    Novel mono-substituted carbohydrate fatty acid (CFA) esters and ethers were investigated for their antibacterial activity against a range of pathogenic and spoilage bacteria focussing on Listeria monocytogenes. Carbohydrate derivatives with structural differences enable comparative studies on the structure/activity relationship for antimicrobial efficacy and mechanism of action. The antimicrobial efficacy of the synthesized compounds was compared with commercially available compounds such as monolaurin and monocaprylin, as well as the pure free fatty acids, lauric acid and caprylic acid, which have proven antimicrobial activity. Compound efficacy was compared using an absorbance based broth microdilution assay to determine the minimum inhibitory concentration (MIC), increase in lag phase and decrease in maximum growth rate. Among the carbohydrate derivatives synthesized, lauric ether of methyl alpha-d-glucopyranoside and lauric ester of methyl alpha-d-mannopyranoside showed the highest growth-inhibitory effect with MIC values of 0.04 mM, comparable to monolaurin. CFA derivatives were generally more active against Gram positive bacteria than Gram negative bacteria. The analysis of both ester and ether fatty acid derivatives of the same carbohydrate, in tandem with alpha and beta configuration of the carbohydrate moiety suggest that the carbohydrate moiety is involved in the antimicrobial activity of the fatty acid derivatives and that the nature of the bond also has a significant effect on efficacy, which requires further investigation. This class of CFA derivatives has great potential for developing antibacterial agents relevant to the food industry, particularly for control of Listeria or other Gram-positive pathogens.

  6. Preparation of unsaturated acrylic prepolymer and electron beam curing of its mixture with vinyl monomers

    International Nuclear Information System (INIS)

    Pyun, H.C.; Park, W.B.; Kim, K.Y.; Sung, K.Y.

    1980-01-01

    Electron beam curable prepolymers were prepared by the addition reaction of methyl methacrylate-glycidyl methacrylate copolymer with methacrylic acid, and electron beam curing was studied for the prepolymer and their mixtures of several kind of vinyl monomers. When the reaction was carried out in the presence of triethylbenzyl ammonium chloride in N,N-dimethyl formamide solution, the rate of addition reaction obeyed first-order kinetics. In the electron beam curing, the rate of gel formation of the prepolymer was slower than that of the mixtures of prepolymer and monomers. In the curing of mixtures of prepolymer with polyethyleneglycol dimethacrylates, the rate of gel formation increased with the increase in the degree of polymerization of polyethylene oxide fraction of polyethyleneglycol dimethacrylate, and decreased with the increase the polyethyleneglycol dimethacrylate content. The properties of cured coatings were also examined. (author)

  7. Nickel-Catalyzed Alkoxy-Alkyl Interconversion with Alkylborane Reagents through C−O Bond Activation of Aryl and Enol Ethers

    KAUST Repository

    Guo, Lin

    2016-11-07

    A nickel-catalyzed alkylation of polycyclic aromatic methyl ethers as well as methyl enol ethers with B-alkyl 9-BBN and trialkylborane reagents that involves the cleavage of stable C(sp2)−OMe bonds is described. The transformation has a wide substrate scope and good chemoselectivity profile while proceeding under mild reaction conditions; it provides a versatile way to form C(sp2)−C(sp3) bonds that does not suffer from β-hydride elimination. Furthermore, a selective and sequential alkylation process by cleavage of inert C−O bonds is presented to demonstrate the advantage of this method.

  8. Colloidal titration of aqueous zirconium solutions with poly(vinyl sulfate) by potentiometric endpoint detection using a toluidine blue selective electrode.

    Science.gov (United States)

    Sakurada, Osamu; Kato, Yasutake; Kito, Noriyoshi; Kameyama, Keiichi; Hattori, Toshiaki; Hashiba, Minoru

    2004-02-01

    Zirconium oxy-salts were hydrolyzed to form positively charged polymer or cluster species in acidic solutions. The zirconium hydrolyzed polymer was found to react with a negatively charged polyelectrolyte, such as poly(vinyl sulfate), and to form a stoichiometric polyion complex. Thus, colloidal titration with poly(vinyl sulfate) was applied to measure the zirconium concentration in an acidic solution by using a Toluidine Blue selective plasticized poly(vinyl chloride) membrane electrode as a potentiometric end-point detecting device. The determination could be performed with 1% of the relative standard deviation. The colloidal titration stoichiometry at pH < or = 2 was one mol of zirconium per equivalent mol of poly(vinyl sulfate).

  9. Temperature-Dependent Alkyl Glycerol Ether Lipid Composition of Mesophilic and Thermophilic Sulfate-Reducing Bacteria

    Directory of Open Access Journals (Sweden)

    Arnauld Vinçon-Laugier

    2017-08-01

    Full Text Available The occurrence of non-isoprenoid alkyl glycerol ether lipids in Bacteria and natural environments is increasingly being reported and the specificity and diagenetic stability of these lipids make them powerful biomarkers for biogeochemical and environmental studies. Yet the environmental controls on the biosynthesis of these peculiar membrane lipids remain poorly documented. Here, the lipid content of two mesophilic (Desulfatibacillum aliphaticivorans and Desulfatibacillum alkenivorans and one thermophilic (Thermodesulfobacterium commune sulfate-reducing bacteria—whose membranes are mostly composed of ether lipids—was investigated as a function of growth temperature (20–40°C and 54–84°C, respectively. For all strains, the cellular lipid content was lower at sub- or supra-optimal growth temperature, but the relative proportions of dialkyl glycerols, monoalkyl glycerols and fatty acids remained remarkably stable whatever the growth temperature. Rather than changing the proportions of the different lipid classes, the three strains responded to temperature changes by modifying the average structural composition of the alkyl and acyl chains constitutive of their membrane lipids. Major adaptive mechanisms concerned modifications of the level of branching and of the proportions of the different methyl branched lipids. Specifically, an increase in temperature induced mesophilic strains to produce less dimethyl branched dialkyl glycerols and 10-methyl branched lipids relative to linear structures, and the thermophilic strain to decrease the proportion of anteiso relative to iso methyl branched compounds. These modifications were in agreement with a regulation of the membrane fluidity. In one mesophilic and the thermophilic strains, a modification of the growth temperature further induced changes in the relative proportions of sn-2 vs sn-1 monoalkyl glycerols, suggesting an unprecedented mechanism of homeoviscous adaptation in Bacteria. Strong

  10. [Inhibition of oxidation of unsaturated fatty acid methyl esters by essential oils].

    Science.gov (United States)

    Misharina, T A; Alinkina, E S; Vorobjeva, A K; Terenina, M B; Krikunova, N I

    2016-01-01

    The essential oils from 16 various spice plants were studied as natural antioxidants for the inhibition of autooxidation of polyunsaturated fatty acids methyl esters isolated from linseed oil. The content of methyl oleate, methyl linoleate, and methyl linolenoate after 1, 2, and 4 months of autooxidation were used as criteria to estimate the antioxidant efficiencies of essential oils. In 4 months, 92% of the methyl linolenoate and 79% of the methyl linoleate were oxidized in a control sample of a model system. It was found that the most effective antioxidants were essential oils from clove bud, cinnamon leaves, and oregano. They inhibited autooxidation of methyl linolenoate by 76–85%. The antioxidant properties of these essential oils were due to phenols— eugenol, carvacrol, and thymol. Essential oil from coriander did not contain phenols, but it inhibited methyl linolenoate oxidation by 38%. Essential oils from thyme, savory, mace, lemon, and tea tree inhibited methyl linolenoate oxidation by 17–24%. The other essential oils had no antioxidant properties.

  11. Preparation and characterization of acrylic acid-grafted poly (vinyl alcohol) hydrogel actuators using γ-ray irradiation

    International Nuclear Information System (INIS)

    An, Sung Jun; Lim, Youn Mook; Gwon, Hui Jeong; Kim, Yun Hye; Youn, Min Ho; Nho, Young Chang; Han, Dong Hyun; Kim, Chong Yeal

    2008-01-01

    Active polymer gels expand and contract in response to certain environmental stimuli, such as the application of an electric field or a change in the pH level of the surroundings. This ability to achieve large, reversible deformations with no external mechanical loading has generated much interest in the use of these gels as biomimetic actuators and artificial muscles. In this study, poly (vinyl alcohol)(PVA) grafted acrylic acid monomer (PVA-g-AAc) hydrogels were prepared by 60 Co γ-ray irradiation and their properties such as degree of grafting and weight swelling in electrostimulation as an artificial muscle and actuator were investigated

  12. X-ray diffraction, vibrational and quantum chemical investigations of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid

    Science.gov (United States)

    Arjunan, V.; Marchewka, Mariusz K.; Pietraszko, A.; Kalaivani, M.

    2012-11-01

    The structural investigations of the molecular complex of 2-methyl-4-nitroaniline with trichloroacetic acid, namely 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid (C11H10Cl6N2O6) have been performed by means of single crystal and powder X-ray diffraction method. The complex was formed with accompanying proton transfer from trichloroacetic acid molecule to 2-methyl-4-nitroaniline. The studied crystal is built up of singly protonated 2-methyl-4-nitroanilinium cations, trichloroacetate anions and neutral trichloroacetic acid molecules. The crystals are monoclinic, space group P21/c, with a = 14.947 Å, b = 6.432 Å, c = 19.609 Å and Z = 4. The vibrational assignments and analysis of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid have also been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings were added from the quantum chemical studies performed with DFT (B3LYP) method using 6-31G**, cc-pVDZ, 6-31G and 6-31++G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of 2M4NATCA were also determined by the DFT methods.

  13. Flavonoids and triterpenes from the nest of the stingless bee Trigona spinipes

    Energy Technology Data Exchange (ETDEWEB)

    Freitas, Marinalva O.; Ponte, Flavio A.F.; Lima, Mary Anne S.; Silveira, Edilberto R. [Universidade Federal do Ceara, Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica. Curso de Pos-Graduacao em Quimica Organica]. E-mail: edil@ufc.br

    2008-07-01

    In the Northeast of Brazil the stingless bee Trigona spinipes Fabricius injures the tree bark of cultivated Eucalyptus citriodora specimens in order to make them exudate. The chemical investigation of the ethanol extract of an entire nest of T. spinipes allowed the isolation of the cycloartane triterpene magniferolic acid and 3{beta}-hydroxy-24-methylenecicloartan-26-oic acid, besides the flavonoids 3'-methyl quercetin, sakuranetin, kaempferol 7-methyl ether, tricetin and aromadendrin 7-methyl ether as the main compounds. The isolation of sakuranetin, kaempferol 7-methyl ether, and aromadendrin 7-methyl ether from both Trigonas spinipes' nest and the exudate from Eucalyptus, may suggest this species as a botanical origin of the nest constituents of these stingless bee in the Northeast of Brazil. The structural characterization of the isolated compounds was accomplished by spectrometric means and comparison with the literature data. (author)

  14. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Chiu, K.-F.; Su, S.-H., E-mail: minimono42@gmail.com

    2013-10-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO{sub 4} were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO{sub 4}, the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance.

  15. Lithiated and sulphonated poly(ether ether ketone) solid state electrolyte films for supercapacitors

    International Nuclear Information System (INIS)

    Chiu, K.-F.; Su, S.-H.

    2013-01-01

    Poly(ether ether ketone) (PEEK) films have been synthesised and used as solid-state electrolytes for supercapacitors. In order to increase their ion conductivity, the PEEK films were sulphonated by sulphuric acid, and various amounts of LiClO 4 were added. The solid-state electrolyte films were characterised by Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis. The ionic conductivities of the electrolyte films were analysed by performing electrochemical impedance spectroscopy. The obtained electrolyte films can be sandwiched or directly coated on activated carbon electrodes to form solid-state supercapacitors. The electrochemical characteristics of these supercapacitors were investigated by performing cyclic voltammetry and charge–discharge tests. Under an optimal content of LiClO 4 , the supercapacitor can provide a capacitance as high as 190 F/g. After 1000 cycles, the supercapacitors show almost no capacitance fading, indicating high stability of the solid-state electrolyte films. - Highlights: • Poly(ether ether ketone) (PEEK) films have been used as solid-state electrolytes. • LiClO4 addition can efficiently improve the ionic conductivity. • Supercapacitors using PEEK electrolyte films deliver high capacitance

  16. Catalytic hydrolysis of Metil Teret Botil Eter in under ground contaminated water

    International Nuclear Information System (INIS)

    Nikpey, A.; Mortazavi, B.; Asilian, H.; Khavanin, A.; Rezaee, A.; Soleimanian, A.; Kazemian, H.

    2005-01-01

    The behavior of ZSM-5 and Mordenite catalyst in the hydrolysis at room temperature of methyl tert-butyl ether was studied with reference to the possibility of its conversion to more biodegradable products in underground water contaminated by methyl tert-butyl ether. Hydrolysis products were determined using a gas chromatograph equipped with a flame ionization detector. The results indicate that acid ZSM-5 catalyst are effective in both adsorption and hydrolysis of methyl tert-butyl ether and may be applied for both in situ underground water remediation and as protection barrier for wells or leaking tanks. However, acid mordenite catalyst completely inactive

  17. Supra-physiological folic acid concentrations induce aberrant DNA methylation in normal human cells in vitro.

    Science.gov (United States)

    Charles, Michelle A; Johnson, Ian T; Belshaw, Nigel J

    2012-07-01

    The micronutrients folate and selenium may modulate DNA methylation patterns by affecting intracellular levels of the methyl donor S-adenosylmethionine (SAM) and/or the product of methylation reactions S-adenosylhomocysteine (SAH). WI-38 fibroblasts and FHC colon epithelial cells were cultured in the presence of two forms of folate or four forms of selenium at physiologically-relevant doses, and their effects on LINE-1 methylation, gene-specific CpG island (CGI) methylation and intracellular SAM:SAH were determined. At physiologically-relevant doses the forms of folate or selenium had no effect on LINE-1 or CGI methylation, nor on intracellular SAM:SAH. However the commercial cell culture media used for the selenium studies, containing supra-physiological concentrations of folic acid, induced LINE-1 hypomethylation, CGI hypermethylation and decreased intracellular SAM:SAH in both cell lines. We conclude that the exposure of normal human cells to supra-physiological folic acid concentrations present in commercial cell culture media perturbs the intracellular SAM:SAH ratio and induces aberrant DNA methylation.

  18. Determination of 4-Chloroindole-3-Acetic Acid Methyl Ester in Lathyrus Vicia and Pisum by Gas Chromatography - Mass Spectrometry

    DEFF Research Database (Denmark)

    Engvild, Kjeld Christensen; Egsgaard, Helge; Larsen, Elfinn

    1980-01-01

    4-Chloroindole-3-acetic acid methyl ester was identified unequivocally in Lathyrus latifolius L., Vicia faba L. and Pisum sativum L. by thin layer chromatography, gas chromatography and mass spectrometry. The gas chromatographic system was able to separate underivatized chloroindole-3-acetic acid...... methyl ester isomers. The quantitative determination of 4-chloroindole-3-acetic acid methyl ester in immature seeds of these three species was performed by gas chromatography – mass spectrometry using deuterium labelled 4-chloro-indole-3-acetic acid methyl ester as an internal standard. P. sativum...

  19. Involvement of a novel enzyme, MdpA, in methyl tert-butyl ether degradation in Methylibium petroleiphilum PM1.

    Science.gov (United States)

    Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R

    2008-11-01

    Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr(59) distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum.

  20. A new cytotoxic sterol methoxymethyl ether from a deep water marine sponge Scleritoderma sp. cf. paccardi.

    Science.gov (United States)

    Gunasekera, S P; Kelly-Borges, M; Longley, R E

    1996-02-01

    24(R)-Methyl-5 alpha-cholest-7-enyl 3 beta-methoxymethyl ether (1), a new sterol ether, has been isolated from a deep-water marine sponge Scleritoderma sp. cf. paccardi. Compound 1 exhibited in vitro cytotoxicity against the cultured murine P-388 tumor cell line with an IC50 of 2.3 micrograms/mL. The isolation and structure elucidation of 1 by NMR spectroscopy is described.

  1. Usage of methyl ester of tall oil fatty acids and resinic acids as alternative diesel fuel

    International Nuclear Information System (INIS)

    Keskin, Ali; Yasar, Abdulkadir; Guerue, Metin; Altiparmak, Duran

    2010-01-01

    In the experimental study, tall oil fatty and resinic acids were investigated as alternative diesel fuels. The fatty acids, obtained by distilling the crude tall oil, were esterified with methanol in order to obtain tall oil methyl ester (biodiesel). Blends of the methyl ester, resinic acids and diesel fuel were prepared for test fuels. Performance and emission tests of the test fuels were carried out in an unmodified direct injection diesel engine on full load conditions. The results showed that the specific fuel consumption (SFC) with the blend fuels did not show a significant change. CO emission and smoke level decreased up to 23.91% and 19.40%, respectively. In general, NO x emissions showed on trend of increasing with the blend fuels (up to 25.42%). CO 2 emissions did not vary with the blend fuels significantly.

  2. Usage of methyl ester of tall oil fatty acids and resinic acids as alternative diesel fuel

    Energy Technology Data Exchange (ETDEWEB)

    Keskin, Ali; Yasar, Abdulkadir [Tarsus Technical Education Faculty, Mersin University, 33500 Mersin (Turkey); Guerue, Metin [Engineering and Architectural Faculty, Gazi University, 06570 Maltepe, Ankara (Turkey); Altiparmak, Duran [Technical Education Faculty, Gazi University, 06500 Ankara (Turkey)

    2010-12-15

    In the experimental study, tall oil fatty and resinic acids were investigated as alternative diesel fuels. The fatty acids, obtained by distilling the crude tall oil, were esterified with methanol in order to obtain tall oil methyl ester (biodiesel). Blends of the methyl ester, resinic acids and diesel fuel were prepared for test fuels. Performance and emission tests of the test fuels were carried out in an unmodified direct injection diesel engine on full load conditions. The results showed that the specific fuel consumption (SFC) with the blend fuels did not show a significant change. CO emission and smoke level decreased up to 23.91% and 19.40%, respectively. In general, NO{sub x} emissions showed on trend of increasing with the blend fuels (up to 25.42%). CO{sub 2} emissions did not vary with the blend fuels significantly. (author)

  3. Synthesis of new fatty acids amides from aminolysis of fatty acid methyl esters (FAMEs)

    International Nuclear Information System (INIS)

    Lopes, Carolina R.; Montes D'Oca, Caroline da Ros; Duarte, Rodrigo da C.; Kurz, Marcia H.S.; Primel, Ednei G.; Clementin, Rosilene M.; Villarreyes, Joaquin Ariel M.; Montes D'Oca, Marcelo G.

    2010-01-01

    Recent biochemical and pharmacological studies have led to the characterization of different fatty acid amides as a new family of biologically active lipids. Here, we describe the synthesis of new amides from C16:0, 18:0, 18:1 and 18:1, OH fatty acids (FFA) families with cyclic and acyclic amines and demonstrate for the first time that these compounds produce cytotoxic effects. Application of this method to the synthesis of fatty acid amides was performed using the esters aminolysis as a key step and various carboxylic amides were prepared in good yield from fatty acid methyl esters (FAMEs). (author)

  4. Chromium–tungsten–titanium mixed oxides solid catalyst for fatty acid methyl ester synthesis from palm fatty acid distillate

    International Nuclear Information System (INIS)

    Wan, Zuraida; Hameed, B.H.

    2014-01-01

    Highlights: • Chromium–tungsten–titanium mixed oxides as solid catalyst. • Catalyst used for esterification of palm fatty acid distillate to methyl esters. • The maximum methyl ester content is 83%. • Catalyst has shown good activity and can be recycled for 4 times. - Abstract: Chromium–tungsten–titanium mixed oxides solid catalysts were prepared and evaluated in the esterification of palm fatty acid distillate (PFAD) to produce fatty acid methyl ester (FAME). Esterification was conducted in a batch reactor at 110–200 °C temperature ranges. The catalysts were characterized by several techniques such as BET, TEM, FTIR, TGA, XRD, EDX and SEM. The treatment conditions during catalyst preparation, effect of reaction parameters, leaching of the active species and the recycled use of the catalyst were investigated. The catalyst with formula CrWTiO 2 was found to be the most active with maximum FAME content of 83% obtained at best reaction conditions of 170 °C for 3 h, 2:1 (methanol to oil molar ratio) and 2 wt.% catalyst dosage. The catalyst can be recycled for 4 times. The results revealed CrWTiO 2 good potentials for use in esterification of high acid value oil

  5. New radioiodinated methyl-branched fatty acids for cardiac studies

    International Nuclear Information System (INIS)

    Knapp, F.F. Jr.; Ambrose, K.R.; Goodman, M.M.

    1986-01-01

    The effects of 3-methyl substitution on the heart retention and metabolism of 3-R,S-methyl-(BMIPP) and 3,3-dimethyl-(DMIPP) analogues of 15-(p-iodophenyl)-pentadecanoic acid (IPP) were studied in rats. Methyl substitution considerably increased the myocardial half-time values in fasted rats: IPP, 5-10 min; BMIPP, 30-45 min; DMIPP, 6-7 h. Because of the observed differences in the relative myocardial uptake and retention of these agents, an evaluation of the subcellular distribution profiles and the distribution of radioactivity within various lipid pools extracted from cell components was performed. Studies with DMIPP in food-deprived rats have shown high levels of the free fatty acid and only slow conversion to triglycerides. These data are in contrast to the rapid clearance of the straight chain IPP analogue and rapid incorporation into triglycerides, and suggest that the prolonged myocardial retention observed with DMIPP in vivo may result from inhibition of β oxidation. Subcellular distribution studies have shown predominant association of DMIPP and BMIPP with the mitochondrial and microsomal fractions, while IPP was primarily found in the cytoplasm. Because of the unique ''trapping'' properties and the high heart: blood ratios, [ 123 I]DMIPP should be useful for evaluation of aberrations in regional myocardial uptake. (orig.)

  6. Thermodynamic study of phase transitions in methyl esters of ortho- meta- and para-aminobenzoic acids

    International Nuclear Information System (INIS)

    Almeida, Ana R.R.P.; Monte, Manuel J.S.

    2012-01-01

    Highlights: ► Vapor pressures of liquid and crystalline phases of methyl esters of the aminobenzoic acids were measured. ► Accurate values of enthalpies of sublimation, vaporization, and fusion were derived. ► The enthalpy of intermolecular NH–O hydrogen bonds in methyl p-aminobenzoate was determined. ► The volatility of the methyl benzoates was compared with the volatility of the parent acids. - Abstract: A static method based on capacitance gauges was used to measure the vapor pressures of the condensed phases of the methyl esters of the three aminobenzoic acids. For methyl o-aminobenzoate the vapor pressures of the liquid phase were measured in the range (285.4 to 369.5) K. For the meta and para isomers vapor pressures of both crystalline and liquid phases were measured in the ranges (308.9 to 376.6) K, and (332.9 to 428.0) K, respectively. Vapor pressures of the latter compound were also measured using the Knudsen effusion method in the temperature range (319.1 to 341.2) K. From the dependence of the vapor pressures on the temperature, the standard molar enthalpies and entropies of sublimation and of vaporization were derived. Differential scanning calorimetry was used to measure the temperatures and molar enthalpies of fusion of the three isomers. The results enabled the estimation of the enthalpy of the intermolecular (N−H … O) hydrogen bond in the crystalline methyl p-aminobenzoate. A correlation relating the temperature of fusion and the enthalpy and Gibbs energy of sublimation of benzene, methyl benzoates and benzoic acids was derived.

  7. Structural analysis of acidic oligosaccharides derived from the methylated, acidic polysaccharide associated with coccoliths of Emiliania huxleyi (lohmann) kamptner

    NARCIS (Netherlands)

    Fichtinger-Schepman, A.M.J.; Kamerling, J.P.; Versluis, C.; Vliegenthart, J.F.G.

    1980-01-01

    A series of acidic oligosaccharides was obtained by graded, acid hydrolysis of the methylated, acidic polysaccharide associated with the coccoliths of the alga Emiliania huxleyi (Lohmann) Kamptner. After fractionation by ion-exchange chromatography, the structures of the oligosaccharides were

  8. Structure of chlorinated poly(vinyl chloride). III. Preparation of poly(vinyl chloride)-β,β-d2 as a model for the study of the mechanism of chlorination and of the chlorinated poly(vinyl chloride) structure

    International Nuclear Information System (INIS)

    Lukas, R.; Kolinsky, M.

    1976-01-01

    A method for the preparation of poly(vinyl chloride)-β,β-d 2 (PVC-β,β-d 2 ) as a model for the investigation of the mechanism of chlorination and of the CPVC structure has been suggested. The conditions of preparation of deuterated intermediates of a multistage synthesis of vinyl chloride-β,β-d 2 and of suspension-polymerized PVC-β,β-d 2 have been described including the mass balance. Malonic acid was used as the starting compound. Tacticity values of a sample of PVC-β,β-d 2 and its infrared and nuclear magnetic resonance (NMR) spectra are presented and compared with the data already published

  9. Effect of postharvest methyl jasmonate treatment on fatty acid composition and phenolic acid content in olive fruits during storage.

    Science.gov (United States)

    Flores, Gema; Blanch, Gracia Patricia; Del Castillo, María Luisa Ruiz

    2017-07-01

    The nutritional effects of both table olives and olive oil are attributed not only to their fatty acids but also to antioxidant phenolics such as phenolic acids. Delays in oil processing usually result in undesirable oxidation and hydrolysis processes leading to formation of free fatty acids. These alterations create the need to process oil immediately after olive harvest. However, phenolic content decreases drastically during olive storage resulting in lower quality oil. In the present study we propose postharvest methyl jasmonate treatment as a mean to avoid changes in fatty acid composition and losses of phenolic acids during olive storage. Contents of fatty acids and phenolic acids were estimated in methyl jasmonate treated olives throughout 30-day storage, as compared with those of untreated olives. Significant decreases of saturated fatty acids were observed in treated samples whereas increases of oleic, linoleic and linolenic acids were respectively measured (i.e. from 50.8% to 64.5%, from 7.2% to 9.1% and from 1.5% to 9.3%). Also, phenolic acid contents increased significantly in treated olives. Particularly, increases of gallic acid from 1.35 to 6.29 mg kg -1 , chlorogenic acid from 9.18 to 16.21 mg kg -1 , vanillic acid from 9.61 to 16.99 mg kg -1 , caffeic acid from 5.12 to 12.55 mg kg -1 , p-coumaric acid from 0.96 to 5.31 mg kg -1 and ferulic acid from 4.05 to 10.43 mg kg -1 were obtained. Methyl jasmonate treatment is proposed as an alternative postharvest technique to traditional methods to guarantee olive oil quality when oil processing is delayed and olive fruits have to necessarily to be stored. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  10. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando

    2016-07-07

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  11. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

    2016-01-01

    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  12. Removal of some basic dyes by poly (Vinyl Alcohol/ acrylic acid)Hydrogel

    International Nuclear Information System (INIS)

    Hegazy, S.A.; Abdel-AAl, S.E.; Abdel-Rehim, H.A.; Khalifa, N.A.; El-Hosseiny, E.M.

    2000-01-01

    A study has made on the preparation and properties of poly (vinyl alcohol/ acrylic acid) hydrogel for the purpose of removal of cationic dyes from aqueous solutions. The effect of dose and monomer concentration on the uptake property of the hydrogel toward dye was studied. The uptake of basic methylene blue-9 dye with PVA/AAc was studied by the batch adsorption technique. The effect of pH on the dye uptake was demonstrated to find out that the suitable pH for maximum uptake occurred at pH 5. It was observed that as the concentration of dye is increased the dye uptake decreased. Furthermore, the uptake of dye by hydrogels increased as the temperature was elevated. The recovery of dye adsorbed is possible by treating the hydrogel with 5% HCl. The results obtained suggested this hydrogel possessed good removal properties towards basic methylene blue-9 dye, and this suggests that such hydrogels could be acceptable for practical uses

  13. Radiosynthesis of N-¹¹C-Methyl-Taurine-Conjugated Bile Acids and Biodistribution Studies in Pigs by PET/CT.

    Science.gov (United States)

    Schacht, Anna Christina; Sørensen, Michael; Munk, Ole Lajord; Frisch, Kim

    2016-04-01

    During cholestasis, accumulation of conjugated bile acids may occur in the liver and lead to hepatocellular damage. Inspired by our recent development of N-(11)C-methyl-glycocholic acid-that is, (11)C-cholylsarcosine-a tracer for PET of the endogenous glycine conjugate of cholic acid, we report here a radiosynthesis of N-(11)C-methyl-taurine-conjugated bile acids and biodistribution studies in pigs by PET/CT. A radiosynthesis of N-(11)C-methyl-taurine-conjugated bile acids was developed and used to prepare N-(11)C-methyl-taurine conjugates derived from cholic, chenodeoxycholic, deoxycholic, ursodeoxycholic, and lithocholic acid. The lipophilicity of these new tracers was determined by reversed-phase thin-layer chromatography. The effect of lipophilicity and structure on the biodistribution was investigated in pigs by PET/CT using the tracers derived from cholic acid (3α-OH, 7α-OH, 12α-OH), ursodeoxycholic acid (3α-OH, 7β-OH), and lithocholic acid (3α-OH). The radiosyntheses of the N-(11)C-methyl-taurine-conjugated bile acids proceeded with radiochemical yields of 61% (decay-corrected) or greater and radiochemical purities greater than 99%. PET/CT in pigs revealed that the tracers were rapidly taken up by the liver and secreted into bile. There was no detectable radioactivity in urine. Significant reflux of N-(11)C-methyl-taurolithocholic acid into the stomach was observed. We have successfully developed a radiosynthesis of N-(11)C-methyl-taurine-conjugated bile acids. These tracers behave in a manner similar to endogenous taurine-conjugated bile acids in vivo and are thus promising for functional PET of patients with cholestatic diseases. © 2016 by the Society of Nuclear Medicine and Molecular Imaging, Inc.

  14. Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

    Directory of Open Access Journals (Sweden)

    Y. I. Hassan

    2012-01-01

    Full Text Available The kinetics of oxidation of diethyl ether (DE with sodium N-chloro-p-toluenesulphonamide (CAT in hydrochloric acid solution has been studied at (313°K.The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

  15. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    Energy Technology Data Exchange (ETDEWEB)

    Peng, X.D.; Toseland, B.A.; Underwood, R.P. [Air Products and Chemicals, Inc., Allentown, PA (United States)

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  16. Radiation synthesis of functionalising polymer and creation of composition materials on their basis

    International Nuclear Information System (INIS)

    Mun, G.A.; Nurkeeva, Z.S.; Akhmetkalieva, G.T.; Urkimbaeva, P.I.; Park, L.K.; Lyssukhin, S.N.; Chakrov, P.V.

    2005-01-01

    critical solution temperature (LCST) in aqueous solutions, which value strongly depends on the ration of hydrophilic and hydrophobic monomeric units in copolymers. The hydrogels of copolymers based on these monomeric pairs possess thermo-sensitivity and undergo contraction upon increase of temperature. The possibility for modification of temperature-responsive properties of hydrogels by interactions with surfactants and polyacrylic acid is shown. pH-sensitive hydrogels were synthesized by copolymerization of systems VBE-acrylic acid (AA), VEEG-VBE-AA, VEEG-HEMA-AA, VEEG- butylmethacrylate-AA as well as by polymerization of AA within PVEEG network. The release of drugs from pH-sensitive hydrogels is studied. Novel hydrophilic films were prepared based on polyacrylic acid (Paa) and poly(vinyl ether of ethyleneglycol) (PVEEG). The films were found to be insoluble in buffer solutions with pH 4.0, which is caused by complex formation between PAA and PVEEG in acidic media via hydrogen bonding. It was shown that PAA-PVEEG films form a cross-linked gel upon thermal and gamma-radiation treatment. The hydrophilic films of PAA-PVEEG with immobilized local anesthetic drug lidocaine hydrochloride were developed. Fundamental knowledge in the area of radiation polymerization of vinyl ethers were effectively realized by them upon executing of research on the synthesis of novel film materials by radiation grafting of functional polymers VEEG and vinyl ether of mono-ethanol amine onto polyethylene and polypropylene with further metallization. It was showed that modified polyolefin films are perspective for application in separation of ions of transition and heavy metals, as a catalyst-active metal platform and conducting materials, etc. The possibility of application of the obtained functionalising polymers in advanced technologies and medicine has been studied

  17. Functional analysis of a tomato salicylic acid methyl transferase and its role in synthesis of the flavor volatile methyl salicylate.

    Science.gov (United States)

    Tieman, Denise; Zeigler, Michelle; Schmelz, Eric; Taylor, Mark G; Rushing, Sarah; Jones, Jeffrey B; Klee, Harry J

    2010-04-01

    Methyl salicylate (MeSA) is a volatile plant secondary metabolite that is an important contributor to taste and scent of many fruits and flowers. It is synthesized from salicylic acid (SA), a phytohormone that contributes to plant pathogen defense. MeSA is synthesized by members of a family of O-methyltransferases. In order to elaborate the mechanism of MeSA synthesis in tomato, we screened a set of O-methyltransferases for activity against multiple substrates. An enzyme that specifically catalyzes methylation of SA, SlSAMT, as well as enzymes that act upon jasmonic acid and indole-3-acetic acid were identified. Analyses of transgenic over- and under-producing lines validated the function of SlSAMT in vivo. The SlSAMT gene was mapped to a position near the bottom of chromosome 9. Analysis of MeSA emissions from an introgression population derived from a cross with Solanum pennellii revealed a quantitative trait locus (QTL) linked to higher fruit methyl salicylate emissions. The higher MeSA emissions associate with significantly higher SpSAMT expression, consistent with SAMT gene expression being rate limiting for ripening-associated MeSA emissions. Transgenic plants that constitutively over-produce MeSA exhibited only slightly delayed symptom development following infection with the disease-causing bacterial pathogen, Xanthomonas campestris pv. vesicatoria (Xcv). Unexpectedly, pathogen-challenged leaves accumulated significantly higher levels of SA as well as glycosylated forms of SA and MeSA, indicating a disruption in control of the SA-related metabolite pool. Taken together, the results indicate that SlSAMT is critical for methyl salicylate synthesis and methyl salicylate, in turn, likely has an important role in controlling SA synthesis.

  18. Synthesis of hydroxylated and methoxylated polybrominated diphenyl ethers

    Institute of Scientific and Technical Information of China (English)

    ZHENG Ke-wen; GAO Li-ping; CAO Jie; YU Hai-wen; ZHANG Zhang

    2009-01-01

    Hydroxylated/methoxylated polybrominated diphenyl ethers (OH/MeO-PBDEs) are not only detected as natural products, but also regarded as metabolites formed from polybrominated diphenyl ethers (PBDEs), which are widely used as flame-retardants in various materials. The aim of the present study was to synthesize authentic OH-PBDEs and MeO-PBDEs, as reference standards for environmental exploration. Twenty OH-PBDEs and their corresponding MeO-PBDEs containing three to six bromine atoms were synthesized via a trial of reactions including coupling, oxidation, bromination, methylation, etc. The products were characterized by GC-MS and 1H-NMR spectroscopy in the work. As results show, all compounds synthesized were up to 99% on purity and be reqarded as authentic standards for detecting the chemical pollutants in the emvironment.

  19. Novel synthesis on poly (vinyl alcohol): characterization, complexation a biological activity

    International Nuclear Information System (INIS)

    El-Sawy, N.M.; Elassar, A.Z.; Al-Fulaij, O.

    2002-01-01

    Poly(vinyl alcohol), PVA, readily condensed with phenyl hydrazine and malononitrile in basic medium to give the hydrazone and pyran derivatives, respectively. PVA reacted with chloroacetonitrile, biuet and thiophene carbonyl chloride to give modified polymeric materials. While addition of PVA to acrylonitrile and phenyl isothiocyanate gives the ether and thiocarbamate ester derivatives, respectively. Hydroxylamine hydrochloride reacted with the modified, carbonitrile containing, polymer to give the amidoxime derivative. The amidoximated products of PVA and carbamate ester of polymeric material were complexed with CUCL2 solution. The complex materials were confirmed by using UV and ESDS measurements. The morphology of PVA and complex with CUII was observed by SEM. Biological activity of some of the prepared compounds was investigated toward bacteria and fungi

  20. The influence of surface oxygen and hydroxyl groups on the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate on pure Pd(1 0 0): A DFT study

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yanping [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072 (China); Dong, Xiuqin [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Yu, Yingzhe, E-mail: yzhyu@tju.edu.cn [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China); Zhang, Minhua, E-mail: mhzhangtj@163.com [Key Laboratory for Green Chemical Technology of Ministry of Education, R& D Center for Petrochemical Technology, Tianjin University, Tianjin (China)

    2016-12-01

    Highlights: • All dehydrogenation reactions in vinyl acetate synthesis on Pd(1 0 0) were studied. • The energy barriers of the transition state of the three reactions were calculated. • The influence of surface Os and OHs on all dehydrogenation actions was discussed. - Abstract: On the basis of a Langmuir–Hinshelwood-type mechanism, the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate (VAH) on pure Pd(1 0 0) with surface oxygen atoms (Os) and hydroxyl groups (OHs) was studied with density functional theory (DFT) method. Our calculation results show that both Os and OHs can consistently reduce the activation energies of dehydrogenation of ethylene, acetic acid and VAH to some degree with only one exception that OHs somehow increase the activation energy of VAH. Based on Langmuir–Hinshelwood mechanism, the three dehydrogenation reactions in presence of surface Os and OHs are almost consistently favored, compared with the corresponding processes on clean Pd(1 0 0) surfaces, and thus a Langmuir–Hinshelwood-type mechanism may not be excluded beforehand when investigating the microscopic performance of the oxygen-assisted vinyl acetate synthesis on Pd(1 0 0) catalysts.

  1. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    Science.gov (United States)

    Smith, L.A. Jr.; Jones, E.M. Jr.; Hearn, D.

    1984-05-08

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

  2. Heteroaryl ethers by oxidative palladium catalysis of pyridotriazol-1-yloxy pyrimidines with arylboronic acids.

    Science.gov (United States)

    Bardhan, Sujata; Wacharasindhu, Sumrit; Wan, Zhao-Kui; Mansour, Tarek S

    2009-06-18

    The oxidative palladium-catalyzed cross-coupling of pyrimidines containing pyridotriazol-1-yloxy (OPt) as either a urea or an amide functional group with arylboronic acids in the presence of Cs(2)CO(3) in DME containing 0.6-1.0% H(2)O is described for the preparation of heteroaryl ethers. The bromo substitution in the case of 3-(5-bromo-pyrimidin-2-yloxy)-3H-[1,2,3]triazolo[4,5-b]pyridine 1 could serve as a handle for further elaborations such as Suzuki coupling for attaching varied aryl groups.

  3. Simultaneous FT-NIR and ESR analysis to study of the kinetics of photo induced polymerization of vinyl radical polymers

    International Nuclear Information System (INIS)

    Le, T.T.; Hill, D.J.T.; Pomery, P.J.

    2000-01-01

    Full text:The rate parameters for free vinyl radical polymerizations are difficult to determine accurately over the whole range of conversion. For systems which polymerize rapidly and for networks, this is a particular problem, because small differences in polymerization conditions, e.g., temperature, initiator concentration, photon flux, etc., can cause a large change in the time evolution of the concentration of carbon double bonds and radicals if these are monitored in separate experiments. The IUPAC Working Party on the Modeling of kinetics and processes of polymerization has the role of recommending the 'best' values for the kinetic parameters, using pulsed-laser polymerization (PLP) in conjunction with molar mass distribution (MMD) to determine k p as a function of temperature (T deg C) for bulk free-radical polymerization of methyl methacrylate at low conversions and ambient temperature. The vinyl radical polymers used in this study were methyl methacrylate and ethylene glycol dimethacrylate. In the past kinetic studies of vinyl photo-polymerization required the time dependence of the monomer and radical concentrations to be monitored separately by using FT-NIR spectroscopy and ESR spectroscopy, respectively. For the systems which polymerize rapidly, small differences in the conditions for two measurements, e.g. temperature and light intensity, can introduce significant errors. Hyphenated experiments involving in-situ ESR and FT-NIR spectroscopies using fibre optic, can overcome these problems. In this paper, the radical and monomer concentrations were measured under the same experimental conditions using the above techniques. The results obtained were used to evaluate the kinetic parameters for free radical vinyl polymerizations

  4. New radioiodinated methyl-branched fatty acids for cardiac studies

    International Nuclear Information System (INIS)

    Knapp, F.F. Jr.; Ambrose, K.R.; Goodman, M.M.

    1985-01-01

    The effects of 3-methyl-substitution on the heart retention and metabolism of 3-R,S-methyl-(BMIPP) and 3,3-dimethyl-(DMIPP) analogues of 15-(p-iodophenyl)-pentadecanoic acid (IPP) have been studied in rats. Methyl-substitution considerably increased the myocardial half-time values in fasted rats: IPP, 5 to 10 min; BMIPP, 30 to 45 min; DMIPP, 6 to 7 h. Because of the observed differences in the relative myocardial uptake and retention of these agents, an evaluation of the subcellular distribution profiles and the distribution of radioactivity within various lipid pools extracted from cell components was performed. Studies with DMIPP in fasted rats have shown high levels of the free fatty acid and only slow conversion to triglycerides. These data are in contrast to the rapid clearance of the straight chain IPP analogue and rapid incorporation into triglycerides. These data suggest that the prolonged myocardial retention observed with DMIPP in vivo may result from inhibition of β-oxidation. Subcellular distribution studies have shown predominate association of DMIPP and BMIPP with the mitochondrial and microsomal fractions, while IPP was primarily found in the cytoplasm. Because of the unique ''trapping'' properties and the high heart:blood ratios, [ 123 I]DMIPP should be useful for evaluation of aberrations in regional myocardial uptake. 7 refs., 9 figs., 1 tab

  5. Preparation of Thermoplastic Poly (vinyl Alcohol), Ethylene Vinyl Acetate and Vinyl Acetate Versatic Ester Blends for Exterior Masonry Coating

    International Nuclear Information System (INIS)

    EL-Nahas, H.H.; Gad, Y.H.; Magida, M.M.

    2013-01-01

    Blend systems including ethylene vinyl acetate (EVA), poly (vinyl alcohol) (PVA) and vinyl acetate versatic copolymer latex (VAcVe) were prepared and used as exterior coatings. Mechanical and thermal properties of the blends were investigated using a testo meter, shore hardness tester, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The water resistance of the samples was measured. Effect of ionizing irradiation on gel content, tensile strength and surface hardness were also followed. The blend offers binder base for exterior masonry coating systems having superior water resistant and mechanical properties

  6. Uric Acid or 1-Methyl Uric Acid in the Urinary Bladder Increases Serum Glucose, Insulin, True Triglyceride, and Total Cholesterol Levels in Wistar Rats

    Directory of Open Access Journals (Sweden)

    T. Balasubramanian

    2003-01-01

    Full Text Available In animals deprived of food for a long period, a drop in the fat mass below 5% of the total body mass results in an increase in blood glucocorticoids and uric acid levels, followed by foraging activity. Since the glucocorticoids increase the uric acid excretion, an increase in the level of uric acid in the bladder urine could be the signal for this feeding behaviour and subsequent fat storage. Accumulation of fat is associated with hyperglycaemia, hyperinsulinaemia, hyperlipidaemia, and hypercholesterolaemia as seen in the metabolic syndrome or hibernation. It is hypothesized that uric acid or its structurally related compound, 1-methyl uric acid (one of the metabolites of the methyl xanthines namely caffeine, theophylline, and theobromine present in coffee, tea, cocoa, and some drugs, can act on the urinary bladder mucosa and increases the blood glucose, insulin, triglyceride, and cholesterol levels. In rats, perfusion of the urinary bladder with saturated aqueous solution of uric acid or 1-methyl uric acid results in a significant increase in the serum levels of glucose, insulin, true triglyceride, and total cholesterol in comparison with perfusion of the bladder with distilled water at 20, 40, and 80 min. The uric acid or the 1-methyl uric acid acts on the urinary bladder mucosa and increases the serum glucose, insulin, true triglyceride, and total cholesterol levels.

  7. Involvement of a Novel Enzyme, MdpA, in Methyl tert-Butyl Ether Degradation in Methylibium petroleiphilum PM1 ▿

    Science.gov (United States)

    Schmidt, Radomir; Battaglia, Vince; Scow, Kate; Kane, Staci; Hristova, Krassimira R.

    2008-01-01

    Methylibium petroleiphilum PM1 is a well-characterized environmental strain capable of complete metabolism of the fuel oxygenate methyl tert-butyl ether (MTBE). Using a molecular genetic system which we established to study MTBE metabolism by PM1, we demonstrated that the enzyme MdpA is involved in MTBE removal, based on insertional inactivation and complementation studies. MdpA is constitutively expressed at low levels but is strongly induced by MTBE. MdpA is also involved in the regulation of tert-butyl alcohol (TBA) removal under certain conditions but is not directly responsible for TBA degradation. Phylogenetic comparison of MdpA to related enzymes indicates close homology to the short-chain hydrolyzing alkane hydroxylases (AH1), a group that appears to be a distinct subfamily of the AHs. The unique, substrate-size-determining residue Thr59 distinguishes MdpA from the AH1 subfamily as well as from AlkB enzymes linked to MTBE degradation in Mycobacterium austroafricanum. PMID:18791002

  8. Functionalized mesoporous silicas with crown ether moieties for selective adsorption of lithium ions in artificial sea water.

    Science.gov (United States)

    Sung, Soo Park; Moorthy, Madhappan Santha; Song, Hyun-Jin; Ha, Chang-Sik

    2014-11-01

    Lithium ion has been increasingly recognized in a wide range of industrial applications. In this work, we studied on the adsorption of Li+ in the artificial seawater with high selectivity using methyl-crown ether (AC-SBA-15) and aza-crown ether (HMC-SBA-15) moieties-functionalized mesoporous silica materials. First, methyl-crown ether and aza-crown ether moieties-functionalized mesoporous silica materials were synthesized via two-step post-synthesis process using a grafting method. The functionalized materials were employed to the metal ion adsorption from aqueous solution (artificial seawater) containing Li+, Co2+, Cr3+ and Hg2+. The prepared hybrid material showed high selectivity for Li+ ion in the artificial seawater at pH 8.0. The absorbed amount of Li+ was 73 times higher than Cr3+ for aza-crown ether containing AC-SBA-15 as an absorbent. The absorbed amount of Co2+ (4.5 x 10(-5) mol/g), Cr3+ (1.5 x 10(-5) mol/g) and Hg2+ (2.25 x 10(-4) mol/g) were remarkably lower than the case of Li+. On the other hand, the absorbed amount of various metal ions of HMC-SBA-15 with amine groups in alky chains and crown ether moieties were 1.1 x 10(-3) mol/g for Li+, 5.0 x 10(-5) mol/g for Co2+, 2.9 x 10(-4) mol/g for Cr3+, 2.8 x 10(-4) mol/g for Hg2+ mol/g, respectively.

  9. Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

    International Nuclear Information System (INIS)

    Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Turks, Maris; Cooper, William J.

    2013-01-01

    Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×10 9 , (1.07±0.07)×10 10 , (7.48±0.17)×10 9 , (7.31±0.29)×10 9 , (5.47±0.25)×10 9 , (6.94±0.10)×10 9 (M −1 s −1 ), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×10 9 , (8.98±0.27)×10 9 , (5.39±0.21)×10 9 , (4.33±0.17)×10 9 , (4.72±0.15)×10 9 , (1.42±0.02)×10 9 (M −1 s −1 ), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated. - Highlights: • Free radical chemistry of salicylic and 4 methyl salicylic acids is investigated. • The transient absorptions spectra for model compounds are measured. • Absolute bimolecular reaction rate constants for hydroxyl radical are determined. • Solvated electron reaction rate constants are calculated. • The use of salicylic acids as models for pharmaceuticals is explored

  10. Deriving Biomonitoring Equivalents for selected E- and P-series glycol ethers for public health risk assessment.

    Science.gov (United States)

    Poet, Torka; Ball, Nicholas; Hays, Sean M

    2016-01-01

    Glycol ethers are a widely used class of solvents that may lead to both workplace and general population exposures. Biomonitoring studies are available that have quantified glycol ethers or their metabolites in blood and/or urine amongst exposed populations. These biomonitoring levels indicate exposures to the glycol ethers, but do not by themselves indicate a health hazard risk. Biomonitoring Equivalents (BEs) have been created to provide the ability to interpret human biomonitoring data in a public health risk context. The BE is defined as the concentration of a chemical or metabolite in a biological fluid (blood or urine) that is consistent with exposures at a regulatory derived safe exposure limit, such as a tolerable daily intake (TDI). In this exercise, we derived BEs for general population exposures for selected E- and P-series glycol ethers based on their respective derived no effect levels (DNELs). Selected DNELs have been derived as part of respective Registration, Evaluation, Authorisation and Regulation of Chemicals (REACh) regulation dossiers in the EU. The BEs derived here are unique in the sense that they are the first BEs derived for urinary excretion of compounds following inhalation exposures. The urinary mass excretion fractions (Fue) of the acetic acid metabolites for the E-series GEs range from approximately 0.2 to 0.7. The Fues for the excretion of the parent P-series GEs range from approximately 0.1 to 0.2, with the exception of propylene glycol methyl ether and its acetate (Fue = 0.004). Despite the narrow range of Fues, the BEs exhibit a larger range, resulting from the larger range in DNELs across GEs. The BEs derived here can be used to interpret human biomonitoring data for inhalation exposures to GEs amongst the general population. Copyright © 2015 Elsevier GmbH. All rights reserved.

  11. Tactical Fuel and Energy Strategy for The Future Modular Force

    Science.gov (United States)

    2009-05-18

    Environmental Protection Agency ESSP Energy Strategic Security Plan EV Electric Vehicle FAME Fatty Acid Methyl Ester Appendix...1992. Methanol can be used to make methyl tertiary-butyl ether (MTBE), oxygenate that is blended with gasoline to enhance octane and create cleaner...Military Occupation Specialty MTBE Methyl Tertiary Butyl Ether MW Megawatt NASA National Aeronautics and Space Administration NATO North

  12. Radium separation through complexation by aqueous crown ethers and ion exchange or solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Chiarizia, R.; Dietz, M.L.; Horwitz, E.P. [Argonne National Lab., IL (United States). Chemistry Div.; Burnett, W.C. [Florida State Univ., Tallahassee, FL (United States). Dept. of Oceanography

    1997-11-01

    The effect of three water-soluble, unsubstituted crown ethers (15-crown-5 (15C5), 18-crown-6 (18C6) and 21-crown-7 (21C7)) on the uptake of Ca, Sr, Ba and Ra cations by a sulfonic acid cation exchange resin, and on the extraction of the same cations by xylene solutions of dinonylnaphthalenesulfonic acid (HDNNS) from aqueous hydrochloric acid solutions has been investigated. The crown ethers enhance the sorption of the larger cations by the ion exchange resin, thereby improving the resin selectivity over calcium, a result of a synergistic interaction between the crown ether and the ionic functional groups of the resin. Similarly, the extraction of the larger alkaline earth cations into xylene by HDNNS is strongly synergized by the presence of the crown ethers in the aqueous phase. Promising results for intra-Group IIa cation separations have been obtained using each of the three crown ethers as the aqueous ligands and the sulfonic acid cation exchange resin. Even greater separation factors for the radium-calcium couple have been measured with the crown-ethers and HDNNS solutions in the solvent extraction mode. The application of the uptake and extraction results to the development of radium separation schemes is discussed and a possible flowchart for the determination of {sup 226}Ra/{sup 228}Ra in natural waters is presented.

  13. Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

    Science.gov (United States)

    Finneran, K T; Lovley, D R

    2001-05-01

    The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

  14. Developmental toxicity evaluation of inhaled tertiary amyl methyl ether in mice and rats.

    Science.gov (United States)

    Welsch, Frank; Elswick, Barbara; James, R Arden; Marr, Melissa C; Myers, Christina B; Tyl, Rochelle W

    2003-01-01

    This evaluation was part of a much more comprehensive testing program to characterize the mammalian toxicity potential of the gasoline oxygenator additive tertiary amyl methyl ether (TAME), and was initiated upon a regulatory agency mandate. A developmental toxicity hazard identification study was conducted by TAME vapor inhalation exposure in two pregnant rodent species. Timed-pregnant CD(Sprague-Dawley) rats and CD-1 mice, 25 animals per group, inhaled TAME vapors containing 0, 250, 1500 or 3500 ppm for 6 h a day on gestational days 6-16 (mice) or 6-19 (rats). The developmental toxicity hazard potential was evaluated following the study design draft guidelines and end points proposed by the United States Environmental Protection Agency. Based on maternal body weight changes during pregnancy, the no-observable-adverse-effect level (NOAEL) was 250 ppm for maternal toxicity in rats and 1500 ppm for developmental toxicity in rats using the criterion of near-term fetal body weights. In mice, more profound developmental toxicity was present than in rats, at both 1500 and 3500 ppm. At the highest concentration, mouse litters revealed more late fetal deaths, significantly reduced fetal body weights per litter and increased incidences of cleft palate (classified as an external malformation), as well as enlarged lateral ventricles of the cerebrum (a visceral variation). At 1500 ppm, mouse fetuses also exhibited an increased incidence of cleft palate and the dam body weights were reduced. Therefore, the NOAEL for the mouse maternal and developmental toxicity was 250 ppm under the conditions of this study. Copyright 2003 John Wiley & Sons, Ltd.

  15. Synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid vinyl-ACCA) derivatives: key intermediates for the preparation of inhibitors of the hepatitis C virus NS3 protease.

    Science.gov (United States)

    Beaulieu, Pierre L; Gillard, James; Bailey, Murray D; Boucher, Colette; Duceppe, Jean-Simon; Simoneau, Bruno; Wang, Xiao-Jun; Zhang, Li; Grozinger, Karl; Houpis, Ioannis; Farina, Vittorio; Heimroth, Heidi; Krueger, Thomas; Schnaubelt, Jürgen

    2005-07-22

    (1R,2S)-1-Amino-2-vinylcyclopropanecarboxylic acid (vinyl-ACCA) is a key building block in the synthesis of potent inhibitors of the hepatitis C virus NS3 protease such as BILN 2061, which was recently shown to dramatically reduce viral load after administration to patients infected with HCV genotype 1. We have developed a scalable process that delivers derivatives of this unusual amino acid in >99% ee. The strategy was based on the dialkylation of a glycine Schiff base using trans-1,4-dibromo-2-butene as an electrophile to produce racemic vinyl-ACCA, which was subsequently resolved using a readily available, inexpensive esterase enzyme (Alcalase 2.4L). Factors that affect diastereoselection in the initial dialkylation steps were examined and the conditions optimized to deliver the desired diastereomer selectively. Product inhibition, which was encountered during the enzymatic resolution step, initially resulted in prolonged cycle times. Enrichment of racemic vinyl-ACCA through a chemical resolution via diastereomeric salt formation or the use of forcing conditions in the enzymatic reaction both led to improvements in throughput and the development of a viable process. The chemistry described herein was scaled up to produce multikilogram quantities of this building block.

  16. Biotransformation of bergapten and xanthotoxin by Glomerella cingulata.

    Science.gov (United States)

    Marumoto, Shinsuke; Miyazawa, Mitsuo

    2010-07-14

    The biotransformation of bergapten (1) by the fungus Glomerella cingulata gave the corresponding reduced acid, 6,7-furano-5-methoxy hydrocoumaric acid (2), a new compound. Xanthotoxin (3) was also converted to the corresponding reduced acid cnidiol b (4) and demethylated metabolite xanthotoxol (5) by G. cingulata. The structure of the new compound 2 was elucidated by high-resolution mass spectrometry, extensive NMR techniques, including (1)H NMR and (13)C NMR, (1)H-(1)H correlation spectroscopy, heteronuclear multiple quantum coherence, and heteonuclear multiple bond coherence. The methyl ester or methyl ether or methyl ester and ether derivatives of 2 and 4 were synthesized. All compounds were tested for the beta-secretase (BACE1) inhibitory activity in vitro. The methyl ester and ether derivative 8 was shown to possess BACE1 inhibitory activity, and a IC(50) value was 0.64 +/- 0.04 mM.

  17. Niobium Pentachloride Activation of Enone Derivatives: Diels-Alder and Conjugate Addition Products

    Directory of Open Access Journals (Sweden)

    Gil Valdo José da Silva

    2002-05-01

    Full Text Available Niobium pentachloride has proven to be a powerful activating agent for Diels-Alder or conjugate addition reactions of cycloenones. The Diels-Alder product was obtained only with an unsubstituted enone (cyclohexenone and the highly reactive diene cyclopentadiene; substituents in the b-position of enones seem to prevent Diels-Alder reaction: oxygenated substituents favor the formation of vinyl chlorides (ethyl ether or dichloromethane as solvents or enol ethers (ethyl acetate as solvent, while a methyl substituent prevents any kind of transformation with NbCl5. Less reactive dienes, furan and 2-methylfuran gave the conjugate addition products of the furan ring to the enone system.

  18. The occurrence of 2-hydroxy-6-methoxybenzoic acid methyl ester in Securidaca longepedunculata Fresen root bark

    Directory of Open Access Journals (Sweden)

    Lognay G.

    2000-01-01

    Full Text Available As part of our ongoing search for natural fumigants from Senegalese plants, we have investigated Securicicidaca longepedunculata root barks and demonstrated that 2-hydroxy-benzoic acid methyl ester (methyl salicylate, I is responsible of their biocide effect against stored grain insects. A second unknown apparented product, II has been systematically observed in all analyzed samples. The present paper describes the identification of this molecule. The analytical investigations including GCMS, GLC and 1H-NMR. spectrometry led to the conclusion that II corresponds to the 2-hydroxy-6-methoxybenzoic acid methyl ester.

  19. Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

    International Nuclear Information System (INIS)

    Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

    1992-01-01

    To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

  20. Quantitative determination of conjugated linoleic acid and polyunsaturated fatty acids in milk with C17:0 as internal marker – Evaluation of different methylation procedures

    Directory of Open Access Journals (Sweden)

    S. Lashkari

    2017-12-01

    Full Text Available Fatty acids are commonly analysed by gas chromatography as their corresponding fatty acid (FA methyl esters (FAME. For quantitative determination of individual FA an internal standard like C17:0 is necessary. Conjugated FA and polyunsaturated fatty acid (PUFA represents a challenge in the methylation steps, as they are sensitive to pH changes and oxidation. The present study was carried out to determine the efficiency of different methylation procedures on quantitative determination of conjugated linoleic acid (CLA, PUFA and response of internal standard. The highest response of internal standard was observed for boron trifluoride (BF3/methanol and methanolic HCl followed by NaOCH3, while cis-9, trans-11 CLA, total CLA and PUFA was higher with methanolic HCl followed by NaOCH3 compared with the BF3 method. These data can be useful for quantitating of milk FA. Keywords: Methylation procedures, Milk fatty acid, Conjugated linoleic acid

  1. 2,6-di-tert-butylphenylvinyl ether: effect of the unshared oxygen electron pair on the /sup 13/C-/sup 13/C spin-spin interaction constant

    Energy Technology Data Exchange (ETDEWEB)

    Krivdin, L.B.; Shcherbakov, V.V.; Glukhikh, N.G.; Sigalov, V.M.; Kalabin, G.A.

    1987-07-10

    Vinyl ethers were prepared by the well-known Favorskii-Shostakovskii method. The purity of the compounds was controlled by GLC and by the PMR and /sup 13/C NMR spectra. The proximity of sp/sup 7/-hybridized unshared pair of oxygen atoms result in a secondary, positive contribution in the constant of spin-spin interaction between neighboring carbon nuclei in the aromatic ring.

  2. On the Formation of the C{sub 2}H{sub 6}O Isomers Ethanol (C{sub 2}H{sub 5}OH) and Dimethyl Ether (CH{sub 3}OCH{sub 3}) in Star-forming Regions

    Energy Technology Data Exchange (ETDEWEB)

    Bergantini, Alexandre; Maksyutenko, Pavlo; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [Department of Chemistry, University of Hawaii at Mānoa, Honolulu, HI 96822 (United States)

    2017-06-01

    The structural isomers ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H{sub 2}O/CH{sub 4}) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C{sub 2}H{sub 6}O isomers: ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical–radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C{sub 3}H{sub 4}), ketene (CH{sub 2}CO), propene (C{sub 3}H{sub 6}), vinyl alcohol (CH{sub 2}CHOH), acetaldehyde (CH{sub 3}CHO), and methyl hydroperoxide (CH{sub 3}OOH), in addition to ethane (C{sub 2}H{sub 6}), methanol (CH{sub 3}OH), and CO{sub 2} detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

  3. DNA methylation perturbations in genes involved in polyunsaturated Fatty Acid biosynthesis associated with depression and suicide risk.

    Science.gov (United States)

    Haghighi, Fatemeh; Galfalvy, Hanga; Chen, Sean; Huang, Yung-Yu; Cooper, Thomas B; Burke, Ainsley K; Oquendo, Maria A; Mann, J John; Sublette, M Elizabeth

    2015-01-01

    Polyunsaturated fatty acid (PUFA) status has been associated with neuropsychiatric disorders, including depression and risk of suicide. Long-chain PUFAs (LC-PUFAs) are obtained in the diet or produced by sequential desaturation and elongation of shorter-chain precursor fatty acids linoleic acid (LA, 18:2n-6) and α-linolenic acid (ALA, 18:3n-3). We compared DNA methylation patterns in genes involved in LC-PUFA biosynthesis in major depressive disorder (MDD) with (n = 22) and without (n = 39) history of suicide attempt, and age- and sex-matched healthy volunteers (n = 59). Plasma levels of selected PUFAs along the LC-PUFA biosynthesis pathway were determined by transesterification and gas chromatography. CpG methylation levels for the main human LC-PUFA biosynthetic genes, fatty acid desaturases 1 (Fads1) and 2 (Fads2), and elongation of very long-chain fatty acids protein 5 (Elovl5), were assayed by bisulfite pyrosequencing. Associations between PUFA levels and diagnosis or suicide attempt status did not survive correction for multiple testing. However, MDD diagnosis and suicide attempts were significantly associated with DNA methylation in Elovl5 gene regulatory regions. Also the relative roles of PUFA levels and DNA methylation with respect to diagnostic and suicide attempt status were determined by least absolute shrinkage and selection operator logistic regression analyses. We found that PUFA associations with suicide attempt status were explained by effects of Elovl5 DNA methylation within the regulatory regions. The observed link between plasma PUFA levels, DNA methylation, and suicide risk may have implications for modulation of disease-associated epigenetic marks by nutritional intervention.

  4. DNA methylation perturbations in genes involved in polyunsaturated fatty acid biosynthesis associated with depression and suicide risk

    Directory of Open Access Journals (Sweden)

    Fatemeh eHaghighi

    2015-04-01

    Full Text Available Polyunsaturated fatty acid (PUFA status has been associated with neuropsychiatric disorders, including depression and risk of suicide. Long-chain PUFAs (LC-PUFAs are obtained in the diet or produced by sequential desaturation and elongation of shorter-chain precursor fatty acids linoleic acid (LA, 18:2n-6 and α-linolenic acid (ALA, 18:3n-3. We compared DNA methylation patterns in genes involved in LC-PUFA biosynthesis in major depressive disorder (MDD with (n=22 and without (n=39 history of suicide attempt, and age- and sex-matched healthy volunteers (n=59. Plasma levels of selected PUFAs along the LC-PUFA biosynthesis pathway were determined by transesterification and gas chromatography. CpG methylation levels for the main human LC-PUFA biosynthetic genes, fatty acid desaturases 1 (Fads1 and 2 (Fads2, and elongation of very long chain fatty acids protein 5 (Elovl5, were assayed by bisulfite pyrosequencing. Associations between PUFA levels and diagnosis or suicide attempt status did not survive correction for multiple testing. However, MDD diagnosis and suicide attempts were significantly associated with DNA methylation in Elovl5 gene regulatory regions. Also the relative roles of PUFA levels and DNA methylation with respect to diagnostic and suicide attempt status were determined by least absolute shrinkage and selection operator (LASSO logistic regression analyses. We found that PUFA associations with suicide attempt status were explained by effects of Elovl5 DNA methylation within the regulatory regions. The observed link between plasma PUFA levels, DNA methylation, and suicide risk may have implications for modulation of disease-associated epigenetic marks by nutritional intervention.

  5. beta-Methyl-15-p-iodophenylpentadecanoic acid metabolism and kinetics in the isolated rat heart.

    Science.gov (United States)

    DeGrado, T R; Holden, J E; Ng, C K; Raffel, D M; Gatley, S J

    1989-01-01

    The use of 15-p-iodophenyl-beta-methyl-pentadecanoic acid (beta Me-IPPA) as an indicator of long chain fatty acid (LCFA) utilization in nuclear medicine studies was evaluated in the isolated, perfused, working rat heart. Time courses of radioactivity (residue curves) were obtained following bolus injections of both beta Me-IPPA and its straight chain counterpart 15-p-iodophenyl-pentadecanoic acid (IPPA). IPPA kinetics clearly indicated flow independent impairment of fatty acid oxidation caused by the carnitine palmitoyltransferase I inhibitor 2[5(4-chlorophenyl)pentyl]oxirane-2-carboxylate (POCA). In contrast, beta Me-IPPA kinetics were insensitive to changes in fatty acid oxidation rate and net utilization of long chain fatty acid. Analysis of radiolabeled species in coronary effluent and heart homogenates showed the methylated fatty acid to be readily incorporated into complex lipids but a poor substrate for oxidation. POCA did not significantly alter metabolism of the tracer, suggesting that the tracer is poorly metabolized beyond beta Me-IPPA-CoA in the oxidative pathway.

  6. beta. -methyl-15-p-iodophenylpentadecanoic acid metabolism and kinetics in the isolated rat heart

    Energy Technology Data Exchange (ETDEWEB)

    DeGrado, T.R.; Holden, J.E.; Ng, C.K.; Raffel, D.M.; Gatley, S.J.

    1989-02-01

    The use of 15-p-iodophenyl-..beta..-methyl-pentadecanoic acid (..beta..Me-IPPA) as an indicator of long chain fatty acid (LCFA) utilization in nuclear medicine studies was evaluated in the isolated, perfused, working rat heart. Time courses of radioactivity (residue curves) were obtained following bolus injections of both ..beta..Me-IPPA and its straight chain counterpart 15-p-iodophenyl-pentadecanoic acid (IPPA). IPPA kinetics clearly indicated flow independent impairment of fatty acid oxidation caused by the carnitine palmitoyltransferase I inhibitor 2(5(4-chlorophenyl)pentyl)oxirane-2-carboxylate (POCA). In contrast, ..beta..Me-IPPA kinetics were insensitive to changes in fatty acid oxidation rate and net utilization of long chain fatty acid. Analysis of radiolabeled species in coronary effluent and heart homogenates showed the methylated fatty acid to be readily incorporated into complex lipids but a poor substrate for oxidation. POCA did not significantly alter metabolism of the tracer, suggesting that the tracer is poorly metabolized beyond ..beta..Me-IPPA-CoA in the oxidative pathway.

  7. Pharmacokinetics of vinyl chloride in the rat

    International Nuclear Information System (INIS)

    Bolt, H.M.; Laib, R.J.; Kappus, H.; Buchter, A.

    1977-01-01

    When rats are exposed to [ 14 C]vinyl chloride in a closed system, the vinyl chloride present in the atmosphere equilibrates with the animals' organism within 15 min. The course of equilibration could be determined using rats which had been given 6-nitro-1,2,3-benzothiadiazole. This compound completely blocks metabolism of vinyl chloride. The enzymes responsible for metabolism of vinyl chloride are saturated at an atmospheric concentration of vinyl chloride of 250 ppm. Pharmacokinetic analysis shows that no significant cumulation of vinyl chloride or its major metabolites is to be expected on repeated administration of vinyl chlorides. This may be consistent with the theory that a reactive, shortly living metabolite which occurs in low concentration only, may be responsible for the toxic effects of vinyl chloride

  8. Influence of Fatty Acid Methyl Esters on Fuel properties of Biodiesel ...

    African Journals Online (AJOL)

    Influence of Fatty Acid Methyl Esters on Fuel properties of Biodiesel Produced from the. Seeds Oil of Curcubita ... Gas chromatograph coupled with mass spectrophotometer (GC-MS). The results indicate ..... Chemical and physical properties of ...

  9. Radical Cationic Pathway for the Decay of Ionized Glyme Molecules in Liquid Solution.

    Science.gov (United States)

    Taletskiy, Konstantin S; Borovkov, Vsevolod I; Schegoleva, Lyudmila N; Beregovaya, Irina V; Taratayko, Andrey I; Molin, Yuriy N

    2015-11-12

    Chemical stability of primary radical cations (RCs) generated in irradiated matter determines substantially the radiation resistance of organic materials. Transformations of the RCs of the glyme molecules, R(-O-CH2-CH2-)nO-R (R = CH3, n = 1-4) has been studied on the nanosecond time scale by measuring the magnetic field effects in the recombination fluorescence from irradiated liquid solutions of the glymes. In all cases, the RCs observed were different from that expected for the primary ones and revealed very similar hyperfine couplings independent of the poly(ethylene oxide) chain length and of the substitution of terminal methyl groups by C2H5 or CH2CH2Cl, as has been shown with diglyme as an example. Quantum chemical analysis of possible chemical transformations for the monoglyme RC as a model system allowed us to discover the reaction pathway yielding the methyl vinyl ether RC. The pathway involves intramolecular proton transfer followed by C-O bond cleavage. Only one (-O-CH2-CH2-O-) fragment is involved in this transformation, which is nearly barrierless due to the catalytic effect of adjacent glyme molecules. The rapid formation of the methyl vinyl ether RC in the irradiated monoglyme was confirmed by the numerical simulation of the experimental curves of the time-resolved magnetic field effect. These findings suggest that the R'-O-CH═CH2(•+) formation is a typical decay pathway for the primary RCs in irradiated liquid glymes.

  10. Methyl tert-butyl ether biodegradation by indigenous aquifer microorganisms under natural and artificial oxic conditions

    Science.gov (United States)

    Landmeyer, J.E.; Chapelle, F.H.; Herlong, H.H.; Bradley, P.M.

    2001-01-01

    Microbial communities indigenous to a shallow groundwater system near Beaufort, SC, degraded milligram per liter concentrations of methyl tert-butyl ether (MTBE) under natural and artificial oxic conditions. Significant MTBE biodegradation was observed where anoxic, MTBE-contaminated groundwater discharged to a concrete-lined ditch. In the anoxic groundwater adjacent to the ditch, concentrations of MTBE were > 1 mg/L. Where groundwater discharge occurs, dissolved oxygen (DO) concentrations beneath the ditch exceeded 1.0 mg/L to a depth of 1.5 m, and MTBE concentrations decreased to CO2 in laboratory liquid culture studies, with no accumulation of intermediate compounds. Upgradient of the ditch in the anoxic, MTBE and BTEX-contaminated aquifer, addition of a soluble oxygen release compound resulted in oxic conditions and rapid MTBE biodegradation by indigenous microorganisms. In an observation well located closest to the oxygen addition area, DO concentrations increased from 0.4 to 12 mg/L in <60 days and MTBE concentrations decreased from 20 to 3 mg/L. In the same time period at a downgradient observation well, DO increased from <0.2 to 2 mg/L and MTBE concentrations decreased from 30 to <5 mg/L. These results indicate that microorganisms indigenous to the groundwater system at this site can degrade milligram per liter concentrations of MTBE under natural and artificial oxic conditions.

  11. Risk characterization of methyl tertiary butyl ether (MTBE) in tap water.

    Science.gov (United States)

    Stern, B R; Tardiff, R G

    1997-12-01

    Methyl tertiary butyl ether (MTBE) can enter surface water and groundwater through wet atmospheric deposition or as a result of fuel leaks and spills. About 30% of the U.S. population lives in areas where MTBE is in regular use. Ninety-five percent of this population is unlikely to be exposed to MTBE in tap water at concentrations exceeding 2 ppb, and most will be exposed to concentrations that are much lower and may be zero. About 5% of this population may be exposed to higher levels of MTBE in tap water, resulting from fuel tank leaks and spills into surface or groundwater used for potable water supplies. This paper describes the concentration ranges found and anticipated in surface and groundwater, and estimates the distribution of doses experienced by humans using water containing MTBE to drink, prepare food, and shower/bathe. The toxic properties (including potency) of MTBE when ingested, inhaled, and in contact with the skin are summarized. Using a range of human toxic potency values derived from animal studies, margins of exposure (MOE) associated with alternative chronic exposure scenarios are estimated to range from 1700 to 140,000. Maximum concentrations of MTBE in tap water anticipated not to cause adverse health effects are determined to range from 700 to 14,000 ppb. The results of this analysis demonstrate that no health risks are likely to be associated with chronic and subchronic human exposures to MTBE in tap water. Although some individuals may be exposed to very high concentrations of MTBE in tap water immediately following a localized spill, these exposures are likely to be brief in duration due to large-scale dilution and rapid volatilization of MTBE, the institution of emergency response and remediation measures to minimize human exposures, and the low taste and odor thresholds of MTBE which ensure that its presence in tap water is readily detected at concentrations well below the threshold for human injury.

  12. Growth and characterization of an organic single crystal: 2-[2-(4-Diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide

    Science.gov (United States)

    Senthil, K.; Kalainathan, S.; Ruban Kumar, A.

    Optically transparent crystal of the organic salt DEASI (2-[2-(4-Diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide) has been synthesized by using knoevenagel condensation reaction method. The synthesized material has been purified by successfully recrystallization process. Single crystals of DEASI have been grown by slow evaporation technique at room temperature. The solubility of the title material has been determined at different temperature in acetonitrile/methanol mixture. The cell parameters and crystallinity of the title crystal were determined by single crystal XRD. The powder diffraction was carried out to study the reflection plane of the grown crystal and diffraction peaks were indexed. The presence of different functional groups in the crystal was confirmed by Fourier transform infrared (FTIR) analysis. 1H NMR spectrum was recorded to confirm the presence of hydrogen nuclei in the synthesized material. The optical property of the title crystal was studied by UV-Vis-NIR spectroscopic analysis. The melting point and thermal property of DEASI were studied using TGA/DSC technique. The Vicker’s hardness (Hv) was carried out to know the category. The dielectric constant and dielectric loss of the compound decreases with an increase in frequencies. Chemical etching studies showed that the DEASI grows in the two dimensional growth mechanisms. The Kurtz-Perry powder second harmonic generation (SHG) test has done for title crystal.

  13. Growth and characterization of an organic single crystal: 2-[2-(4-diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide.

    Science.gov (United States)

    Senthil, K; Kalainathan, S; Ruban Kumar, A

    2014-05-05

    Optically transparent crystal of the organic salt DEASI (2-[2-(4-Diethylamino-phenyl)-vinyl]-1-methyl-pyridinium iodide) has been synthesized by using knoevenagel condensation reaction method. The synthesized material has been purified by successfully recrystallization process. Single crystals of DEASI have been grown by slow evaporation technique at room temperature. The solubility of the title material has been determined at different temperature in acetonitrile/methanol mixture. The cell parameters and crystallinity of the title crystal were determined by single crystal XRD. The powder diffraction was carried out to study the reflection plane of the grown crystal and diffraction peaks were indexed. The presence of different functional groups in the crystal was confirmed by Fourier transform infrared (FTIR) analysis. (1)H NMR spectrum was recorded to confirm the presence of hydrogen nuclei in the synthesized material. The optical property of the title crystal was studied by UV-Vis-NIR spectroscopic analysis. The melting point and thermal property of DEASI were studied using TGA/DSC technique. The Vicker's hardness (Hv) was carried out to know the category. The dielectric constant and dielectric loss of the compound decreases with an increase in frequencies. Chemical etching studies showed that the DEASI grows in the two dimensional growth mechanisms. The Kurtz-Perry powder second harmonic generation (SHG) test has done for title crystal. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Polyoxyethylene alkyl ether carboxylic acids: An overview of a neglected class of surfactants with multiresponsive properties.

    Science.gov (United States)

    Chiappisi, Leonardo

    2017-12-01

    In this work, an overview on aqueous solutions of polyoxyethylene alkyl ether carboxylic acids is given. Unique properties arise from the combination of the nonionic, temperature-responsive polyoxyethylene block with the weakly ionic, pH-responsive carboxylic acid termination in a single surfactant headgroup. Accordingly, this class of surfactant finds broad application across very different sectors. Despite their large use on an industrial and a technical scale, the literature lacks a systematic and detailed characterization of their physico-chemical properties which is provided herein. In addition, a comprehensive overview is given of their self-assembly and interfacial behavior, of their use as colloidal building blocks and for large-scale applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Responses of the L51781Y tk/sup +//tk/sup -/ mouse lymphoma cell forward mutation assay: III. 72 coded chemicals

    Energy Technology Data Exchange (ETDEWEB)

    McGregor, D.B.; Brown, A.; Cattanach, P.; Edwards, I.; McBride, D.; Riach, C.; Caspary, W.J.

    1988-01-01

    Seventy-two chemicals were tested for their mutagenic potential in the L51781Y tk/sup +///sup -/ mouse lymphoma cell forward mutation assay, using procedures based upon those described previously. Cultures were exposed to the chemicals for 4 hr, then cultured for 2 days before planting in soft agar with or without trifluorothymidine (TFT), 3 ..mu..g/ml. The chemicals were tested at least twice. Significant responses were obtained with allyl isothiocyanate, p-benzoquinone dioxime, benzyl acetate, 2-biphenylamine HCl, bis(2-chloro-1-methylethyl)ether, cadmium chloride, chlordane, chlorobenzene, chlorobenzilate, 2-chloroethanol, chlorothalonil, cytarabine x HCl, p,p'-DDE, diazinon, 2,6-dichloro-p-phenylenediamine, N,N-diethylthiourea, diglycidylresorcinol ether, 2,4-dimethoxy aniline x HCl, disperse yellow 3, endosulfan, 1,2-epoxyhexadecane, ethyl acrylate, ethyl benzene, ethylene thiourea, F D and C yellow Number 6, furan, heptachlor, isophorone, mercuric chloride, 4,4'-methylenedianiline x 2 HCl, methyl viologen, nickel sulfate x 6H/sub 2/O, 4,4'-oxydianiline, pentachloroethane, piperonyl butoxide, propyl gallate, quinoline, rotenone, 2,4,5,6-tetrachloro-4-nitro-anisole, 1,1,1,2-tetrachloroethane, trichlorfon, 2,4,6-trichlorophenol, 2,4,5-trimethoxybenzaldehyde, 1,1,3-trimethyl-2-thiourea, 1-vinyl-3-cyclopetene dioxide, vinyl toluene, and ziram. The assay was incapable of providing a clear indication of whether some chemicals were mutagens; these benzyl alcohol, 1,4-dichlorobenzene, phenol, succinic acid-2,2-dimethyl hydrazide, and toluene.

  16. Ferrocene Compounds. XXVI. C- and O-Ferrocenylalkylation of Methyl Salicylate

    OpenAIRE

    Kovač, Veronika; Rapić, Vladimir; Alagić, Jasmina; Barišić, Lidija

    1999-01-01

    Reaction of equimolar amounts of methyl salicylate, sodium and N,N,N-trimethylferrocylammonium iodide (1a) in ethanol gave 55% of ethyl 1-ferrocenylethyl ether (4). By refluxing a solution of 9 mmol sodium and 3 mmol of FcCHRNMe3I (1a, R = H; 1b, R = Me; 1c, R = Ph) in a large excess of methyl salicylate for 2-3 hours, the corresponding methyl 5-ferrocylsalicylates (5) (10-23%) and methyl-3-ferrocylsalicylates (6) (12-20%) were obtained. During conversion of salt 1b, besides of 5b and 6b, 20%...

  17. 21 CFR 172.225 - Methyl and ethyl esters of fatty acids produced from edible fats and oils.

    Science.gov (United States)

    2010-04-01

    ... from edible fats and oils. 172.225 Section 172.225 Food and Drugs FOOD AND DRUG ADMINISTRATION... Methyl and ethyl esters of fatty acids produced from edible fats and oils. Methyl esters and ethyl esters of fatty acids produced from edible fats and oils may be safely used in food, subject to the...

  18. Crystallisation of hydroxyapatite in phosphorylated poly(vinyl alcohol) as a synthetic route to tough mechanical hybrid materials

    International Nuclear Information System (INIS)

    Kusakabe, Akane; Hirota, Ken; Mizutani, Tadashi

    2017-01-01

    Partially phosphorylated poly(vinyl alcohol) was prepared by treating poly(vinyl alcohol) with 100% phosphoric acid, and 5, 10 and 20% of the hydroxyl groups were converted to phosphoric acid ester. Addition of Ca 2+ to an aqueous solution of phosphorylated poly(vinyl alcohol) gave a transparent gel. Five cycles of alternate soaking of the gel in aqueous CaCl 2 and aqueous (NH 4 ) 2 HPO 4 were carried out to crystallise hydroxyapatite (HAP) in the phosphorylated poly(vinyl alcohol) matrix. The X-ray diffraction peaks of HAP formed in 5% phosphorylated PVA were sharp, while those of HAP formed in 20% phosphorylated PVA were broad. The contents of inorganic phase in the hybrid powder were increased from 58 to 76 wt% as the fraction of phosphate groups in the gel was decreased from 20% to 5%. The hybrid powder was first subjected to uniaxial pressing, followed by cold isostatic pressing (CIP) and warm isostatic pressing (WIP) at 120 °C at pressures of 300–980 MPa, to obtain the specimens for three-point bending test. These hybrid specimens showed bending strengths of 15–53 MPa. The hybrid compacts prepared from 10% phosphorylated poly(vinyl alcohol) showed the smallest Young's modulus, the largest displacement at break, and the largest fracture energy, showing that it has the highest toughness among the hybrid materials prepared from poly(vinyl alcohol) with varying degrees of phosphorylation. - Graphical abstract: Densification of hydroxyapatite crystallised in 10% phosphorylated poly(vinyl alcohol) gave the toughest compact. - Highlights: • Hydroxyapatite was crystallised in phosphorylated poly(vinyl alcohol) gels. • Crystallite size of hydroxyapatite decreased as phosphate density was increased. • The hybrid specimens prepared in 10% phosphorylated gel was the toughest. • Phosphate density in organic matrix regulated the mechanical properties of the hybrid.

  19. Crystallisation of hydroxyapatite in phosphorylated poly(vinyl alcohol) as a synthetic route to tough mechanical hybrid materials

    Energy Technology Data Exchange (ETDEWEB)

    Kusakabe, Akane; Hirota, Ken; Mizutani, Tadashi, E-mail: tmizutan@mail.doshisha.ac.jp

    2017-01-01

    Partially phosphorylated poly(vinyl alcohol) was prepared by treating poly(vinyl alcohol) with 100% phosphoric acid, and 5, 10 and 20% of the hydroxyl groups were converted to phosphoric acid ester. Addition of Ca{sup 2+} to an aqueous solution of phosphorylated poly(vinyl alcohol) gave a transparent gel. Five cycles of alternate soaking of the gel in aqueous CaCl{sub 2} and aqueous (NH{sub 4}){sub 2}HPO{sub 4} were carried out to crystallise hydroxyapatite (HAP) in the phosphorylated poly(vinyl alcohol) matrix. The X-ray diffraction peaks of HAP formed in 5% phosphorylated PVA were sharp, while those of HAP formed in 20% phosphorylated PVA were broad. The contents of inorganic phase in the hybrid powder were increased from 58 to 76 wt% as the fraction of phosphate groups in the gel was decreased from 20% to 5%. The hybrid powder was first subjected to uniaxial pressing, followed by cold isostatic pressing (CIP) and warm isostatic pressing (WIP) at 120 °C at pressures of 300–980 MPa, to obtain the specimens for three-point bending test. These hybrid specimens showed bending strengths of 15–53 MPa. The hybrid compacts prepared from 10% phosphorylated poly(vinyl alcohol) showed the smallest Young's modulus, the largest displacement at break, and the largest fracture energy, showing that it has the highest toughness among the hybrid materials prepared from poly(vinyl alcohol) with varying degrees of phosphorylation. - Graphical abstract: Densification of hydroxyapatite crystallised in 10% phosphorylated poly(vinyl alcohol) gave the toughest compact. - Highlights: • Hydroxyapatite was crystallised in phosphorylated poly(vinyl alcohol) gels. • Crystallite size of hydroxyapatite decreased as phosphate density was increased. • The hybrid specimens prepared in 10% phosphorylated gel was the toughest. • Phosphate density in organic matrix regulated the mechanical properties of the hybrid.

  20. Synthesis and Characterization of Fatty Acid Methyl Ester by In-Situ Transesterification in Capparis Deciduas Seed

    Directory of Open Access Journals (Sweden)

    Prasad E FUNDE

    2008-12-01

    Full Text Available (FAME Fatty acid methyl ester is made virgin or used vegetable oils (both edible and non-edible and animal fats. Fatty acid methyl ester operates in compression ignition engines like petro-diesel. Fatty acid methyl ester can be blended in any ratio with petroleum diesel fuels. It can be stored just like the petroleum diesel fuel. Petrodiesel can be replaced by biodiesel due to its superiority. It has various advantages. The seeds of Capparis deciduas are found to contain non-edible oil in the range of about 63.75 %. The percentage of biodiesel yield increases with concentration of KOH as a catalyst. The aim of this article is to demonstrate the cost effective new source of energy by single step reaction i.e. production of oil by combining extraction and reaction of extract with the mixture of alcohols. In this article the effect of catalyst concentration, time, water content and temperature on in-situ transesterification is studied to obtain optimum yield and Fatty acid methyl ester (Biodiesel Fuel characterization tests show the striking similarity of various physical & chemical properties and campers to ASTM standards.

  1. 4-[(2-Hydroxy-4-pentadecyl-benzylidene-amino]-benzoic Acid Methyl Ester

    Directory of Open Access Journals (Sweden)

    Gadada Naganagowda

    2013-11-01

    Full Text Available A new Schiff base, 4-[(2-hydroxy-4-pentadecyl-benzylidene-amino]-benzoic acid methyl ester was synthesized and its UV, IR, 1H-NMR, 13C-NMR and ESI-MS spectroscopic data are presented.

  2. Alternative fuel properties of tall oil fatty acid methyl ester-diesel fuel blends

    Energy Technology Data Exchange (ETDEWEB)

    Altiparmak, D.; Keskin, A.; Koca, A. [Gazi University, Ankara (Turkey). Technical Education Faculty; Guru, M. [Gazi University, Ankara (Turkey). Engineering and Architectural Faculty

    2007-01-15

    In this experimental work, tall oil methyl ester-diesel fuel blends as alternative fuels for diesel engines were studied. Tall oil methyl ester was produced by reacting tall oil fatty acids with methyl alcohol under optimum conditions. The blends of tall oil methyl ester-diesel fuel were tested in a direct injection diesel engine at full load conditions. The effects of the new fuel blends on the engine performance and exhaust emission were tested. It was observed that the engine torque and power output with tall oil methyl ester-diesel fuel blends increased up to 6.1% and 5.9%, respectively. It was also seen that CO emissions decreased to 38.9% and NO{sub x} emissions increased up to 30% with the new fuel blends. The smoke capacity did not vary significantly. (author)

  3. Alternative fuel properties of tall oil fatty acid methyl ester-diesel fuel blends.

    Science.gov (United States)

    Altiparmak, Duran; Keskin, Ali; Koca, Atilla; Gürü, Metin

    2007-01-01

    In this experimental work, tall oil methyl ester-diesel fuel blends as alternative fuels for diesel engines were studied. Tall oil methyl ester was produced by reacting tall oil fatty acids with methyl alcohol under optimum conditions. The blends of tall oil methyl ester-diesel fuel were tested in a direct injection diesel engine at full load condition. The effects of the new fuel blends on the engine performance and exhaust emission were tested. It was observed that the engine torque and power output with tall oil methyl ester-diesel fuel blends increased up to 6.1% and 5.9%, respectively. It was also seen that CO emissions decreased to 38.9% and NO(x) emissions increased up to 30% with the new fuel blends. The smoke opacity did not vary significantly.

  4. Calcium carbonate growth in the presence of water soluble cellulose ethers

    International Nuclear Information System (INIS)

    Zhang Fengju; Yang Xinguo; Tian Fei

    2009-01-01

    Calcium carbonate precipitation was performed in the presence of methyl cellulose (MC) and two kinds of hydroxyethyl cellulose (HEC FD-10000, HEC FD-30000). The results demonstrated that the final product morphology and structure of CaCO 3 crystals are highly sensitive to the concentration of the cellulose ethers aqueous solution. By precisely controlling their concentrations, all these three cellulose ethers solutions have the ability of protecting metastable vaterite from thermodynamically transforming into stable calcite. The intermediate products investigation showed to some extent the phase transformation of calcium carbonate in its growing process from metastable vaterite to calcite and indicated that the calcium carbonate crystal growth in HEC solutions occurs through dissolution and reprecipitation process. Calcium carbonate growth in both presence of HEC and ethanol or Mg 2+ was also examined. This work demonstrates the potential of water soluble cellulose ethers in controlling biominerals crystallization and growth. The results are revelatory for biomineralization and fabricating new organic-inorganic hybrids based on cellulose derivatives.

  5. No effect of folic acid supplementation on global DNA methylation in men and women with moderately elevated homocysteine.

    Directory of Open Access Journals (Sweden)

    Audrey Y Jung

    Full Text Available A global loss of cytosine methylation in DNA has been implicated in a wide range of diseases. There is growing evidence that modifications in DNA methylation can be brought about by altering the intake of methyl donors such as folate. We examined whether long-term daily supplementation with 0.8 mg of folic acid would increase global DNA methylation compared with placebo in individuals with elevated plasma homocysteine. We also investigated if these effects were modified by MTHFR C677T genotype. Two hundred sixteen participants out of 818 subjects who had participated in a randomized double-blind placebo-controlled trial were selected, pre-stratified on MTHFR C677T genotype and matched on age and smoking status. They were allocated to receive either folic acid (0.8 mg/d; n = 105 or placebo treatment (n = 111 for three years. Peripheral blood leukocyte DNA methylation and serum and erythrocyte folate were assessed. Global DNA methylation was measured using liquid chromatography-tandem mass spectrometry and expressed as a percentage of 5-methylcytosines versus the total number of cytosine. There was no difference in global DNA methylation between those randomized to folic acid and those in the placebo group (difference = 0.008, 95%CI = -0.05,0.07, P = 0.79. There was also no difference between treatment groups when we stratified for MTHFR C677T genotype (CC, n = 76; CT, n = 70; TT, n = 70, baseline erythrocyte folate status or baseline DNA methylation levels. In moderately hyperhomocysteinemic men and women, long-term folic acid supplementation does not increase global DNA methylation in peripheral blood leukocytes.ClinicalTrials.gov NCT00110604.

  6. No effect of folic acid supplementation on global DNA methylation in men and women with moderately elevated homocysteine.

    Science.gov (United States)

    Jung, Audrey Y; Smulders, Yvo; Verhoef, Petra; Kok, Frans J; Blom, Henk; Kok, Robert M; Kampman, Ellen; Durga, Jane

    2011-01-01

    A global loss of cytosine methylation in DNA has been implicated in a wide range of diseases. There is growing evidence that modifications in DNA methylation can be brought about by altering the intake of methyl donors such as folate. We examined whether long-term daily supplementation with 0.8 mg of folic acid would increase global DNA methylation compared with placebo in individuals with elevated plasma homocysteine. We also investigated if these effects were modified by MTHFR C677T genotype. Two hundred sixteen participants out of 818 subjects who had participated in a randomized double-blind placebo-controlled trial were selected, pre-stratified on MTHFR C677T genotype and matched on age and smoking status. They were allocated to receive either folic acid (0.8 mg/d; n = 105) or placebo treatment (n = 111) for three years. Peripheral blood leukocyte DNA methylation and serum and erythrocyte folate were assessed. Global DNA methylation was measured using liquid chromatography-tandem mass spectrometry and expressed as a percentage of 5-methylcytosines versus the total number of cytosine. There was no difference in global DNA methylation between those randomized to folic acid and those in the placebo group (difference = 0.008, 95%CI = -0.05,0.07, P = 0.79). There was also no difference between treatment groups when we stratified for MTHFR C677T genotype (CC, n = 76; CT, n = 70; TT, n = 70), baseline erythrocyte folate status or baseline DNA methylation levels. In moderately hyperhomocysteinemic men and women, long-term folic acid supplementation does not increase global DNA methylation in peripheral blood leukocytes.ClinicalTrials.gov NCT00110604.

  7. Radiation-induced graft copolymerization of methyl acrylate and acrylic acid onto rubber wood fiber

    International Nuclear Information System (INIS)

    Saliza Jam; Mansor Ahmad; Wan Md Zin Wan Yunus; Khairul Zaman Mohd Dahlan

    2001-01-01

    Graft copolymerization of methyl acrylate and acrylic acid monomers onto rubber wood fiber (RWF) was carried out by simultaneous radiation-induced technique. The parameters affecting the grafting reaction were investigated and the optimum conditions for both monomers obtained are as follows: impregnation time = 16 hours, total dose = 30 kGy, methanol : water ratio, 3:1, monomers concentration = 40 v/v % and sulphuric acid concentration = 0.1 mol/L. Fourier Transform Infrared (FTIR), thermogravimetry analysis (TGA), and scanning electron microscope (SEM) analyses used to characterize graft copolymers. The structural investigation by x-ray diffraction (XRD) shows the degree of crystallinity of rubber wood fiber decreased with the incorporation of poly(methyl acrylate) and poly(acrylic acid) grafts. (Author)

  8. Behaviour of Some Activated Nitriles Toward Barbituric Acid, Thiobarbituric Acid and 3-Methyl-1-Phenylpyrazol-5-one

    Directory of Open Access Journals (Sweden)

    M. M. Habashy

    2000-05-01

    Full Text Available The effect of some active methylene containing heterocyclic compounds, namely barbituric acid, thiobarbituric acid and 3-methyl-1-phenylpyrazol-5-one on a-cyano-3,4,5-trimethoxycinnamonitrile and ethyl a-cyano-3,4,5-trimethoxycinnamate (1a,b was investigated. The structure of the new products was substantiated by their IR,1H-NMR and mass spectra.

  9. Decontamination efficiency of a sheet of vinyl wall paper as a surface material in radioisotope laboratory

    International Nuclear Information System (INIS)

    Furukawa, Kazuhiko; Funadera, Kanako

    1989-01-01

    It has long been desired to prevent surface materials from cracking in a radioisotope laboratory. We applied a sheet of nonflammable wall paper, vinyl cloth, as a surface material to cover concrete wall. It was sufficiently resistant to the reinforced concrete wall cracking. The efficiency of the decontamination of the vinyl cloth was compared with those of stainless steel, iron and painted plates. The contamination and decontamination indices were determined in these surface materials after contamination with [ 32 P]orthophosphate (pH 3, 7 and 11) for 0 to 48 h. Both of the indices of the vinyl cloth were higher than those of the other materials. Further, it was confirmed that the vinyl cloth was resistant to acid and alkaline conditions and radioisotopes could not be permeable. The wipe off efficiency was also investigated in these materials by use of several decontamination detergents. In any reagents tested, the wipe of efficiency of the vinyl cloth was more than 80%. Thus, the vinyl cloth could be used for the surface material and is one of good surface materials in a radioisotope laboratory. (author)

  10. 8-Methoxypsoralen-nucleic acid photoreaction. Effect of methyl substitution on pyrone vs. furan photoaddition

    International Nuclear Information System (INIS)

    Kanne, D.; Rapoport, H.; Hearst, J.E.

    1984-01-01

    We have synthesized a series of 8-[3H]methoxypsoralens in which methyl and hydrogen are systematically varied at the 4- and 5'-positions. Analysis of the products resulting from the photoaddition of these four psoralens with the nucleic acid poly(dA-dT) reveals that the product distribution depends on the presence or absence of a 4-methyl substituent. Compounds with the 4-methyl group show an overwhelming preference (approximately 98%) for addition to the furan double bond, while compounds without the 4-methyl show a substantial amount (approximately 18%) of addition to the pyrone double bond

  11. Synthesis of acetylenic derivatives of hydroxynaphthoquinone

    International Nuclear Information System (INIS)

    Sanchez Kopper, Andres

    2010-01-01

    The acetylene derivatives synthesis 2-hydroxy-1 ,4-naphthoquinones was studied using different reaction conditions: coupling with copper and silver acetylides, Sonogashira reaction with and without CU (I) as cocatalyst. The reaction conditions are optimized for coupling of iodine lawson and ylide phenyl lawsone of iodine with various terminal acetylenes: phenyl acetylene, propargyl alcohol, 1-heptin and 2-methyl-3-butyne-2-ol. Also, reactants such as bromides of hidroxinaphthoquinones were used with protecting groups such as acetate, methoxy, phenyloxy, benzyloxy and tricloroetoxy. The synthesis of 2-hydroxy-3-(3-hydroxy-3-ynyl-1-methylbutane)-1,4-naphthoquinone, 2-methoxy-3-(2-phenylethynyl) -1,4-naphthoquinone and 2-(2-phenylethynyl)-3-(2,2,2-tricloroetoxy)-1,4-naphthoquinone was performed with rates of return of 22%, 57% and 67% respectively. The reaction of the yodolawsona was obtained with 3-chloro-3-methyl-1-butyne in the presence of CuI, CsI and Cs 2 Co 3 obtaining the enol ether: 3,3-dimethyl-2-methyl-2 ,3-dihydronaphto [2 ,3-b]furan-4,9-dione (dehydro-α-dunion), with a rate of return of 58%. This enol ether was used as a reactant for the formation, through a regioselective hydrogenation with PtO 2 /t-butanol of α-dunion with a yield of 50%. Furthermore, by acid hydrolysis with H 2 SO 4 has been possible to obtain a percentage yield of 75% streptocarpone. Both, α-dunion and streptocarpone, natural products extracted from Streptocarpus dunni shrub, with antiparasitic activity, and which so far had not presented an efficient synthesis. A mechanism is proposed for the reaction of formation of the enol ether where it is presumed the presence of a zwitterion-vinyl carbene as key intermediate of the reaction. All products were characterized by spectroscopy 1 H and 13 C-NMR, UV-Vis and IR. (author) [es

  12. Influence of Chemical Blends on Palm Oil Methyl Esters’ Cold Flow Properties and Fuel Characteristics

    Directory of Open Access Journals (Sweden)

    Obed M. Ali

    2014-07-01

    Full Text Available Alternative fuels, like biodiesel, are being utilized as a renewable energy source and an effective substitute for the continuously depleting supply of mineral diesel as they have similar combustion characteristics. However, the use of pure biodiesel as a fuel for diesel engines is currently limited due to problems relating to fuel properties and its relatively poor cold flow characteristics. Therefore, the most acceptable option for improving the properties of biodiesel is the use of a fuel additive. In the present study, the properties of palm oil methyl esters with increasing additive content were investigated after addition of ethanol, butanol and diethyl ether. The results revealed varying improvement in acid value, density, viscosity, pour point and cloud point, accompanied by a slight decrease in energy content with an increasing additive ratio. The viscosity reductions at 5% additive were 12%, 7%, 16.5% for ethanol, butanol and diethyl ether, respectively, and the maximum reduction in pour point was 5 °C at 5% diethyl ether blend. Engine test results revealed a noticeable improvement in engine brake power and specific fuel consumption compared to palm oil biodiesel and the best performance was obtained with diethyl ether. All the biodiesel-additive blend samples meet the requirements of ASTM D6751 biodiesel fuel standards for the measured properties.

  13. Chromatographic analyses of fatty acid methyl esters by HPLC-UV and GC-FID

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, Myller S.; Pinho, David M.M.; Suarez, Paulo A.Z., E-mail: psuarez@unb.br [Laboratorio de Materiais e Combustiveis, Instituto de Quimica, Universidade de Brasilia, DF (Brazil); Mendonca, Marcio A. [Faculdade de Agronomia e Medicina Veterinaria, Universidade de Brasilia, DF (Brazil); Resck, Ines S. [Laboratorio de Ressonancia Magnetica Nuclear, Universidade de Brasilia, DF (Brazil)

    2012-04-15

    An analytical method using high performance liquid chromatography with UV detection (HPLC-UV) (method A) was used for simultaneous determination of total amounts of triacylglycerides, diacylglycerides, monoacylglycerides and fatty acid methyl esters in alcoholysis of different oil (cotton, canola, sunflower, corn and soybean) samples. Analyses were carried out at 40 deg C for 20 min using a gradient of methanol (MeOH) and 2-propanol-hexane 5:4 (v/v) (PrHex): 100% of MeOH in 0 min, 50% of MeOH and 50% of PrHex in 10 min maintained with isocratic elution for 10 min. Another HPLC-UV method (method B) with acetonitrile isocratic elution for 34 min was used to determine the fatty acid composition of oils analyzing their methyl ester derivatives. Contents were determined with satisfactory repeatability (relative standard deviation, RSD < 3%), linearity (r{sup 2} > 0.99) and sensitivity (limit of quantification). Method B was compared with an official gas chromatographic method with flame ionization detection (GC-FID) from American Oil Chemists' Society (AOCS) in the determination of fatty acid methyl esters (FAME) in biodiesel real samples. (author)

  14. Blood pharmacokinetics of tertiary amyl methyl ether in male and female F344 rats and CD-1 mice after nose-only inhalation exposure.

    Science.gov (United States)

    Sumner, Susan C J; Janszen, Derek B; Asgharian, Bahman; Moore, Timothy A; Bobbitt, Carol M; Fennell, Timothy R

    2003-01-01

    Interest in understanding the biological behavior of aliphatic ethers has increased owing to their use as gasoline additives. The purpose of this study was to investigate the blood pharmacokinetics of the oxygenate tertiary amyl methyl ether (TAME), its major metabolite tertiary amyl alcohol (TAA) and acetone in rats and mice following inhalation exposure to TAME. Species differences in the area under the curve (AUC) for TAME were significant at each exposure concentration. For rats, the blood TAME AUC increased in proportion with an increase in exposure concentration. For mice, an increase in exposure concentration (100-500 ppm) resulted in a disproportional increase in the TAME AUC. Mice had greater (two- to threefold) blood concentrations of TAA compared with rats following exposure to 2500 or 500 ppm TAME. Mice had a disproportional increase in the TAA AUC with an increase in exposure concentration (100-500 ppm). This difference could result from saturation of a process (e.g. oxidation, glucuronide conjugation) that is involved in the further metabolism of TAA. For each species, gender and exposure concentration, acetone increased during exposure and returned to control values by 16 h following exposure. The source of acetone could be both as a metabolite of TAA or an effect on endogenous metabolism produced by exposure to TAME. Copyright 2003 John Wiley & Sons, Ltd.

  15. Vinyl Sulfonate/Vinyl Amide Copolymers and Different Surfactants As Suitable Systems in Eorat Higher Temperatures and Salinities Utilisation de mélanges de copolymères vinyl sulfonate/vinyl amide et de différents tensio-actifs en RAP dans des conditions de fortes salinités et de températures élevées

    Directory of Open Access Journals (Sweden)

    Von Halasz S. P.

    2006-11-01

    Full Text Available For enhanced oil recovery flooding processes there will be an increasing demand for polymers having high temperature and electrolyte stability. High molecular weight copolymers based on vinyl sulfonate, vinyl amide, and acryl amide show high performances in matching these demanding requirements. Surfactants are also known that are stable under these conditions, resulting in high deoiling rates. The aim of the present article is to demonstrate the influence of alkylphenol ethoxylates and their corresponding ether sulfonates on VS/VA/AM copolymer solutions. Aqueous solutions of such copolymers were added to varying quantities of nonionic and anionic surfactants at different temperatures using salinity scans. This article discusses the results of experiments with solutions of copolymers and surfactants in terms of compatibility, viscosity yield, flow properties, shear stability, injectability, thermostability, and oil recovery. Solutions of alkylphenol ethoxylates and/or ether sulfonates show nearly the same compatibility within a broad range of temperature and salinity, both with and without polymers. Relatively small amounts of surfactants are able to influence the EOR (Enhanced Oil Recovery properties of the polymer solutions, giving several interesting aspects for improved oil recovery. L'utilisation des polymères en récupération assistée du pétrole a fait apparaître un besoin croissant de polymères stables à haute température et à forte salinité. Les performances des terpolymères vinyl sulfonate/vinyl amide/acrylamide (VS/VA/VM ont montré que ces polymères remplissent de tels critères d'utilisation. On connaît également des tensio-actifs chimiquement stables dans ces mêmes conditions qui pourraient donc permettre d'obtenir des taux de récupération d'huile élevés. L'objectif de ce travail est de mettre en évidence l'influence de la présence d'alkylphénols éthoxyIates et des éthers sulfonates correspondants sur les

  16. Methylation of ribonucleic acid by the carcinogens dimethyl sulphate, N-methyl-N-nitrosourea and N-methyl-N′-nitro-N-nitrosoguanidine. Comparisons of chemical analyses at the nucleoside and base levels

    Science.gov (United States)

    Lawley, P. D.; Shah, S. A.

    1972-01-01

    1. The following methods for hydrolysis of methyl-14C-labelled RNA, and for chromatographic isolation and determination of the products, were investigated: enzymic digestion to nucleosides at pH6 or 8; alkaline hydrolysis and conversion into nucleosides; hydrolysis by acid to pyrimidine nucleotides and purine bases, or completely to bases; chromatography on Dowex 50 (NH4+ form) at pH6 or 8.9, or on Dowex 50 (H+ form), or on Sephadex G-10. 2. The suitability of the various methods for determination of methylation products was assessed. The principal product, 7-methylguanosine, was unstable under the conditions used for determinations of nucleosides. 3- and 7-Methyladenine and 3- and 7-methylguanine are best determined as bases; 1-methyladenine and 3-methylcytosine can be isolated as either nucleosides or bases; O6-methylguanine is unstable under the acid hydrolysis conditions used and can be determined as the nucleoside; 3-methyluracil was detected, but may be derived from methylation of the ionized form of uracil. 3. Differences between the patterns of methylation of RNA and homopolyribonucleotides by the N-methyl-N-nitroso compounds and dimethyl sulphate were found: the nitroso compounds were able to methylate O-6 of guanine, were relatively more reactive at N-7 of adenine and probably at N-3 of guanine, but less reactive at N-1 of adenine, N-3 of cytosine and probably at N-3 of uridine. They probably reacted more with the ribose–phosphate chain, but no products from this were identified. 4. The possible influences of these differences on biological action of the methylating agents is discussed. Nitroso compounds may differ principally in their ability to induce miscoding in the Watson–Crick sense by reaction at O-6 of guanine. Both types of agent may induce miscoding to a lesser extent through methylation at N-3 of guanine; both can methylate N atoms, presumably preventing Watson–Crick hydrogen-bonding. N-Methyl-N-nitrosourea can degrade RNA, possibly

  17. Adhesive PEG-based binder for aqueous fabrication of thick Li4Ti5O12 electrode

    International Nuclear Information System (INIS)

    Tran, Binh; Oladeji, Isaiah O.; Wang, Zedong; Calderon, Jean; Chai, Guangyu; Atherton, David; Zhai, Lei

    2013-01-01

    We report the first fully compressed Li 4 Ti 5 O 12 electrode designed by an aqueous process. An adhesive, elastomeric, and lithium ion conductive PEG-based copolymer is used as a binder for the aqueous fabrication thick, flexible, and densely packed Li 4 Ti 5 O 12 (LTO) electrodes. Self-adherent cathode films exceeding 200 μm in thickness and withholding high active mass loadings of 28 mg/cm 2 deliver 4.2 mAh/cm 2 at C/2 rate. Structurally defect-free electrodes are fabricated by casting aqueous cathode slurries onto nickel foam, dried, and hard-calendared at 10 tons/cm 2 . As a multifunctional material, the binder is synthesized by the copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA), methyl methacrylate (MMA), and isobutyl vinyl ether (IBVE) in optimal proportions. Furthermore, coordinating the binder with lithium salt is necessary for the electrode to function

  18. Alanine/epr pellet dosimeter using poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) copolymer as a binder for radiation dosimetry

    International Nuclear Information System (INIS)

    Beshir, W.B.; Ezz El-Din, H.M.; Abdel-fatth, A.A.; Ebraheem, S.

    2005-01-01

    A new alanine pellet dosimeter was developed for gamma and electron beam radiation dosimetry. Alanine powder was mixed with a new binding material, poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) copolymer. Pellets were prepared by pressing fine powder alanine with 60% copolymer binder by using hydraulic press and a specially designed pressing die. The radiation-formed stable free radicals were analysed by using electron paramagnetic resonance (EPR) spectroscopy. The useful dose range of these pellets was found to ranges from 1 to 80 kGy. The stability of the radiation- induced response was also studied

  19. Effective utilization of B20 blend with diethyl ether and ethanol as oxygenated additives

    Directory of Open Access Journals (Sweden)

    Upadrasta-Satya Vara-Prasad

    2011-01-01

    Full Text Available In the recent times' fatty acid methyl ester popularly called as biodiesel has become more prominent alternate fuel for compression ignition engines based on a single fuel concept. Since, use of neat biodiesel on a large scale is raising certain difficulties and is being adopted in a blended form with petro-diesel fuel and B20 blend has become standardized. However, the HC and NOx emissions of B20 are still on the higher side. Present work aims at experimental evaluation of a single cylinder water-cooled diesel engine by adopting various proportions of ethanol and diethyl ether blends in order to improve performance and emission characteristics of B20 blend. Besides employing different amounts of ethanol and diethyl ether, simultaneous influence of injector nozzle hole size and fuel injection pressure are also investigated to arrive at an optimum configuration. Brake specific fuel consumption and hydrocarbon emissions values are lower with B20 and DEE 5 whereas B20 with DEE15 yielded lower NOx emissions. It is observed that addition of oxygenates have improved the combustion process and lower emissions are obtained. The present investigation revealed that blends with oxygenated additives having higher Cetane rating are superior to neat blend.

  20. Microbial reductive dehalogenation of vinyl chloride

    Science.gov (United States)

    Spormann, Alfred M [Stanford, CA; Muller, Jochen A [Baltimore, MD; Rosner, Bettina M [Berlin, DE; Von Abendroth, Gregory [Nannhein, DE; Meshulam-Simon, Galit [Los Altos, CA; McCarty, Perry L [Stanford, CA

    2011-11-22

    Compositions and methods are provided that relate to the bioremediation of chlorinated ethenes, particularly the bioremediation of vinyl chloride by Dehalococcoides-like organisms. An isolated strain of bacteria, Dehalococcoides sp. strain VS, that metabolizes vinyl chloride is provided; the genetic sequence of the enzyme responsible for vinyl chloride dehalogenation; methods of assessing the capability of endogenous organisms at an environmental site to metabolize vinyl chloride; and a method of using the strains of the invention for bioremediation.

  1. β-methyl-15-p-iodophenylpentadecanoic acid metabolism and kinetics in the isolated rat heart

    International Nuclear Information System (INIS)

    DeGrado, T.R.; Holden, J.E.; Ng, C.K.; Raffel, D.M.; Gatley, S.J.

    1989-01-01

    The use of 15-p-iodophenyl-β-methyl-pentadecanoic acid (βMe-IPPA) as an indicator of long chain fatty acid (LCFA) utilization in nuclear medicine studies was evaluated in the isolated, perfused, working rat heart. Time courses of radioactivity (residue curves) were obtained following bolus injections of both βMe-IPPA and its straight chain counterpart 15-p-iodophenyl-pentadecanoic acid (IPPA). IPPA kinetics clearly indicated flow independent impairment of fatty acid oxidation caused by the carnitine palmitoyltransferase I inhibitor 2[5(4-chlorophenyl)pentyl]oxirane-2-carboxylate (POCA). In contrast, βMe-IPPA kinetics were insensitive to changes in fatty acid oxidation rate and net utilization of long chain fatty acid. Analysis of radiolabeled species in coronary effluent and heart homogenates showed the methylated fatty acid to be readily incorporated into complex lipids but a poor substrate for oxidation. POCA did not significantly alter metabolism of the tracer, suggesting that the tracer is poorly metabolized beyond βMe-IPPA-CoA in the oxidative pathway. (orig.)

  2. [Biodegradation of methyl tert-butyl ether by stabilized immobilized Methylibium petroleiphilum PM1 cells and its biodegradation kinetics analysis].

    Science.gov (United States)

    Cheng, Zhuo-wei; Fu, Ling-xiao; Jiang, Yi-feng; Chen, Jian-meng; Zhang, Rong

    2011-05-01

    Methylibium petroleiphilum PM1, which is capable of degrading methyl tert-butyl ether (MTBE) , was immobilized in calcium alginate gel beads. Several methods were explored to increase the strength of these gel beads. The central composite design analysis indicated that the introduction of 0.2 mol x L(-1) Ca2+ into the crosslinking solution, 1.38 mmol x L(-1) Ca2+ into the growth medium and 0.1% polyethyleneimine (PEI) as the chemical crosslinking agent could increase the stability of the Ca-alginate gel beads with no loss of biodegradation activity. The stabilized immobilized cells could be used 400 h continuously with no breakage and no bioactivity loss. Examination of scanning electron microscope demonstrated that a membrane surrounding the gel beads was formed and the cells could grow and breed well in the stabilized calcium alginate gel beads. Kinetic analysis of the gel bead-degradation indicated that the rate-limiting step was biochemical process instead of intraparticle diffusion process. The diameter of 3 mm affected the biodegradability less while high concentration of PEI induced much more serious mass transfer restraint.

  3. Prospects and potential of fatty acid methyl esters of some non-traditional seed oils for use as biodiesel in India

    Energy Technology Data Exchange (ETDEWEB)

    Mohibbe Azam, M.; Waris, Amtul; Nahar, N.M. [Central Arid Zone Research Institute, Jodhpur 342003 (India)

    2005-10-01

    Fatty acid profiles of seed oils of 75 plant species having 30% or more fixed oil in their seed/kernel were examined. Saponification number (SN), iodine value (IV) and cetane number (CN) of fatty acid methyl esters of oils were empirically determined and they varied from 169.2 to 312.5, 4.8 to 212 and 20.56 to 67.47, respectively. Fatty acid compositions, IV and CN were used to predict the quality of fatty acid methyl esters of oil for use as biodiesel. Fatty acid methyl ester of oils of 26 species including Azadirachta indica, Calophyllum inophyllum, Jatropha curcas and Pongamia pinnata were found most suitable for use as biodiesel and they meet the major specification of biodiesel standards of USA, Germany and European Standard Organization. The fatty acid methyl esters of another 11 species meet the specification of biodiesel standard of USA only. These selected plants have great potential for biodiesel. (author)

  4. Prospects and potential of fatty acid methyl esters of some non-traditional seed oils for use as biodiesel in India

    International Nuclear Information System (INIS)

    Mohibbe Azam, M.; Waris, Amtul; Nahar, N.M.

    2005-01-01

    Fatty acid profiles of seed oils of 75 plant species having 30% or more fixed oil in their seed/kernel were examined. Saponification number (SN), iodine value (IV) and cetane number (CN) of fatty acid methyl esters of oils were empirically determined and they varied from 169.2 to 312.5, 4.8 to 212 and 20.56 to 67.47, respectively. Fatty acid compositions, IV and CN were used to predict the quality of fatty acid methyl esters of oil for use as biodiesel. Fatty acid methyl ester of oils of 26 species including Azadirachta indica, Calophyllum inophyllum, Jatropha curcas and Pongamia pinnata were found most suitable for use as biodiesel and they meet the major specification of biodiesel standards of USA, Germany and European Standard Organization. The fatty acid methyl esters of another 11 species meet the specification of biodiesel standard of USA only. These selected plants have great potential for biodiesel

  5. Genomic DNA Methylation Changes in Response to Folic Acid Supplementation in a Population-Based Intervention Study among Women of Reproductive Age

    Science.gov (United States)

    Berry, Robert J.; Hao, Ling; Li, Zhu; Maneval, David; Yang, Thomas P.; Rasmussen, Sonja A.; Yang, Quanhe; Zhu, Jiang-Hui; Hu, Dale J.; Bailey, Lynn B.

    2011-01-01

    Folate is a source of one-carbons necessary for DNA methylation, a critical epigenetic modification necessary for genomic structure and function. The use of supplemental folic acid is widespread however; the potential influence on DNA methylation is unclear. We measured global DNA methylation using DNA extracted from samples from a population-based, double-blind randomized trial of folic acid supplementation (100, 400, 4000 µg per day) taken for 6 months; including a 3 month post-supplementation sample. We observed no changes in global DNA methylation in response to up to 4,000 µg/day for 6 months supplementation in DNA extracted from uncoagulated blood (approximates circulating blood). However, when DNA methylation was determined in coagulated samples from the same individuals at the same time, significant time, dose, and MTHFR genotype-dependent changes were observed. The baseline level of DNA methylation was the same for uncoagulated and coagulated samples; marked differences between sample types were observed only after intervention. In DNA from coagulated blood, DNA methylation decreased (−14%; Pmethylation decreased an additional 23% (Pmethylation of ≥25% (vs. methylation between DNA extracted from coagulated and uncoagulated samples in response to folic acid supplementation is an important finding for evaluating use of folic acid and investigating the potential effects of folic acid supplementation on coagulation. PMID:22163281

  6. On the complexing of phosphoric acid vinyl esters with praseodymium (3) and europium (3) nitrates in acetonitrile

    International Nuclear Information System (INIS)

    Goryushko, A.G.; Gololobov, Yu.G.; Boldeskul, A.E.; Oganesyan, A.S.; Yartsev, V.G.

    1990-01-01

    By the methods of electron, IR and PMR spectroscopy interaction of vinyl esters of phosphoric acid with praseodymium (3) and europium (3) nitrates in acetonitrile solutions has been studied. It is shown that the character of metal-ligand interaction is determined by chemical nature of the ligands: for a compound of ionic structure partially covalent bond is formed, and for a compound of betaine structure the interaction has mainly dipole character. Addition of molecule with betaine structure to praseodymium nitrate causes a change in geometry of Pr 3+ close surrounding and increase in its coordination number. The possibility of formation of the complex with metal-ligand ratio equal to 1:3 is shown

  7. Investigation on the thermal properties of new thermo-reversible networks based on poly(vinyl furfural and multifunctional maleimide compounds

    Directory of Open Access Journals (Sweden)

    C. Gaina

    2012-02-01

    Full Text Available New thermo-reversible networks were obtained from poly(vinyl furfural and multifunctional maleimide monomers by Diels-Alder (DA and retro-DA reactions. The poly(vinyl furfural having acetalization degree of 15 and 25% were obtained by the acid-catalyzed homogenous acetalization of poly(vinyl alcohol with 2-furfural in a nonaqueous media. The thermal and viscoelastic behaviour of the cross-linked materials have been studied via differential scanning calorimetry, dynamic mechanical analysis and thermogravimetric analysis. The networks exhibit considerable swelling in those organic solvents that dissolve both poly(vinyl furfural and bismaleimides; by heating in aprotic dipolar solvents at 150°C, they become soluble.

  8. Gas chromatographic determination of organic acids from fruit juices by combined resin mediated methylation and extraction in supercritical carbon dioxide.

    Science.gov (United States)

    Barden, T J; Croft, M Y; Murby, E J; Wells, R J

    1997-10-17

    A procedure in which anionic analytes, trapped on ion exchange resin, are simultaneously methylated and released using methyl iodide in either supercritical carbon dioxide or acetonitrile has been extended to polyfunctional organic acids. The combined SFE methylation of fruit juice acids trapped onto ion exchange resin proceeds in good yield producing the methyl esters of fumaric, succinic, malic, tartaric, isocitric and citric acids which are readily separated by GC. Using this procedure low concentrations of one acid can be detected and quantitated in the presence of very high concentrations of another. This new method detects tartaric acid at levels of 10 ppm in juices containing 10,000 ppm citric acid. Quantitation was performed either by using GC-FID with triethyl citrate or diethyl tartrate as internal standards or with the element specific calibration capability of the GC-AED. A simple new technique for the determination of citric/isocitric acid ratio is now available. Also, in contrast to HPLC methods, the identity of an analyte is readily confirmed by GC-MS.

  9. Chemical Composition and Cytotoxic Activities of Petroleum Ether ...

    African Journals Online (AJOL)

    Methods: The composition of petroleum ether extract was analyzed by gas ... acids, sterides, pregnanones, terpenes, alkaloids, alkenes, alcohols, ketones, aldehydes and other compounds. .... and mass spectra with those obtained from the.

  10. Chemical modification of poly(vinyl alcohol): evaluation of hydrophilic/lipophilic balance

    International Nuclear Information System (INIS)

    Aranha, Isabele B.; Lucas, Elizabete F.

    2001-01-01

    Poly(vinyl alcohol) terpolymers have been obtained by reaction of partially hydrolized poly(vinyl alcohol) with different acid chlorides. The objective is the preparation of polymers with slight differences in their hydrophilic/lipophilic balance and in the interfacial activities of their solutions. The chemical modifications were characterized by means of 1 H NMR and the polymer properties were evaluated in terms of changes in solubility and surface tension. By chemical modification, polymers with low percentage of hydrophobic group were obtained. The water-soluble polymers obtained did not have the surface tension of their solutions altered. The solubility of the modified polymers decreased markedly, even with low contents of hydrophobic groups. (author)

  11. A microfluidic device for the automated derivatization of free fatty acids to fatty acid methyl esters.

    Science.gov (United States)

    Duong, Cindy T; Roper, Michael G

    2012-02-21

    Free fatty acid (FFA) compositions are examined in feedstock for biodiesel production, as source-specific markers in soil, and because of their role in cellular signaling. However, sample preparation of FFAs for gas chromatography-mass spectrometry (GC-MS) analysis can be time and labor intensive. Therefore, to increase sample preparation throughput, a glass microfluidic device was developed to automate derivatization of FFAs to fatty acid methyl esters (FAMEs). FFAs were delivered to one input of the device and methanolic-HCl was delivered to a second input. FAME products were produced as the reagents traversed a 29 μL reaction channel held at 55 °C. A Design of Experiment protocol was used to determine the combination of derivatization time (T(der)) and ratio of methanolic-HCl:FFA (R(der)) that maximized the derivatization efficiencies of tridecanoic acid and stearic acid to their methyl ester forms. The combination of T(der) = 0.8 min and R(der) = 4.9 that produced optimal derivatization conditions for both FFAs within a 5 min total sample preparation time was determined. This combination of T(der) and R(der) was used to derivatize 12 FFAs with a range of derivatization efficiencies from 18% to 93% with efficiencies of 61% for tridecanoic acid and 84% for stearic acid. As compared to a conventional macroscale derivatization of FFA to FAME, the microfluidic device decreased the volume of methanolic-HCl and FFA by 20- and 1300-fold, respectively. The developed microfluidic device can be used for automated preparation of FAMEs to analyze the FFA compositions of volume-limited samples.

  12. Experimental and numerical investigations on spray characteristics of fatty acid methyl esters.

    Science.gov (United States)

    Lanjekar, R D; Deshmukh, D

    2018-02-01

    A comparative experimental and numerical study is conducted to establish the significance of the use of single-component over multi-component representatives of biodiesel, diesel and their blend for predicting spray tip penetration. Methyl oleate and methyl laurate are used as single-component representative fuels for biodiesel. The pure components n -heptane, n -dodecane and n -tetradecane are used as single-component representative fuels for diesel. Methyl laurate is found to represent biodiesel of coconut, whereas methyl oleate is found to represent biodiesel having high percentage of long-chain fatty acid esters. The spray tip penetration of methyl oleate is found to be in good agreement with the measured spray tip penetration of karanja biodiesel. The spray tip penetration prediction of n -heptane fuel is closely following diesel spray tip penetration along with that of n -tetradecane and n -dodecane. The study suggests that the knowledge of the single-component representatives of biodiesel, diesel and their blend is sufficient to predict the spray tip penetration of the corresponding biodiesel, diesel and their blend under non-evaporating environment.

  13. Experimental and numerical investigations on spray characteristics of fatty acid methyl esters

    Science.gov (United States)

    Lanjekar, R. D.; Deshmukh, D.

    2018-02-01

    A comparative experimental and numerical study is conducted to establish the significance of the use of single-component over multi-component representatives of biodiesel, diesel and their blend for predicting spray tip penetration. Methyl oleate and methyl laurate are used as single-component representative fuels for biodiesel. The pure components n-heptane, n-dodecane and n-tetradecane are used as single-component representative fuels for diesel. Methyl laurate is found to represent biodiesel of coconut, whereas methyl oleate is found to represent biodiesel having high percentage of long-chain fatty acid esters. The spray tip penetration of methyl oleate is found to be in good agreement with the measured spray tip penetration of karanja biodiesel. The spray tip penetration prediction of n-heptane fuel is closely following diesel spray tip penetration along with that of n-tetradecane and n-dodecane. The study suggests that the knowledge of the single-component representatives of biodiesel, diesel and their blend is sufficient to predict the spray tip penetration of the corresponding biodiesel, diesel and their blend under non-evaporating environment.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hashim, Nordiana; Ali, Ab Malik Marwan [Ionic Material and Devices Research Laboratory, Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam (Malaysia); Lepit, Ajis; Rasmidi, Rosfayanti [Faculty of Applied Sciences, Universiti Teknologi MARA Sabah, Beg Berkunci 71, 88997 Kota Kinabalu (Malaysia); Subban, Ri Hanum Yahaya [Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam (Malaysia); Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam (Malaysia); Yahya, Muhd Zu Azhan [Faculty of Defence Science & Technology, Universiti Pertahanan Nasional Malaysia, 57000 Kuala Lumpur (Malaysia)

    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.

  15. Synthesis of [methyl-14C]crotonobetaine from DL-[methyl-14C]carnitine

    International Nuclear Information System (INIS)

    Loester, H.; Seim, H.

    1996-01-01

    The causes of carnitine deficiency syndromes are not completely understood, but decomposition of L-carnitine in vivo is likely to be involved. Carnitine is metabolized to γ-butyrobetaine, and crotonobetaine is probably an intermediate in this pathway. To validate experimentally the precursor-product relationship between the three physiologically occuring γ-betaines - L-carnitine, crotonobetaine, γ-butyrobetaine - labelling with stable or radioactive isotopes became necessary. Methyl-labelled carnitine isomers (L(-)-, D(+)- or DL-) or γ-butyrobetaine can be easily synthesized by methylation of 4-amino-3-hydroxybutyric acid isomers or 4-aminobutyric acid, respectively. Because of problems with the 4-aminocrotonic acid, we synthesized labelled crotonbetaine from labelled carnitine. Thus, DL-[methyl- 14 C]carnitine was dehydrated by reaction with concentrated sulfuric acid. After removal of the latter the products were separated and purified by ion exchange chromatography on DOWEX 50 WX8 (200 - 400 mesh) and gradient elution with hydrochloric acid. In addition to the labelled main product [methyl- 14 C]crotonobetaine (yield about 50 %), [methyl- 14 C]glycine betaine and [methyl- 14 C]acetonyl-trimethylammonium (ATMA) were formed. The end products were identified by combined thin layer chromatography/autoradiography and quantified by liquid scintillation counting. (Author)

  16. A model compound (methyl oleate, oleic acid, triolein) study of triglycerides hydrodeoxygenation over alumina-supported NiMo sulfide

    NARCIS (Netherlands)

    Coumans, A.E.; Hensen, E.J.M.

    We studied hydrodeoxygenation of model compounds for vegetable oil into diesel-range hydrocarbons on a sulfided NiMo/γ-Al2O3 catalyst under trickle-flow conditions. Methyl oleate (methyl ester of oleic acid, a C18 fatty acid with one unsaturated bond in the chain) represented the C18 alkyl esters in

  17. Comparison of Properties among Dendritic and Hyperbranched Poly(ether ether ketones and Linear Poly(ether ketones

    Directory of Open Access Journals (Sweden)

    Atsushi Morikawa

    2016-02-01

    Full Text Available Poly(ether ether ketone dendrimers and hyperbranched polymers were prepared from 3,5-dimethoxy-4′-(4-fluorobenzoyldiphenyl ether and 3,5-dihydroxy-4′-(4-fluorobenzoyldiphenyl ether through aromatic nucleophilic substitution reactions. 1-(tert-Butyldimethylsiloxy-3,5-bis(4-fluorobenzoylbenzene was polycondensed with bisphenols, followed by cleavage of the protective group to form linear poly(ether ketones 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.

  18. Potentiation of insulin release in response to amino acid methyl esters correlates to activation of islet glutamate dehydrogenase activity

    DEFF Research Database (Denmark)

    Kofod, Hans; Lernmark, A; Hedeskov, C J

    1986-01-01

    Column perifusion of mouse pancreatic islets was used to study the ability of amino acids and their methyl esters to influence insulin release and activate islet glutamate dehydrogenase activity. In the absence of L-glutamine, L-serine and the methyl ester of L-phenylalanine, but neither L...... glutamate dehydrogenase activity showed that only the two methyl esters of L-phenylalanine and L-serine activated the enzyme. It is concluded that the mechanism by which methyl esters of amino acids potentiate insulin release is most likely to be mediated by the activation of pancreatic beta-cell glutamate...

  19. Ether-Directed ortho-C–H Olefination with a PdII/MPAA Catalyst**

    Science.gov (United States)

    Li, Gang; Leow, Dasheng; Wan, Li; Yu, Jin-Quan

    2013-01-01

    Weak coordination is powerful! A PdII-catalyzed olefination of ortho-C–H bonds of arenes directed by weakly coordinating ethers is developed using mono-protected amino acid (MPAA) ligands. This finding provides a method for chemically modifying ethers, which are abundant in natural products and drug molecules. PMID:23239120

  20. Alkaline earth layered benzoates as reusable heterogeneous catalysts for the methyl esterification of benzoic acid

    Directory of Open Access Journals (Sweden)

    Swamy Arêa Maruyama

    2012-01-01

    Full Text Available This paper describes the synthesis and characterization of layered barium, calcium and strontium benzoates and evaluates the potential of these materials as catalysts in the synthesis of methyl benzoate. The methyl esterification of benzoic acid was investigated, where the effects of temperature, alcohol:acid molar ratio and amount of catalyst were evaluated. Ester conversions of 65 to 70% were achieved for all the catalysts under the best reaction conditions. The possibility of recycling these metallic benzoates was also demonstrated, evidenced by unaltered catalytic activity for three consecutive reaction cycles.

  1. Enhancement of the Biodegradability of Methyl tert- Butyl Ether (MTBE by Advanced Oxidation

    Directory of Open Access Journals (Sweden)

    Mehraban Sadeghi

    2006-06-01

    Full Text Available The effectiveness of ozone treatment for improving the biodegradability of recalcitrant pollutants has been proved by investigating the ozonation reaction of Methyl tert-Butyl Ether (MTBE as a bioresistant gasoline oxygenate. Laboratory scale experiments have been carried out at room temperature by bubbling for 120 minutes ozonated air (3.4 ppm/min into 3 liter of an alkaline (pH=11.5 aqueous solution (100 mg/L of MTBE. The experimental results indicated that during the ozonation, complete MTBE degradation occurs in 100 minutes and after this time, ozone consumption goes on very slowly. At the end of the ozonation, after 100 minutes, the initial value of COD (256 mg O2/L is 98 and corresponds to a relative removal of about 62%. As for MTBE solution biodegradability expressed as (BOD5 / (COD ratio, during the first 90 minutes, its value regularly increases from lowest 0.01 up to a maximum of 0.68 that corresponds to an ozone consumption of 1.25 mg per each mg of COD initially present in the solution. The research showed that partial degradation of MTBE in the advanced oxidation processes results an increase in its biological degradation. But more oxidation results lower  (BOD5 / (COD ratio. Also the research showed that for idealization of the chemical oxidation conditions of MTBE, it needs to decrease COD to 46-68% before the biological degradation. The experimental results for determining the rate of MTBE removal due to stripping showed that about 14% of MTBE strips out after an hour of sparging with oxygen gas. The fraction of MTBE oxidized and/or striped increases to about 28% (in pH=7 and 70% (in pH=11.5 with ozonation over the same time period.

  2. Chemical modification of nanocellulose with canola oil fatty acid methyl ester

    Science.gov (United States)

    Liqing Wei; Umesh P. Agarwal; Kolby C. Hirth; Laurent M. Matuana; Ronald C. Sabo; Nicole M. Stark

    2017-01-01

    Cellulose nanocrystals (CNCs), produced from dissolving wood pulp, were chemically functionalized by transesterification with canola oil fatty acid methyl ester (CME). CME performs as both the reaction reagent and solvent. Transesterified CNC (CNCFE) was characterized for their chemical structure, morphology, crystalline structure, thermal stability, and hydrophobicity...

  3. Colorful and transparent poly(vinyl alcohol) composite films filled with layered zinc hydroxide salts, intercalated with anionic orange azo dyes (methyl orange and orange II)

    International Nuclear Information System (INIS)

    Neves da Silva, Marlon Luiz; Marangoni, Rafael; Cursino, Ana Cristina Trindade; Schreiner, Wido Herwig; Wypych, Fernando

    2012-01-01

    Highlights: ► Zinc hydroxide salts were successfully intercalated with anionic orange azo dyes. ► The anionic dye was co-intercalated with hydrated chloride anions. ► The orange materials were used as fillers for poly(vinyl alcohol). ► Transparent, homogeneous, colorful PVA films were obtained by wet casting. ► Some composites stored at lower humidity exhibited improved mechanical properties. - Abstract: Layered zinc hydroxide salts (zinc LHS) were intercalated with anionic orange azo dyes, namely methyl orange (MO) and orange II (OII), and co-intercalated with hydrated chloride anions. After characterization by X-ray diffraction (XRD), thermal analysis (TGA/DTA), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), the materials were used as fillers for poly(vinyl alcohol) (PVA). Colorful transparent films were obtained by wet casting, revealing good dispersion of the material into the polymer. In the case of zinc LHS/OII, PVA was intercalated between the zinc LHS layers. Evaluation of the mechanical properties of the PVA composite films revealed that the layered colorful materials were able to increase the mechanical properties of the PVA films only when the films were stored under lower relative humidity. As expected, films with higher water content displayed reduced tensile strength and modulus because of the plasticizing effect of water. As for the films stored at 43% relative humidity, more pronounced improvement of modulus was observed for 1 and 4% zinc LHS/OII, and enhanced tensile strength was achieved for 0.5 and 1% zinc LHS/OII. This effect can be attributed to better dispersion of the layered filler and its better adhesion to the PVA matrix.

  4. Gamma radiolysis and vinyl esters

    International Nuclear Information System (INIS)

    De Bruyn, H.; Balic, R.; Gilbert, R.G.

    1998-01-01

    The principle behind γ relaxation of free-radical polymerizations is that the source of initiating radicals can be switched off 'instantaneously'. In the absence of initiating radicals the only kinetic events remaining are propagation, transfer and termination. For monomers whose propagation rate coefficients have been determined, relaxation behaviour can be interpreted to determine radical-loss rate coefficients and test models of loss mechanisms. This technique has been employed successfully on styrene and MMA emulsion polymerizations. In the present study, vinyl acetate and vinyl neo-decanoate (a ten-carbon-branched homologue of vinyl acetate) were studied, with the propagation rate coefficients for both monomers being established by pulsed-laser polymerization. Both were found to exhibit rapid γ relaxation rates in emulsion polymerization. This is a surprising result because mechanisms for rapid relaxation in emulsion polymerizations require that chain transfer to monomer (which is rapid for both monomers) is followed by exit from the particle into the aqueous phase with subsequent re-entry into a radical-containing particle leading to bimolecular termination. It is not unreasonable to suppose that this may be possible for vinyl acetate which is fairly water soluble (∼0.3 M). However, vinyl neo-decanoate is virtually insoluble (∼0.00004 M) and hence desorption is extremely unlikely. The most likely explanation for the observed rapid relaxations is that some of the radicals produced by γ radiolysis are slow to initiate vinyl esters and hence act as radical traps. As vinyl esters are known to be particularly unreactive monomers. it is feasible that this experimental artifact affects them to a much greater extent than some of the monomers studied successfully with this technique in the past

  5. Synthesis of vinyl phosphites

    International Nuclear Information System (INIS)

    Kabachnik, M.M.; Novikova, Z.S.; Neganova, E.G.; Lutsenko, I.F.

    1986-01-01

    The authors investigated the reactions of phosphoriodidites and phosphinous iodides with a number of aldehydes and ketones in presence of tertiary amines (triethylamine, pyridine, N,N-diethylaniline), and they have shown that as a result of the reactions the corresponding vinyl esters of phosphorus acids are formed. The reactions of phosphoriodidites (and phosphorodiamidous iodides) with aliphatic aldehydes (acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde) go at a molar reactant ratio of 1:1 in either at room temperature and are practically complete in 5-6 h. The yields of the alkenyl phosphites (phosphorodiamidites) were 45-70%. The compositions and structures of the compounds obtained were confirmed by elemental analysis and the IR and 1 H and 31 P NMR spectra

  6. Numerical analysis of spray characteristics of dimethyl ether and diethyl ether fuel

    International Nuclear Information System (INIS)

    Mohan, Balaji; Yang, Wenming; Yu, Wenbin; Tay, Kun Lin

    2017-01-01

    Highlights: • Thermo-physical properties of liquid DME and DEE are reported. • Ether fuels tend to cavitate higher compared to that of diesel fuel. • Spray tip penetration and SMD are found to be lesser for ether fuels. • Ether fuels shows excellent atomization behavior. - Abstract: In this work, the spray characteristics of ether fuels such as dimethyl ether (DME) and diethyl ether (DEE) have been numerically investigated using KIVA-4 CFD code. A new hybrid spray model developed by coupling the standard KHRT model to cavitation sub model was used. The detailed thermo-physical properties of ether fuels have been predicted and validated with experimental results available from literature. The cavitation inception inside the injector nozzle hole has been studied for ether fuels in comparison with diesel fuel. It was found that ether fuels cavitates higher compared to that of conventional diesel fuel because of its low viscosity. The spray tip penetration of diesel fuel was longer than that of ether fuels due to high viscosity and density of diesel fuel. Ether fuels characterized by low Ohnesorge number and high Reynolds number showed better atomization behavior compared to that of the diesel fuel.

  7. Preparation of Syndiotactic Poly(vinyl alcohol)/Poly(vinyl pivalate/vinyl acetate) Microspheres with Radiopacity Using Suspension Copolymerization and Saponification

    Science.gov (United States)

    Seok Lyoo, Won; Wook Cha, Jin; Young Kwak, Kun; Jae Lee, Young; Yong Jeon, Han; Sik Chung, Yong; Kyun Noh, Seok

    2010-06-01

    To prepare Poly(vinyl pivalate/vinyl acetate) [P(VPi/VAc)] microspheres with radiopacity, the suspension copolymerization approach in the presence of aqueous radiopaque nanoparticles was used. After, The P(VPi/VAc) microspheres with radiopacity were saponified in heterogeneous system, and then P(VPi/VAc) microspheres without aggregates were converted to s-PVA/P(VPi/VAc) microspheres of skin/core structure through the heterogeneous surface saponification. Radiopacity of microspheres was confirmed with Computed tomography (CT).

  8. Dietary and supplemental maternal methyl-group donor intake and cord blood DNA methylation.

    Science.gov (United States)

    Pauwels, Sara; Ghosh, Manosij; Duca, Radu Corneliu; Bekaert, Bram; Freson, Kathleen; Huybrechts, Inge; A S Langie, Sabine; Koppen, Gudrun; Devlieger, Roland; Godderis, Lode

    2017-01-02

    Maternal nutrition is critically involved in the development and health of the fetus. We evaluated maternal methyl-group donor intake through diet (methionine, betaine, choline, folate) and supplementation (folic acid) before and during pregnancy in relation to global DNA methylation and hydroxymethylation and gene specific (IGF2 DMR, DNMT1, LEP, RXRA) cord blood methylation. A total of 115 mother-infant pairs were enrolled in the MAternal Nutrition and Offspring's Epigenome (MANOE) study. The intake of methyl-group donors was assessed using a food-frequency questionnaire. LC-MS/MS and pyrosequencing were used to measure global and gene specific methylation, respectively. Dietary intake of methyl-groups before and during pregnancy was associated with changes in LEP, DNMT1, and RXRA cord blood methylation. Statistically significant higher cord blood LEP methylation was observed when mothers started folic acid supplementation more than 6 months before conception compared with 3-6 months before conception (34.6 ± 6.3% vs. 30.1 ± 3.6%, P = 0.011, LEP CpG1) or no folic acid used before conception (16.2 ± 4.4% vs. 13.9 ± 3%, P = 0.036 for LEP CpG3 and 24.5 ± 3.5% vs. 22.2 ± 3.5%, P = 0.045 for LEP mean CpG). Taking folic acid supplements during the entire pregnancy resulted in statistically significantly higher cord blood RXRA methylation as compared with stopping supplementation in the second trimester (12.3 ± 1.9% vs. 11.1 ± 2%, P = 0.008 for RXRA mean CpG). To conclude, long-term folic acid use before and during pregnancy was associated with higher LEP and RXRA cord blood methylation, respectively. To date, pregnant women are advised to take a folic acid supplement of 400 µg/day from 4 weeks before until 12 weeks of pregnancy. Our results suggest significant epigenetic modifications when taking a folic acid supplement beyond the current advice.

  9. Radiation-Induced Graft Polymerization of Vinyl Monomers with Anion Groups onto MWNT Supports and Their Application as Electrogenerated Chemiluminescence (ECL Biosensors

    Directory of Open Access Journals (Sweden)

    Ji-Hye Park

    2014-01-01

    Full Text Available Vinyl polymer-grafted multiwalled carbon nanotube (MWNT supports with anion groups were prepared for use as biosensor supports by radiation-induced graft polymerization (RIGP of the vinyl monomers acryloyl diphosphoric acid (ADPA, acrylic acid (AA, sodium styrenesulfonate (NaSS, and methacrylic acid (MA onto the surface of MWNTs. The electrogenerated chemiluminescence sensors based on a glass carbon electrode (ECL-GCE and a screen printed electrode (ECL-SPE were fabricated by immobilization of Ru(bpy3 2+ complex after coating of vinyl polymer-grafted MWNT inks on the surface of the GCE and SPE without any polymer binders in order to obtain high electrogenerated chemiluminescence intensity. For detection of alcohol concentration, alcohol dehydrogenase (ADH was immobilized onto an ECL-GCE sensor prepared by poly(NaSS-g-MWNT supports. The prepared biosensor based on ADH is suitable for the detection of ethanol concentration in commercial drinks.

  10. The uptake, distribution, metabolism, and excretion of methyl tertiary-butyl ether inhaled alone and in combination with gasoline vapor.

    Science.gov (United States)

    Benson, Janet M; Tibbetts, Brad M; Barr, Edward B

    2003-06-13

    The purpose of these studies was to evaluate the tissue uptake, distribution, metabolism, and excretion of methyl tertiary-butyl ether (MTBE) in rats and to determine the effects of coinhalation of the volatile fraction of unleaded gasoline on these parameters. Male F344 rats were exposed nose-only once for 4 h to 4, 40, or 400 ppm 14C-MTBE and to 20 and 200 ppm of the light fraction of unleaded gasoline (LFG) containing 4 and 40 ppm 14C-MTBE, respectively. To evaluate the effects of repeated inhalation of LFG on the fate of inhaled MTBE, rats were exposed for 7 consecutive days to 20 and 200 ppm LFG followed on d 8 by exposure to LFG containing 14C-MTBE. Three subgroups of rats were included for evaluation of respiratory parameters, rates and routes of excretion, and tissue distribution and elimination. MTBE and its chief metabolite, tertiary-butyl alcohol, were quantitated in blood and kidney (immediately after exposure), and the major urinary metabolites, 2-hydroxyisobutyric acid and 2-methyl-1,2- propanediol, were identified and quantified in urine. Inhalation of MTBE alone or as a component of LFG had no concentration-dependent effect on respiratory minute volume. The initial body burdens (IBBs) of MTBE equivalents achieved after 4 h of exposure to MTBE did not increase linearly with exposure concentration. MTBE equivalents rapidly distributed to all tissues examined, with the largest percentages distributed to liver. Between 40 and 400 ppm, there was a significant reduction in percentage of the IBB present in the major organs examined, both immediately and 72 h after exposure. At 400 ppm, the elimination rates of MTBE equivalents from tissues changed significantly. Furthermore, at 400 ppm there was a significant decrease in the elimination half-time of volatile organic compounds (VOCs) in breath and a significant increase in the percentage of the IBB of MTBE equivalents eliminated as VOCs in breath. LFG coexposure significantly decreased the percentage of the

  11. Development of natural rubber membranes for separation of methyl tert-butyl ether and methanol

    International Nuclear Information System (INIS)

    Nur Azrini Ramlee; Ghazali Mohd Nawawi; Khairul Zaman Dahlan

    2010-01-01

    As a new commercial process, membrane separation raises significant expectations in the process plant of the future and therefore this research was being initiated to develop and characterize pervaporation membrane based on natural rubber (NR). Natural Rubber SMR-L grade which was supplied by Malaysia Rubber Research Institute (MRRI) was used for the development of the membranes via interpenetrating polymer network (IPN) techniques. Polystyrene (PS) was used to modify the natural rubber to further improve their mechanical and chemical properties. The membranes were prepared with various blend ratios of natural rubber, polystyrene and divinyl benzene as cross linker with constant 1 % of dicumyl peroxide as the initiator. The developed membranes were then characterized to study the functional group presence, membranes morphology, crosslink density, tear strength, adsorption of the membranes and pervaporation separation of Methyl-Tert-Butyl-Ether (MTBE) and Methanol. Pervaporation process was conducted by using varies of MTBE concentration 10, 30, 50 and 70 wt % and at differ operation temperature, 25 degree Celsius and 55 degree Celsius. Separation performance of IPN NR/ PS membranes were based on the presented permeation flux and separation factor. Examination through Fourier Transform Infrared Spectroscopy (FTIR), determined crosslink density and tear strength, 6 series of IPN NR/ PS membranes were successfully developed using natural rubber. Observation from Scanning Electron Microscopy (SEM) showed that the membranes were dense and appropriated for the pervaporation process application. From the pervaporation of MTBE and Methanol, IPN NR/ PS membranes of series D4N30 shown low permeation flux of MTBE but high separation factor while D2N70 membranes was vice versa for both temperature of 25 degree Celsius and 55 degree Celsius. (author)

  12. Methylated Fatty Acids from Heartwood and Bark of Pinus sylvestris, Abies alba, Picea abies, and Larix decidua: Effect of Strong Acid Treatment

    Directory of Open Access Journals (Sweden)

    Mohamed Zidan Mohamed Salem

    2015-09-01

    Full Text Available Methylated fatty acid (FA compounds in the heartwood and bark of some softwood species, specifically Pinus sylvestris, Abies alba, Picea abies, and Larix decidua, grown in the Czech Republic were evaluated. Strong H2SO4 was used for methylation of the lipids. The highest content of lipid was found in P. abies bark (40.132 mg/g o.d. sample, and the lowest content was in A. alba wood (11.027 mg/g o.d. sample. The highest concentration of FAs was observed in L. decidua bark. The highest percentages of FAs in wood of P. sylvestris were arachidic acid and oleic acid. In bark, the highest percentages of FAs were stearic acid, palmitic acid, and oleic acid. The FAs with the highest concentrations in A. alba wood were arachidic acid, palmitic acid, pentadecanoic acid, and margarinic, and those in bark were behenic acid, lignoceric acid, and arachidic acid. P. abies wood FAs showed arachidic acid, palmitic acid, and margarinic acid, and the bark contained lignoceric acid and arachidic acid. The FAs of L. decidua wood were arachidic acid, palmitic acid, and stearic acid, and in bark they were pentacosylic acid, docosahexaenoic acid (DHA, lignoceric acid, arachidic acid, and behenic acid. The lack of typically dominant unsaturated fatty acids (e.g. 18:1, 18:2, compared to literature values were attributed to the application of strong acid for the hydrolysis.

  13. Isotopic exchange of cyclic ethers with deuterium over metal catalysts

    International Nuclear Information System (INIS)

    Duchet, J.C.; Cornet, D.

    1976-01-01

    The exchange reaction between deuterium and cyclic ethers (oxolane and α-methyl derivatives) has been investigated using rhodium and palladium catalysts. The first hydrogen undergoing exchange has been found to be located on a β-carbon. This fact, and the poisoning of the exchange of cyclopentane in the presence of ether, suggest that the O atom participates in the exchange mechanism of ethers. It appears, however, that the oxygen--metal bonding occurs only during this simple exchange process; simultaneous adsorption of oxygen and a vicinal carbon causes hydrogenolysis of the O--C bond. In each case multiple exchange is important. In the oxolane molecule two sets of exchangeable hydrogens are distinguished according to their reactivities, as could be expected by analogy with cycloalkanes. However, this distinction is not so clear in the exchange patterns of substituted oxolanes, since intermediate maxima are observed in these cases. It is suggested that the conformational properties of the substituted rings cause a constraint in the formation of 3,4-diadsorbed oxolanes. Thus, multiple exchange, based on α,β-process, and epimerization via the ''roll-over'' mechanism occur preferentially in certain parts of the molecules

  14. Synthesis of Similars of the Retinoic Acid with Anti-Cancer Potential

    International Nuclear Information System (INIS)

    Marin Cordoba, R.

    2001-01-01

    Three precursors were synthesized in the route toward new structures similar of the retinoic acid. They are the bromocetones 15, 35 and 36. Two new similar of the retinoic acid were synthesized; they are the acids 39 and 40. The mechanism for the formation of 1,1,4,4-tetramethyl-1, 2,3,4-tetrahydronaphthalene (17), starting from benzene and 2,5-dimethyl-2, 5-dichlorine-hexane was studied. This reaction intended to be carried out in four elementary reactions. Under the used conditions, the product is isolated in 95%. Also, the effect of the dilution in the yield of the tetramethyltehydro-naphthalene was studied; the good relationship of benzene to the compound dichloride was of 29:1. It is determined that the bromocetones 15, 35 and 36 are little reactive toward the joining of Heck when the crotonic acid is used. Probably, the presence of the groups metoxyle and hydroxyle to the halogen in the bromocetones 15 and 36, respectively, affect the reactivity. In the case of the bromocetone 35, to make this reaction, the group protective acilo gets lost before being made the vinylation of Heck, becoming the bromocetone 36. The joining of Heck between the acrylic acid and the bromocetone 15 in an isolated yield of 33% was possible to be made. It indicates that besides the electronic effects that affect to the bromocetone in this type of reaction, the vinyllic methyl in the crotonic acid causes a low reactivity in this joining, for this substrate in particular. (Author) [es

  15. Design and biological properties of iodine-123 labeled β-methyl-branched fatty acids

    International Nuclear Information System (INIS)

    Knapp, F.F. Jr.; Goodman, M.M.

    1984-01-01

    The synthetic strategy, synthesis, preclinical evaluation and potential clinical applications of 3-methyl-branched radioiodinated iodophenyl- and iodovinyl-substituted fatty acids are reviewed for use as myocardial imaging agents. 50 references, 6 figures

  16. Direct transformation of silyl enol ethers into functionalized allenes.

    Science.gov (United States)

    Langer, P; Döring, M; Seyferth, D; Görls, H

    2001-02-02

    The first elimination reactions of silyl enol ethers to lithiated allenes are reported. These reactions allow a direct transformation of readily available silyl enol ethers into functionalized allenes. The action of three to four equivalents of lithium diisopropylamide (LDA) on silyl enol ethers results in the formation of lithiated allenes by initial allylic lithiation, subsequent elimination of a lithium silanolate, and finally, lithiation of the allene thus formed. Starting with amide-derived silyl imino ethers, lithiated ketenimines are obtained. A variety of reactions of the lithiated allenes with electrophiles (chlorosilanes, trimethylchlorostannane, dimethyl sulfate and ethanol) were carried out. Elimination of silanolate is observed only for substrates that contain the hindered SiMe2tBu or Si(iPr)3 moiety, but not for the SiMe3 group. The reaction of 1,1-dilithio-3,3-diphenylallene with ketones provides a convenient access to novel 1,1-di(hydroxymethyl)allenes which undergo a domino Nazarov-Friedel-Crafts reaction upon treatment with p-toluenesulfonic acid.

  17. Preservation of urine free catecholamines and their free O-methylated metabolites with citric acid as an alternative to hydrochloric acid for LC-MS/MS-based analyses.

    Science.gov (United States)

    Peitzsch, Mirko; Pelzel, Daniela; Lattke, Peter; Siegert, Gabriele; Eisenhofer, Graeme

    2016-01-01

    Measurements of urinary fractionated metadrenalines provide a useful screening test to diagnose phaeochromocytoma. Stability of these compounds and their parent catecholamines during and after urine collection is crucial to ensure accuracy of the measurements. Stabilisation with hydrochloric acid (HCl) can promote deconjugation of sulphate-conjugated metadrenalines, indicating a need for alternative preservatives. Urine samples with an intrinsically acidic or alkaline pH (5.5-6.9 or 7.1-8.7, respectively) were used to assess stability of free catecholamines and their free O-methylated metabolites over 7 days of room temperature storage. Stabilisation with HCl was compared with ethylenediaminetetraacetic acid/metabisulphite and monobasic citric acid. Catecholamines and metabolites were measured by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Free catecholamines and their O-methylated metabolites were stable in acidic urine samples over 7 days of room temperature storage, independent of the presence or absence of any stabilisation method. In contrast, free catecholamines, but not the free O-methylated metabolites, showed rapid degradation within 24 h and continuing degradation over 7 days in urine samples with an alkaline pH. Adjustment of alkaline urine samples to a pH of 3-5 with HCl or 4.8-5.4 with citric acid completely blocked degradation of catecholamines. Ethylenediaminetetraacetic acid/metabisulphite, although reducing the extent of degradation of catecholamines in alkaline urine, was largely ineffectual as a stabiliser. Citric acid is equally effective as HCl for stabilisation of urinary free catecholamines and minimises hazards associated with use of strong inorganic acids while avoiding deconjugation of sulphate-conjugated metabolites during simultaneous LC-MS/MS measurements of free catecholamines and their free O-methylated metabolites.

  18. Poly(vinyl chloride) catheters modified with pH-responsive poly(methacrylic acid) with affinity for antimicrobial agents

    Science.gov (United States)

    Zuñiga-Zamorano, Ivette; Meléndez-Ortiz, H. Iván; Costoya, Alejandro; Alvarez-Lorenzo, Carmen; Concheiro, Angel; Bucio, Emilio

    2018-01-01

    Radiation-grafting of pH-responsive methacrylic acid (MAA) onto poly(vinyl chloride) (PVC) was carried out by the pre-irradiation method using gamma rays, which demonstrated to be an efficient and fast procedure for obtaining PVC-g-MAA copolymers. The influence of preparation conditions, such as absorbed dose, monomer concentration, reaction time, and reaction temperature on the grafting yield was studied. The grafting of MAA onto PVC catheters was confirmed by means of Fourier transform infrared spectroscopy (FT-IR), thermogravimetry analysis (TGA), and differential scanning calorimetry (DSC). The pH-responsiveness of the grafted copolymers (critical point 8.5) was measured by swelling under cyclic changes in the pH of the medium. Interestingly, PVC-g-MAA showed enhanced capability to immobilize benzalkonium chloride and, particularly, ciprofloxacin and to sustain the release this antimicrobial agent at both acid and alkaline pH. Tests carried out with Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus point out that the developed functionalized catheters may play a role in the prevention/management of urinary tract infections.

  19. The fungal phytotoxin alternariol 9-methyl ether and some of its synthetic analogues inhibit the photosynthetic electron transport chain.

    Science.gov (United States)

    Demuner, Antonio Jacinto; Barbosa, Luiz Cláudio Almeida; Miranda, Ana Cristina Mendes; Geraldo, Guilherme Carvalho; da Silva, Cleiton Moreira; Giberti, Samuele; Bertazzini, Michele; Forlani, Giuseppe

    2013-12-27

    Alternariol and monomethylalternariol are natural phytotoxins produced by some fungal strains, such as Nimbya and Alternaria. These substances confer virulence to phytopathogens, yet no information is available concerning their mode of action. Here we show that in the micromolar range alternariol 9-methyl ether is able to inhibit the electron transport chain (IC50 = 29.1 ± 6.5 μM) in isolated spinach chloroplasts. Since its effectiveness is limited by poor solubility in water, several alternariol analogues were synthesized using different aromatic aldehydes. The synthesized 6H-benzo[c]cromen-6-ones, 5H-chromene[4,3-b]pyridin-5-one, and 5H-chromene[4,3-c]pyridin-5-one also showed inhibitory properties, and three 6H-benzo[c]cromen-6-ones were more effective (IC50 = 12.8-22.8 μM) than the lead compound. Their addition to the culture medium of a cyanobacterial model strain was found to inhibit algal growth, with a relative effectiveness that was consistent with their activity in vitro. In contrast, the growth of a nonphotosynthetic plant cell culture was poorly affected. These compounds may represent a novel lead for the development of new active principles targeting photosynthesis.

  20. Method detection limit determination and application of a convenient headspace analysis method for methyl tert-butyl ether in water.

    Science.gov (United States)

    O'Neill, Dennis T; Rochette, Elizabeth A; Ramsey, Philip J

    2002-11-15

    Methyl tert-butyl ether (MTBE) is a common groundwater contaminant, introduced to the environment by leaking petroleum storage tanks, urban runoff, and motorized watercraft. In this study. a simplified (static) headspace analysis method was adapted for determination of MTBE in water samples and soil water extracts. The MDL of the headspace method was calculated to be 2.0 microg L(-1) by the EPA single-concentration design method(1) and 1.2 microg L(-1) by a calibration method developed by Hubaux and Vos (Hubaux, A.; Vos, G. Anal. Chem. 1970,42, 849-855). The MDL calculated with the Hubaux and Vos method was favored because it considers both a true positive and a false positive. The static headspace method was applied to analysis of a tap water sample and a monitoring well sample from a gasoline service station, a river sample, and aqueous extracts from soil excavated during removal of a leaking underground storage tank (LUST). The water samples examined in this study had MTTBE concentrations ranging from 6 to 19 microg L(-1). Aqueous extracts of a soil sample taken from the LUST site had 8 microg L(-1) MTBE.

  1. Assessing soil ecotoxicity of methyl tert-butyl ether using earthworm bioassay; closed soil microcosm test for volatile organic compounds

    International Nuclear Information System (INIS)

    An, Youn-Joo

    2005-01-01

    An earthworm bioassay was conducted to assess ecotoxicity in methyl tert-butyl ether (MTBE)-amended soils. Ecotoxicity of MTBE to earthworms was evaluated by a paper contact method, natural field soil test, and an OECD artificial soil test. All tests were conducted in closed systems to prevent volatilization of MTBE out of test units. Test earthworm species were Perionyx excavatus and Eisenia andrei. Mortality and abnormal morphology of earthworms exposed to different concentrations of MTBE were examined. MTBE was toxic to both earthworm species and the severity of response increased with increasing MTBE concentrations. Perionyx excavatus was more sensitive to MTBE than Eisenia andrei in filter papers and two different types of soils. MTBE toxicity was more severe in OECD artificial soils than in field soils, possibly due to the burrowing behavior of earthworms into artificial soils. The present study demonstrated that ecotoxicity of volatile organic compounds such as MTBE can be assessed using an earthworm bioassay in closed soil microcosm with short-term exposure duration. - Earthworm bioassay can be a good protocol to assess soil ecotoxicity of volatile organic compounds such as MTBE

  2. Quantiifcation of methyl esters of fatty acids in the oil of Physalis minima by GC-MS

    Institute of Scientific and Technical Information of China (English)

    Muhammad Nasimullah Qureshi; Fazal Wajid; Inayat-ur-Rahman

    2015-01-01

    Objective:To investigate quantification of methyl esters of fatty acids in the oil extracted from Physalis minima (P. minima) using gas chromatography-mass spectrometer. Methods: Oil was extracted from the shade dried plant with n-hexane through Soxhlet extraction. Fatty acids that present in the oil were derivatized to fatty acid methyl esters and analysed through gas chromatography-mass spectrometer. Results:A total of nine fatty acids were detected in quantifiable amount in the oil. Both the saturated fatty acids and unsaturated fatty acids were identified. Palmitic acid was found in the highest concentration as 46.83%. Linoleic acid (ω-6) and linolenic acid (ω-3) were obtained in appreciable amount as 16.98%and 14.80%respectively among the unsaturated fatty acids in the oil under study. From the literature review, it appeared that fatty acids were determined for the first time in the oil of P. minima. Conclusions: Presence of these important fatty acids in high amount makes P. minima oil beneficial for health, which can be used in the preparation of phytopharmaceutical or pharmaceutical preparations. Moreover, the results of this study are useful for the phytopharmaceutical industries to establish their quality control profile.

  3. Quantification of methyl esters of fatty acids in the oil of Physalis minima by GC-MS

    Directory of Open Access Journals (Sweden)

    Muhammad Nasimullah Qureshi

    2015-02-01

    Full Text Available Objective: To investigate quantification of methyl esters of fatty acids in the oil extracted from Physalis minima (P. minima using gas chromatography-mass spectrometer. Methods: Oil was extracted from the shade dried plant with n-hexane through Soxhlet extraction. Fatty acids that present in the oil were derivatized to fatty acid methyl esters and analysed through gas chromatography-mass spectrometer. Results: A total of nine fatty acids were detected in quantifiable amount in the oil. Both the saturated fatty acids and unsaturated fatty acids were identified. Palmitic acid was found in the highest concentration as 46.83%. Linoleic acid (ω-6 and linolenic acid (ω-3 were obtained in appreciable amount as 16.98% and 14.80% respectively among the unsaturated fatty acids in the oil under study. From the literature review, it appeared that fatty acids were determined for the first time in the oil of P. minima. Conclusions: Presence of these important fatty acids in high amount makes P. minima oil beneficial for health, which can be used in the preparation of phytopharmaceutical or pharmaceutical preparations. Moreover, the results of this study are useful for the phytopharmaceutical industries to establish their quality control profile.

  4. MECHANICAL PROPERTIES OF BLENDS OF PAMAM DENDRIMERS WITH POLY(VINYL CHLORIDE) AND POLY(VINYL ACETATE)

    Science.gov (United States)

    Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonacne ...

  5. Design and biological properties of iodine-123 labeled. beta. -methyl-branched fatty acids

    Energy Technology Data Exchange (ETDEWEB)

    Knapp, F.F. Jr.; Goodman, M.M.

    1984-01-01

    The synthetic strategy, synthesis, preclinical evaluation and potential clinical applications of 3-methyl-branched radioiodinated iodophenyl- and iodovinyl-substituted fatty acids are reviewed for use as myocardial imaging agents. 50 references, 6 figures. (ACR)

  6. Synthesis of Novel Ether Thionocarbamates and Study on Their Flotation Performance for Chalcopyrite

    Directory of Open Access Journals (Sweden)

    Gang Zhao

    2016-09-01

    Full Text Available Novel ether thionocarbamates, O-butoxy isopropyl-N-ethoxycarbonyl thionocarbamate (BIPECTC and O-(2-butoxy-1-methylethoxy isopropyl-N-ethoxycarbonyl thionocarbamate (BMIPECTC, were synthesized in this study. Their collecting efficiencies in the flotation of chalcopyrite were investigated using flotation tests, adsorption measurements, ultraviolet spectra (UV and Fourier transform-infrared spectroscopy (FT-IR and density functional theory (DFT calculations. The synthesized ether thionocarbamates showed better frothing properties than methyl-isobutyl-carbinol (MIBC and stronger affinity to chalcopyrite compared with O-isopropyl-N-ethyl thionocarbamate (IPETC and O-isobutyl-N-ethoxycarbonyl thionocarbamate (IBECTC. UV spectra analysis showed that the ether thionocarbamates react with Cu2+, with the exception of Fe2+, Ni2+, Zn2+ and Pb2+. Additionally, it was further confirmed by FTIR spectra that a chemical reaction occurs between copper ion and BIPECTC and BMIPECTC. The adsorption capacity measurements revealed that chalcopyrite exhibits good adsorption ability for ether thionocarbamates at an approximate pH of 8–10, which agrees with the flotation tests. The quantum chemistry calculation results indicated that the ether thionocarbamates exhibit stronger collecting ability for copper mineral in terms of frontier molecular orbital analysis, binding model simulation with copper ions and the molecular hydrophobicity compared with IPETC and IBECTC. The computational results are in very good agreement with the experimental results.

  7. Folic Acid Reduces Tau Phosphorylation by Regulating PP2A Methylation in Streptozotocin-Induced Diabetic Mice

    Science.gov (United States)

    Zheng, Miaoyan; Zou, Chen; Li, Mengyue; Huang, Guowei; Gao, Yuxia; Liu, Huan

    2017-01-01

    High incidence rate of Alzheimer’s disease (AD) is observed in patients with type 2 diabetes. Aggregated β-amyloid (Aβ) and hyperphosphorylated tau are the hallmarks of AD. Hyperphosphorylated tau has been detected in diabetic animals as well as in diabetic patients. Folates mediate the transfer of one carbon unit, required in various biochemical reactions. The effect of folate on tau phosphorylation in diabetic models still remains unknown. In this study, we investigated the effect and mechanism of folic acid on hyperphosphorylation of tau in streptozotocin (STZ)-induced diabetic mice. Diabetic mice induced by STZ, at the age of 10 weeks, were administered with three levels of folic acid: folic acid-deficient diet, diet with normal folic acid content, and 120 μg/kg folic acid diet for 8 weeks. Levels of serum folate and blood glucose were monitored. Tau phosphorylation, protein phosphatase 2A (PP2A) methylation, and Glycogen synthase kinase 3β (GSK-3β) phosphorylation were detected using Western blot. The S-adenosyl methionine:S-adenosyl homocysteine ratio (SAM:SAH) in brain tissues was also determined. DNA methyltransferase (DNMT) mRNA expression levels were detected using real-time PCR. Folic acid reduced tau hyperphosphorylation at Ser396 in the brain of diabetes mellitus (DM) mice. In addition, PP2A methylation and DNMT1 mRNA expression were significantly increased in DM mice post folic acid treatment. GSK-3β phosphorylation was not regulated by folic acid administration. Folic acid can reduce tau phosphorylation by regulating PP2A methylation in diabetic mice. These results support that folic acid can serve as a multitarget neuronal therapeutic agent for treating diabetes-associated cognitive dysfunction. PMID:28422052

  8. Validation of methodologies for the analysis of lead and methyl-ether in gasoline, using the techniques of atomic emission with plasma source coupled inductively and micellar liquid chromatography

    International Nuclear Information System (INIS)

    Redondo Escalante, M.

    1995-01-01

    This study established and optimized the experimental variables for the lead quantization through the Icp-Aes technique, in aqueous media. A comparative study of several proposal methods, that appears in the literature for the extraction in aqueous media of the lead in gasoline was made. It determined that it is not possible, to make this procedure using the reaction of hydrolysis of tetraethyl lead. The op tim conditions were established, for the lead quantization in gasoline, using methyl-isobutyl-ketone and also ethanol as dis solvents. The conditions of the proposed methodologies were optimized, and the variables of analytical performance were defined. It was demonstrated, that it is possible to prepare lead dissolution patterns, in organic media, starting from inorganic salts of this metal. The techniques of chromatography of gases and of liquid chromatography of high pressure, in the analysis of methyl-ter butyl-ether (Mtbe), were compared. It demonstrated that it is possible, to quantize the Mtbe through the HPLC technique, and it found that the 'micellar' liquid chromatography. (author) [es

  9. Effect of degree of sulfonation and casting solvent on sulfonated poly(ether ether ketone) membrane for vanadium redox flow battery

    Science.gov (United States)

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

    2015-07-01

    The properties of sulfonated poly(ether ether ketone) (SPEEK) membranes with various degree of sulfonation (DS) and casting solvent are investigated for vanadium redox flow battery (VRFB). The optimum DS of SPEEK membrane is firstly confirmed by various characterizations such as physicochemical properties, ion selectivity, and VRFB single-cell performance. Subsequently the optimum casting solvent is selected for the optimum DS SPEEK membrane within N,N‧-dimethylformamide (DMF), N,N‧-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The different performance of SPEEK membranes prepared with various casting solvents can be attributed to the different interaction between solvent and -SO3H group of SPEEK. In the VRFB single-cell test, the optimum SPEEK membrane with DS of 67% and casting solvent of DMF (S67-DMF membrane) exhibits higher VRFB efficiencies and better cycle-life performance at 80 mA cm-2. The investigation of various DS and casting solvent will be effective guidance on the selection and modification of SPEEK membrane towards VRFB application.

  10. Sugar-Responsive Layer-by-Layer Film Composed of Phenylboronic Acid-Appended Insulin and Poly(vinyl alcohol).

    Science.gov (United States)

    Takei, Chihiro; Ohno, Yui; Seki, Tomohiro; Miki, Ryotaro; Seki, Toshinobu; Egawa, Yuya

    2018-01-01

    Previous studies have shown that reversible chemical bond formation between phenylboronic acid (PBA) and 1,3-diol can be utilized as the driving force for the preparation of layer-by-layer (LbL) films. The LbL films composed of a PBA-appended polymer and poly(vinyl alcohol) (PVA) disintegrated in the presence of sugar. This type of LbL films has been recognized as a promising approach for sugar-responsive drug release systems, but an issue preventing the practical application of LbL films is combining them with insulin. In this report, we have proposed a solution for this issue by using PBA-appended insulin as a component of the LbL film. We prepared two kinds of PBA-appended insulin derivatives and confirmed that they retained their hypoglycemic activity. The LbL films composed of PBA-appended insulin and PVA were successfully prepared through reversible chemical bond formation between the boronic acid moiety and the 1,3-diol of PVA. The LbL film disintegrated upon treatment with sugars. Based on the results presented herein, we discuss the suitability of the PBA moiety with respect to hypoglycemic activity, binding ability, and selectivity for D-glucose.

  11. Role of dietary fatty acids in liver injury caused by vinyl chloride metabolites in mice

    Energy Technology Data Exchange (ETDEWEB)

    Anders, Lisanne C [Department of Pharmacology and Toxicology, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Department of Medicine, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Yeo, Heegook; Kaelin, Brenna R; Lang, Anna L; Bushau, Adrienne M; Douglas, Amanda N [Department of Pharmacology and Toxicology, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Cave, Matt [Department of Pharmacology and Toxicology, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Department of Medicine, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Hepatobiology and Toxicology Program, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Diabetes and Obesity Center, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Robley Rex Louisville VAMC, Louisville, KY 40206 (United States); Arteel, Gavin E [Department of Pharmacology and Toxicology, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Hepatobiology and Toxicology Program, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); McClain, Craig J [Department of Pharmacology and Toxicology, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Department of Medicine, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Hepatobiology and Toxicology Program, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Diabetes and Obesity Center, University of Louisville Health Sciences Center, Louisville, KY 40292 (United States); Robley Rex Louisville VAMC, Louisville, KY 40206 (United States); and others

    2016-11-15

    Background: Vinyl chloride (VC) causes toxicant-associated steatohepatitis at high exposure levels. Recent work by this group suggests that underlying liver disease may predispose the liver to VC hepatotoxicity at lower exposure levels. The most common form of underlying liver disease in the developed world is non-alcoholic fatty liver disease (NAFLD). It is well-known that the type of dietary fat can play an important role in the pathogenesis of NAFLD. However, whether the combination of dietary fat and VC/metabolites promotes liver injury has not been studied. Methods: Mice were administered chloroethanol (CE - a VC metabolite) or vehicle once, 10 weeks after being fed diets rich in saturated fatty acids (HSFA), rich in poly-unsaturated fatty acids (HPUFA), or the respective low-fat control diets (LSFA; LPUFA). Results: In control mice, chloroethanol caused no detectable liver injury, as determined by plasma transaminases and histologic indices of damage. In HSFA-fed mice, chloroethanol increased HSFA-induced liver damage, steatosis, infiltrating inflammatory cells, hepatic expression of proinflammatory cytokines, and markers of endoplasmic reticulum (ER) stress. Moreover, markers of inflammasome activation were increased, while markers of inflammasome inhibition were downregulated. In mice fed HPUFA all of these effects were significantly attenuated. Conclusions: Chloroethanol promotes inflammatory liver injury caused by dietary fatty acids. This effect is far more exacerbated with saturated fat, versus poly-unsaturated fat; and strongly correlates with a robust activation of the NLRP3 inflammasome in the saturated fed animals only. Taken together these data support the hypothesis that environmental toxicant exposure can exacerbate the severity of NAFLD/NASH. - Highlights: • CE promotes inflammatory liver injury caused by dietary fatty acids. • This effect is stronger with saturated than with unsaturated fatty acids. • Damage caused by saturated fat and CE

  12. Role of dietary fatty acids in liver injury caused by vinyl chloride metabolites in mice

    International Nuclear Information System (INIS)

    Anders, Lisanne C; Yeo, Heegook; Kaelin, Brenna R; Lang, Anna L; Bushau, Adrienne M; Douglas, Amanda N; Cave, Matt; Arteel, Gavin E; McClain, Craig J

    2016-01-01

    Background: Vinyl chloride (VC) causes toxicant-associated steatohepatitis at high exposure levels. Recent work by this group suggests that underlying liver disease may predispose the liver to VC hepatotoxicity at lower exposure levels. The most common form of underlying liver disease in the developed world is non-alcoholic fatty liver disease (NAFLD). It is well-known that the type of dietary fat can play an important role in the pathogenesis of NAFLD. However, whether the combination of dietary fat and VC/metabolites promotes liver injury has not been studied. Methods: Mice were administered chloroethanol (CE - a VC metabolite) or vehicle once, 10 weeks after being fed diets rich in saturated fatty acids (HSFA), rich in poly-unsaturated fatty acids (HPUFA), or the respective low-fat control diets (LSFA; LPUFA). Results: In control mice, chloroethanol caused no detectable liver injury, as determined by plasma transaminases and histologic indices of damage. In HSFA-fed mice, chloroethanol increased HSFA-induced liver damage, steatosis, infiltrating inflammatory cells, hepatic expression of proinflammatory cytokines, and markers of endoplasmic reticulum (ER) stress. Moreover, markers of inflammasome activation were increased, while markers of inflammasome inhibition were downregulated. In mice fed HPUFA all of these effects were significantly attenuated. Conclusions: Chloroethanol promotes inflammatory liver injury caused by dietary fatty acids. This effect is far more exacerbated with saturated fat, versus poly-unsaturated fat; and strongly correlates with a robust activation of the NLRP3 inflammasome in the saturated fed animals only. Taken together these data support the hypothesis that environmental toxicant exposure can exacerbate the severity of NAFLD/NASH. - Highlights: • CE promotes inflammatory liver injury caused by dietary fatty acids. • This effect is stronger with saturated than with unsaturated fatty acids. • Damage caused by saturated fat and CE

  13. Clinical Significance of Retinoic Acid Receptor Beta Promoter Methylation in Prostate Cancer: A Meta-Analysis.

    Science.gov (United States)

    Dou, MengMeng; Zhou, XueLiang; Fan, ZhiRui; Ding, XianFei; Li, LiFeng; Wang, ShuLing; Xue, Wenhua; Wang, Hui; Suo, Zhenhe; Deng, XiaoMing

    2018-01-01

    Retinoic acid receptor beta (RAR beta) is a retinoic acid receptor gene that has been shown to play key roles during multiple cancer processes, including cell proliferation, apoptosis, migration and invasion. Numerous studies have found that methylation of the RAR beta promoter contributed to the occurrence and development of malignant tumors. However, the connection between RAR beta promoter methylation and prostate cancer (PCa) remains unknown. This meta-analysis evaluated the clinical significance of RAR beta promoter methylation in PCa. We searched all published records relevant to RAR beta and PCa in a series of databases, including PubMed, Embase, Cochrane Library, ISI Web of Science and CNKI. The rates of RAR beta promoter methylation in the PCa and control groups (including benign prostatic hyperplasia and normal prostate tissues) were summarized. In addition, we evaluated the source region of available samples and the methods used to detect methylation. To compare the incidence and variation in RAR beta promoter methylation in PCa and non-PCa tissues, the odds ratio (OR) and 95% confidence interval (CI) were calculated accordingly. All the data were analyzed with the statistical software STATA 12.0. Based on the inclusion and exclusion criteria, 15 articles assessing 1,339 samples were further analyzed. These data showed that the RAR beta promoter methylation rates in PCa tissues were significantly higher than the rates in the non-PCa group (OR=21.65, 95% CI: 9.27-50.57). Subgroup analysis according to the source region of samples showed that heterogeneity in Asia was small (I2=0.0%, P=0.430). Additional subgroup analysis based on the method used to detect RAR beta promoter methylation showed that the heterogeneity detected by MSP (methylation-specific PCR) was relatively small (I2=11.3%, P=0.343). Although studies reported different rates for RAR beta promoter methylation in PCa tissues, the total analysis demonstrated that RAR beta promoter methylation

  14. Clinical Significance of Retinoic Acid Receptor Beta Promoter Methylation in Prostate Cancer: A Meta-Analysis

    Directory of Open Access Journals (Sweden)

    MengMeng Dou

    2018-03-01

    Full Text Available Background/Aims: Retinoic acid receptor beta (RAR beta is a retinoic acid receptor gene that has been shown to play key roles during multiple cancer processes, including cell proliferation, apoptosis, migration and invasion. Numerous studies have found that methylation of the RAR beta promoter contributed to the occurrence and development of malignant tumors. However, the connection between RAR beta promoter methylation and prostate cancer (PCa remains unknown. This meta-analysis evaluated the clinical significance of RAR beta promoter methylation in PCa. Materials and Methods: We searched all published records relevant to RAR beta and PCa in a series of databases, including PubMed, Embase, Cochrane Library, ISI Web of Science and CNKI. The rates of RAR beta promoter methylation in the PCa and control groups (including benign prostatic hyperplasia and normal prostate tissues were summarized. In addition, we evaluated the source region of available samples and the methods used to detect methylation. To compare the incidence and variation in RAR beta promoter methylation in PCa and non-PCa tissues, the odds ratio (OR and 95% confidence interval (CI were calculated accordingly. All the data were analyzed with the statistical software STATA 12.0. Results: Based on the inclusion and exclusion criteria, 15 articles assessing 1,339 samples were further analyzed. These data showed that the RAR beta promoter methylation rates in PCa tissues were significantly higher than the rates in the non-PCa group (OR=21.65, 95% CI: 9.27-50.57. Subgroup analysis according to the source region of samples showed that heterogeneity in Asia was small (I2=0.0%, P=0.430. Additional subgroup analysis based on the method used to detect RAR beta promoter methylation showed that the heterogeneity detected by MSP (methylation-specific PCR was relatively small (I2=11.3%, P=0.343. Conclusion: Although studies reported different rates for RAR beta promoter methylation in PCa

  15. Thermal and Dielectric Behavior Studies of Poly(Arylene Ether Sulfones with Sulfonated and Phosphonated Pendants

    Directory of Open Access Journals (Sweden)

    Shimoga D. Ganesh

    2016-01-01

    Full Text Available The present paper discusses the aspects of the synthesizing valeric acid based poly(ether sulfones with active carboxylic acid pendants (VALPSU from solution polymerization technique via nucleophilic displacement polycondensation reaction among 4,4′-dichlorodiphenyl sulfone (DCDPS and 4,4′-bis(4-hydroxyphenyl valeric acid (BHPA. The conditions necessary to synthesize and purify the polymer were investigated in some detail. The synthesized poly(ether sulfones comprise sulfone and ether linkages in addition to reactive carboxylic acid functionality; these active carboxylic acid functional groups were exploited to hold the phenyl sulphonic acid and phenyl phosphonic acid pendants. The phenyl sulphonic acid pendants in VALPSU were easily constructed by altering active carboxylic acid moieties by sulfanilic acid using N,N′-dicyclohexylcarbodiimide (DCC mediated mild synthetic route, whereas the latter one was built in two steps. Initially, polyphosphoric acid condensation with VALPSU by 4-bromoaniline and next straightforward palladium catalyzed synthetic route, in both of which acidic pendants are clenched by polymer backbone via amide linkage. Without impairing the primary polymeric backbone modified polymers were prepared by varying the stoichiometric ratios of respective combinations. All the polymers were physicochemically characterized and pressed into tablets; electrical contacts were established to study the dielectric properties. Finally, the influence of the acidic pendants on the dielectric properties was examined.

  16. Coriander seed oil methyl esters as biodiesel fuel: Unique fatty acid composition and excellent oxidative stability

    International Nuclear Information System (INIS)

    Moser, Bryan R.; Vaughn, Steven F.

    2010-01-01

    Coriander (Coriandrum sativum L.) seed oil methyl esters were prepared and evaluated as an alternative biodiesel fuel and contained an unusual fatty acid hitherto unreported as the principle component in biodiesel fuels: petroselinic (6Z-octadecenoic; 68.5 wt%) acid. Most of the remaining fatty acid profile consisted of common 18 carbon constituents such as linoleic (9Z,12Z-octadeca-dienoic; 13.0 wt%), oleic (9Z-octadecenoic; 7.6 wt%) and stearic (octadecanoic; 3.1 wt%) acids. A standard transesterification procedure with methanol and sodium methoxide catalyst was used to provide C. sativum oil methyl esters (CSME). Acid-catalyzed pretreatment was necessary beforehand to reduce the acid value of the oil from 2.66 to 0.47 mg g -1 . The derived cetane number, kinematic viscosity, and oxidative stability (Rancimat method) of CSME was 53.3, 4.21 mm 2 s -1 (40 o C), and 14.6 h (110 o C). The cold filter plugging and pour points were -15 o C and -19 o C, respectively. Other properties such as acid value, free and total glycerol content, iodine value, as well as sulfur and phosphorous contents were acceptable according to the biodiesel standards ASTM D6751 and EN 14214. Also reported are lubricity, heat of combustion, and Gardner color, along with a comparison of CSME to soybean oil methyl esters (SME). CSME exhibited higher oxidative stability, superior low temperature properties, and lower iodine value than SME. In summary, CSME has excellent fuel properties as a result of its unique fatty acid composition.

  17. Cosmic Ether

    CERN Document Server

    Tomaschitz, R

    1998-01-01

    A prerelativistic approach to particle dynamics is explored in an expanding Robertson-Walker cosmology. The receding galactic background provides a distinguished frame of reference and a unique cosmic time. In this context the relativistic, purely geometric space-time concept is criticized. Physical space is regarded as a permeable medium, the cosmic ether, which effects the world-lines of particles and rays. We study in detail a Robertson-Walker universe with linear expansion factor and negatively curved, open three-space; we choose the permeability tensor of the ether in such a way that the semiclassical approximation is exact. Galactic red-shifts depend on the refractive index of the ether. In the local Minkowskian limit the ether causes a time variation of mass, which scales inversely proportional to cosmic time. In the globally geodesic rest frames of galactic observers the ether manifests itself in an unbounded speed of signal transfer, in bifurcations of world-lines, and in time inversion effects.

  18. Compliant gel polymer electrolyte based on poly(methyl acrylate-co-acrylonitrile)/poly(vinyl alcohol) for flexible lithium-ion batteries

    International Nuclear Information System (INIS)

    Ma, Xianguo; Huang, Xinglan; Gao, Jiandong; Zhang, Shu; Deng, Zhenghua; Suo, Jishuan

    2014-01-01

    Highlights: •Compliant gel polymer electrolyte based on P(MA-co-AN)/PVA is facilely prepared for flexible lithium-ion batteries. •The compliant gel polymer electrolyte displays high ionic conductivity, self-standing and mechanical flexible. •The compliant gel polymer electrolyte exhibits excellent chemical and electrochemical performances. -- Abstract: In this report, mechanically compliant gel polymer electrolyte (GPE) for flexible lithium-ion batteries is facilely fabricated. The GPE that based on the poly(methyl acrylate-co-acrylonitrile)/poly(vinyl alcohol) (P(MA-co-AN)/PVA) was prepared via emulsion polymerization. Herein, the P(MA-co-AN) copolymer is anticipated to exert beneficial for the bendability of the GPE, as well as swollen with the liquid electrolyte to provide a facile pathway for ion movement. The PVA serves as a stabilizer during the emulsion polymerization and a mechanical framework for the compliant polymer membrane. Performance benefits of the mechanically compliant membrane are elucidated in terms of mechanical behavior, thermostability and ionic conductivity. The GPE is still self-standing and mechanical flexible after swollen with liquid electrolyte. The GPE displays a conductivity of 0.98 mS cm −1 with the uptake electrolyte up to 150% of its own weight at 30 °C, excellent electrochemical stability window (5.2 V vs. Li/Li + ) and favorable interfacial characteristics. When used in flexible lithium-ion batteries, such a GPE demonstrates satisfactory compatibility with LiCoO 2 and graphite electrodes

  19. Classification of bacteria by simultaneous methylation-solid phase microextraction and gas chromatography/mass spectrometry analysis of fatty acid methyl esters.

    Science.gov (United States)

    Lu, Yao; Harrington, Peter B

    2010-08-01

    Direct methylation and solid-phase microextraction (SPME) were used as a sample preparation technique for classification of bacteria based on fatty acid methyl ester (FAME) profiles. Methanolic tetramethylammonium hydroxide was applied as a dual-function reagent to saponify and derivatize whole-cell bacterial fatty acids into FAMEs in one step, and SPME was used to extract the bacterial FAMEs from the headspace. Compared with traditional alkaline saponification and sample preparation using liquid-liquid extraction, the method presented in this work avoids using comparatively large amounts of inorganic and organic solvents and greatly decreases the sample preparation time as well. Characteristic gas chromatography/mass spectrometry (GC/MS) of FAME profiles was achieved for six bacterial species. The difference between Gram-positive and Gram-negative bacteria was clearly visualized with the application of principal component analysis of the GC/MS data of bacterial FAMEs. A cross-validation study using ten bootstrap Latin partitions and the fuzzy rule building expert system demonstrated 87 +/- 3% correct classification efficiency.

  20. Preparation and characterization of sulfonated amine-poly(ether sulfone)s for proton exchange membrane fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Seo, Dong-Wan; Lim, Young-Don; Lee, Soon-Ho; Jeong, Young-Gi; Kim, Whan-Gi [Department of Applied Chemistry/RIC-ReSEM, Konkuk University, Chungju-si, Chungbuk 380-701 (Korea, Republic of); Hong, Tae-Whan [Department of Materials Sci and Engineering/RIC-ReSEM, Chungju National University, Chungju, Chungbuk (Korea, Republic of)

    2010-12-15

    Sulfonated amine-poly(ether sulfone)s (S-APES)s were prepared by nitration, reduction and sulfonation of poly(ether sulfone) (ultrason {sup registered} -S6010). Poly(ether sulfone) was reacted with ammonium nitrate and trifluoroacetic anhydride to produce the nitrated poly(ether sulfone), and was followed by reduction using tin(II)chloride and sodium iodide as reducing agents to give the amino-poly(ether sulfone). The S-APES was obtained by reaction of 1,3-propanesultone and the amino-poly(ether sulfone) (NH{sub 2}-PES) with sodium methoxide. The different degrees of nitration and reduction of poly(ether sulfone) were successfully synthesized by an optimized process. The reduction of nitro group to amino was done quantitatively, and this controlled the contents of the sulfonic acid group. The films were converted from salt to acid forms with dilute hydrochloric acid. Different contents of sulfonated unit of the S-APES were studied by FT-IR, {sup 1}H NMR spectroscopy, differential scanning calorimetry (DSC), and thermo gravimetric analysis (TGA). Sorption experiments were conducted to observe the interaction of sulfonated polymers with water and methanol. The ion exchange capacity (IEC), a measure of proton conductivity, was evaluated. The S-APES membranes exhibit conductivities (25 C) from 1.05 x 10{sup -3} to 4.83 x 10{sup -3} S/cm, water swell from 30.25 to 66.50%, IEC from 0.38 to 0.82 meq/g, and methanol diffusion coefficients from 3.10 x 10{sup -7} to 4.82 x 10{sup -7} cm{sup 2}/S at 25 C. (author)

  1. The Effects of Reaction Variables on Solution Polymerization of Vinyl Acetate and Molecular Weight of Poly(vinyl alcohol Using Taguchi Experimental Design

    Directory of Open Access Journals (Sweden)

    M.H. Navarchian

    2009-12-01

    Full Text Available Poly(vinyl acetate is synthesized via solution polymerization, and then it is converted to poly(vinyl alcohol by alkaline alcoholysis. The aim of the work study was to investigate statistically the  influence of reaction variables in vinyl acetate polymerization, the conversion of this monomer to polymer, degree of branching of acetyl group in poly(vinyl acetate, as well as the molecular weight of poly(vinyl alcohol, using Taguchi experimental design approach. The reaction variables were polymerization time, molar ratio of initiator to monomer, and volume ratio of monomer to solvent. The statistical analysis of variance of the results revealed that all factors have significantly influenced the conversion and degree of branching. Volume ratio of monomer to solvent is the only factor affecting the molecular weight of poly(vinyl alcohol, and has the greatest influence on all responses. By increasing this ratio, the conversion, degree of branching of acetyl group in poly(vinyl acetate, and molecular weight of poly(vinyl alcohol were increased.

  2. Separation and Analysis of Microwave-assisted Liquefied Products of Corn Stover

    Directory of Open Access Journals (Sweden)

    Weihua Xiao

    2014-10-01

    Full Text Available Corn stover was successfully liquefied by microwave heating at 160 °C with ethylene glycol (EG used as the solvent and sulfuric acid as a catalyst. Gas chromatography and mass spectrometry (GC-MS data indicated that methyl esters, including 3-(2-methyl-1,3-doxolane-2-yl propionic acid methyl ester (PAME, levulinic acid isopropyl ester (LAE, methyl laurate, and methyl palmitate were the major degradation compounds, in addition to EG derivatives in the liquefied product of corn stover (LPCS. For high value-added utilization of LPCS, solvent extraction was applied to characterize the components and to separate it into useful fractions. After being dispersed in water, the water-soluble fraction of the LPCS was then extracted with organic solvents, including hexane, chloroform, diethyl ether, and ethyl acetate. Levulinic acid isopropyl ester showed the highest distribution in chloroform and ethyl acetate, while the lowest in hexane and ether. Levulinic acid isopropyl ester was selectively enriched to 28.76% and 43.65% by sequential extraction with chloroform and ethyl acetate, respectively, in accordance with the quantitative analysis.

  3. Thermal and Optical Properties of New Poly(amide-imide)/Nanocomposite Reinforced by Layer Silicate Containing Diphenyl Ether Moieties

    Science.gov (United States)

    Faghihi, Khalil; Faramarzi, Ellahe; Shabanian, Meisam

    2011-04-01

    New poly(amide-imide)-montmorillonite reinforced nanocomposites containing Bis(4-N-trimellitylimido) diphenyl ether moiety in the main chain were synthesized by a convenient solution intercalation technique. Poly(amide-imide) (PAI) 4 was synthesized by the direct polycondensation reaction of Bis(4-N-trimellitylimido) diphenyl ether 3 with 4,4'-diamino diphenyl ether 2 in the presence of triphenyl phosphite (TPP), CaCl2, pyridine and N-methyl-2-pyrrolidone (NMP). Morphology and structure of the resulting PAI-nanocomposite films 4a and 4b with 10 and 20 mass% silicate particles respectively, were characterized by FT-IR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The properties of nanocomposites films were investigated by using Uv-vis spectroscopy, thermogravimetric analysis (TGA) and water uptake measurements.

  4. Stereospecific enzymatic transformation of alpha-ketoglutarate to (2S,3R)-3-methyl glutamate during acidic lipopeptide biosynthesis.

    Science.gov (United States)

    Mahlert, Christoph; Kopp, Florian; Thirlway, Jenny; Micklefield, Jason; Marahiel, Mohamed A

    2007-10-03

    The acidic lipopeptides, including the calcium-dependent antibiotics (CDA), daptomycin, and A54145, are important macrocyclic peptide natural products produced by Streptomyces species. All three compounds contain a 3-methyl glutamate (3-MeGlu) as the penultimate C-terminal residue, which is important for bioactivity. Here, biochemical in vitro reconstitution of the 3-MeGlu biosynthetic pathway is presented, using exclusively enzymes from the CDA producer Streptomyces coelicolor. It is shown that the predicted 3-MeGlu methyltransferase GlmT and its homologues DptI from the daptomycin producer Streptomyces roseosporus and LptI from the A54145 producer Streptomyces fradiae do not methylate free glutamic acid, PCP-bound glutamate, or Glu-containing CDA in vitro. Instead, GlmT, DptI, and LptI are S-adenosyl methionine (SAM)-dependent alpha-ketoglutarate methyltransferases that catalyze the stereospecific methylation of alpha-ketoglutarate (alphaKG) leading to (3R)-3-methyl-2-oxoglutarate. Subsequent enzyme screening identified the branched chain amino acid transaminase IlvE (SCO5523) as an efficient catalyst for the transformation of (3R)-3-methyl-2-oxoglutarate into (2S,3R)-3-MeGlu. Comparison of reversed-phase HPLC retention time of dabsylated 3-MeGlu generated by the coupled enzymatic reaction with dabsylated synthetic standards confirmed complete stereocontrol during enzymatic catalysis. This stereospecific two-step conversion of alphaKG to (2S,3R)-3-MeGlu completes our understanding of the biosynthesis and incorporation of beta-methylated amino acids into the nonribosomal lipopeptides. Finally, understanding this pathway may provide new possibilities for the production of modified peptides in engineered microbes.

  5. Formation of molecular complexes of salicylic acid, acetylsalicylic acid, and methyl salicylate in a mixture of supercritical carbon dioxide with a polar cosolvent

    Science.gov (United States)

    Petrenko, V. E.; Antipova, M. L.; Gurina, D. L.; Odintsova, E. G.

    2015-08-01

    The solvate structures formed by salicylic acid, acetylsalicylic acid, and methyl salicylate in supercritical (SC) carbon dioxide with a polar cosolvent (methanol, 0.03 mole fractions) at a density of 0.7 g/cm3 and a temperature of 318 K were studied by the molecular dynamics method. Salicylic and acetylsalicylic acids were found to form highly stable hydrogen-bonded complexes with methanol via the hydrogen atom of the carboxyl group. For methyl salicylate in which the carboxyl hydrogen is substituted by a methyl radical, the formation of stable hydrogen bonds with methanol was not revealed. The contribution of other functional groups of the solute to the interactions with the cosolvent was much smaller. An analysis of correlations between the obtained data and the literature data on the cosolvent effect on the solubility of the compounds in SC CO2 showed that the dissolving ability of SC CO2 with respect to a polar organic substance in the presence of a cosolvent increased only when stable hydrogen-bonded complexes are formed between this substance and the cosolvent.

  6. Methylation of food commodities during fumigation with methyl bromide

    International Nuclear Information System (INIS)

    Starratt, A.N.; Bond, E.J.

    1990-01-01

    Sites of methylation in several commodities (wheat, oatmeal, peanuts, almonds, apples, oranges, maize, alfalfa and potatoes) during fumigation with 14 C-methyl bromide were studied. Differences were observed in levels of the major volatiles: methanol, dimethyl sulphide and methyl mercaptan, products of O- and S-methylation, resulting from treatment of the fumigated materials with 1N sodium hydroxide. In studies of maize and wheat, histidine was the amino acid which underwent the highest level of N-methylation. (author). 24 refs, 3 tabs

  7. Antimalarial effects of vinyl sulfone cysteine proteinase inhibitors.

    OpenAIRE

    Rosenthal, P J; Olson, J E; Lee, G K; Palmer, J T; Klaus, J L; Rasnick, D

    1996-01-01

    We evaluated the antimalarial effects of vinyl sulfone cysteine proteinase inhibitors. A number of vinyl sulfones strongly inhibited falcipain, a Plasmodium falciparum cysteine proteinase that is a critical hemoglobinase. In studies of cultured parasites, nanomolar concentrations of three vinyl sulfones inhibited parasite hemoglobin degradation, metabolic activity, and development. The antimalarial effects correlated with the inhibition of falcipain. Our results suggest that vinyl sulfones or...

  8. Adsorption of {alpha}-amylase onto poly(N-vinyl 2-pyrrolidone/itaconic acid) hydrogels

    Energy Technology Data Exchange (ETDEWEB)

    Tuemtuerk, Hayrettin; Caykara, Tuncer; Kantoglu, Oemer; Gueven, Olgun

    1999-05-02

    {alpha}-Amylase enzyme was adsorbed on poly(N-vinyl 2-pyrrolidone/itaconic acid) (P(VP/IA)) hydrogels prepared by irradiating the ternary mixtures of VP/IA/water by {gamma}-rays at ambient temperature. The adsorption capacity of the hydrogels was determined to increase from 2.30 to 3.40 mg {alpha}-amylase/g dry gel with increasing amount of IA in gel system. Kinetic parameters were calculated as 2.51 g/dm{sup 3} for K{sub m} and 1.67x10{sup -3} g/dm{sup 3} min for V{sub max} for free enzyme and in the range of 3.88-5.02 g/dm{sup 3} for K{sub m} and 1.62x10{sup -3}-2.27 x 10{sup -3} g/dm{sup 3} min for V{sub max} depending on the amount of IA in the hydrogel. Enzyme activities were found to increase from 49.9% to 77.4% with increasing amount of IA in the gel system and retained their activities for one month storage. On the other hand, the free enzyme loses its activity completely after 20 days.

  9. A highly sensitive and selective dimethyl ether sensor based on cataluminescence.

    Science.gov (United States)

    Zhang, Runkun; Cao, Xiaoan; Liu, Yonghui; Peng, Yan

    2010-07-15

    A sensor for detecting dimethyl ether was designed based on the cataluminescence phenomenon when dimethyl ether vapors were passing through the surface of the ceramic heater. The proposed sensor showed high sensitivity and selectivity to dimethyl ether at an optimal temperature of 279 degrees C. Quantitative analysis were performed at a wavelength of 425 nm, the flow rate of carrier air is around 300 mL/min. The linear range of the cataluminescence intensity versus concentration of dimethyl ether is 100-6.0x10(3) ppm with a detection limit of 80 ppm. The sensor response time is 2.5 s. Under the optimized conditions, none or only very low levels of interference were observed while the foreign substances such as benzene, formaldehyde, ammonia, methanol, ethanol, acetaldehyde, acetic acid, acrolein, isopropyl ether, ethyl acetate, glycol ether and 2-methoxyethanol were passing through the sensor. Since the sensor does not need to prepare and fix up the granular catalyst, the simple technology reduces cost, improves stability and extends life span. The method can be applied to facilitate detection of dimethyl ether in the air. The possible mechanism of cataluminescence from the oxidation of dimethyl ether on the surface of ceramic heater was discussed based on the reaction products. Copyright 2010 Elsevier B.V. All rights reserved.

  10. Co-solvents transesterification of cotton seed oil into biodiesel: Effects of reaction conditions on quality of fatty acids methyl esters

    International Nuclear Information System (INIS)

    Alhassan, Y.; Kumar, N.; Bugaje, I.M.; Pali, H.S.; Kathkar, P.

    2014-01-01

    Highlights: • Using co-solvent systems reduce reaction time by 60%. • Only small volume of co-solvent is required to improve the process. • Greater than 90% yields were obtained within the first 10 min. • Physico-chemical and fuel properties of FAMEs were within standard limits. • Acetone was found to be the best co-solvent for the transesterification. - Abstract: Solvent Technology, is gaining the interest of researchers in improving transesterification process recently. Transesterification of cotton seed oil into biodiesel using different mixtures of methanol with Diethyl Ether (DEE), Dichlorobenzene (CBN) or Acetone (ACT) co-solvent systems was conducted. Potassium hydroxide (KOH) was used as the catalyst all through. The reaction conditions optimized include; the molar ratio of co-solvent in methanol, reaction temperature and time. The catalyst concentration was also optimized. The optimization was based on the percentage yields of Fatty Acids Methyl Esters (FAMEs) produced. In addition, the effects of co-solvent systems on physico-chemical properties (Acid value and fatty acids composition) and fuel properties (viscosity, density and calorific value) were investigated as well. The result obtained, indicated 10% (v/v) addition of co-solvents CBN and ACT in methanol was the optimal volume. The optimal reaction temperature was 55 ° 0 C for 10 min when the catalyst concentration of 0.75% (w/w) weight of oil was used. Fuel properties were within the acceptable limit of ASTM and not significantly affected by the co-solvent systems except for the calorific value. It was concluded that the addition of co-solvent reduced the reaction time and improved some fuel properties of the biodiesel produced

  11. The surface modifications of multi-walled carbon nanotubes for multi-walled carbon nanotube/poly(ether ether ketone) composites

    International Nuclear Information System (INIS)

    Cao, Zongshuang; Qiu, Li; Yang, Yongzhen; Chen, Yongkang; Liu, Xuguang

    2015-01-01

    Graphical abstract: Multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites incorporating surface modified multi-walled carbon nanotubes (MWCNTs) as fillers were fabricated in a solution blending method in order to explore the dynamic mechanical and tribological properties of MWCNT/PEEK composites systematically. It is evident that surface modifications of MWCNTs have a significant impact on dispersibility of MWCNTs in PEEK, dynamic mechanical and tribological properties of MWCNT/PEEK composites. Typically, a clear effect of surface modifications of MWCNTs on tribological properties of MWCNT/PEEK composites was observed. A significant reduction in frictional coefficient of MWCNT/PEEK composites with the MWCNTs modified with ethanolamine has been achieved and the self-lubricating film on their worn surfaces was also observed. - Highlights: • The dispersibility of surface modified MWCNTs in PEEK has been studied. • MWCNTs modified with ethanolamine have showed a good dispersion in PEEK. • Surface modifications of MWCNTs have a significant impact on both dynamic mechanical and tribological properties of MWCNT/PEEK composites. - Abstract: The effects of surface modifications of multi-walled carbon nanotubes (MWCNTs) on the morphology, dynamic mechanical and tribological properties of multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites have been investigated. MWCNTs were treated with mixed acids to obtain acid-functionalized MWCNTs. Then the acid-functionalized MWCNTs were modified with ethanolamine (named e-MWCNTs). The MWCNT/PEEK composites were prepared by a solution-blending method. A more homogeneous distribution of e-MWCNTs within the composites was found with scanning electron microscopy. Dynamic mechanical analysis demonstrated a clear increase in the storage modulus of e-MWCNT/PEEK composites because of the improved interfacial adhesion strength between e-MWCNTs and PEEK. Furthermore, the presence of e

  12. The surface modifications of multi-walled carbon nanotubes for multi-walled carbon nanotube/poly(ether ether ketone) composites

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Zongshuang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); Research Center of Advanced Material Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Qiu, Li [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China); Yang, Yongzhen, E-mail: yyztyut@126.com [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); Research Center of Advanced Material Science and Technology, Taiyuan University of Technology, Taiyuan 030024 (China); Chen, Yongkang, E-mail: y.k.chen@herts.ac.uk [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); University of Hertfordshire, School of Engineering and Technology, Hatfield, Hertfordshire AL10 9AB (United Kingdom); Liu, Xuguang [Key Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024 (China); College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024 (China)

    2015-10-30

    Graphical abstract: Multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites incorporating surface modified multi-walled carbon nanotubes (MWCNTs) as fillers were fabricated in a solution blending method in order to explore the dynamic mechanical and tribological properties of MWCNT/PEEK composites systematically. It is evident that surface modifications of MWCNTs have a significant impact on dispersibility of MWCNTs in PEEK, dynamic mechanical and tribological properties of MWCNT/PEEK composites. Typically, a clear effect of surface modifications of MWCNTs on tribological properties of MWCNT/PEEK composites was observed. A significant reduction in frictional coefficient of MWCNT/PEEK composites with the MWCNTs modified with ethanolamine has been achieved and the self-lubricating film on their worn surfaces was also observed. - Highlights: • The dispersibility of surface modified MWCNTs in PEEK has been studied. • MWCNTs modified with ethanolamine have showed a good dispersion in PEEK. • Surface modifications of MWCNTs have a significant impact on both dynamic mechanical and tribological properties of MWCNT/PEEK composites. - Abstract: The effects of surface modifications of multi-walled carbon nanotubes (MWCNTs) on the morphology, dynamic mechanical and tribological properties of multi-walled carbon nanotube/poly(ether ether ketone) (MWCNT/PEEK) composites have been investigated. MWCNTs were treated with mixed acids to obtain acid-functionalized MWCNTs. Then the acid-functionalized MWCNTs were modified with ethanolamine (named e-MWCNTs). The MWCNT/PEEK composites were prepared by a solution-blending method. A more homogeneous distribution of e-MWCNTs within the composites was found with scanning electron microscopy. Dynamic mechanical analysis demonstrated a clear increase in the storage modulus of e-MWCNT/PEEK composites because of the improved interfacial adhesion strength between e-MWCNTs and PEEK. Furthermore, the presence of e

  13. Gene mdpC plays a regulatory role in the methyl-tert-butyl ether degradation pathway of Methylibium petroleiphilum strain PM1.

    Science.gov (United States)

    Joshi, Geetika; Schmidt, Radomir; Scow, Kate M; Denison, Michael S; Hristova, Krassimira R

    2015-04-01

    Among the few bacteria known to utilize methyl tert-butyl ether (MTBE) as a sole carbon source, Methylibium petroleiphilum PM1 is a well-characterized organism with a sequenced genome; however, knowledge of the genetic regulation of its MTBE degradation pathway is limited. We investigated the role of a putative transcriptional activator gene, mdpC, in the induction of MTBE-degradation genes mdpA (encoding MTBE monooxygenase) and mdpJ (encoding tert-butyl alcohol hydroxylase) of strain PM1 in a gene-knockout mutant mdpC(-). We also utilized quantitative reverse transcriptase PCR assays targeting genes mdpA, mdpJ and mdpC to determine the effects of the mutation on transcription of these genes. Our results indicate that gene mdpC is involved in the induction of both mdpA and mdpJ in response to MTBE and tert-butyl alcohol (TBA) exposure in PM1. An additional independent mechanism may be involved in the induction of mdpJ in the presence of TBA. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  14. Folic Acid Supplementation Delays Atherosclerotic Lesion Development by Modulating MCP1 and VEGF DNA Methylation Levels In Vivo and In Vitro

    Science.gov (United States)

    Cui, Shanshan; Li, Wen; Lv, Xin; Wang, Pengyan; Gao, Yuxia; Huang, Guowei

    2017-01-01

    The pathogenesis of atherosclerosis has been partly acknowledged to result from aberrant epigenetic mechanisms. Accordingly, low folate levels are considered to be a contributing factor to promoting vascular disease because of deregulation of DNA methylation. We hypothesized that increasing the levels of folic acid may act via an epigenetic gene silencing mechanism to ameliorate atherosclerosis. Here, we investigated the atheroprotective effects of folic acid and the resultant methylation status in high-fat diet-fed ApoE knockout mice and in oxidized low-density lipoprotein-treated human umbilical vein endothelial cells. We analyzed atherosclerotic lesion histology, folate concentration, homocysteine concentration, S-adenosylmethionine (SAM) and S-adenosylhomocysteine (SAH), and DNA methyltransferase activity, as well as monocyte chemotactic protein-1 (MCP1) and vascular endothelial growth factor (VEGF) expression and promoter methylation. Folic acid reduced atherosclerotic lesion size in ApoE knockout mice. The underlying folic acid protective mechanism appears to operate through regulating the normal homocysteine state, upregulating the SAM: SAH ratio, elevating DNA methyltransferase activity and expression, altering MCP1 and VEGF promoter methylation, and inhibiting MCP1 and VEGF expression. We conclude that folic acid supplementation effectively prevented atherosclerosis by modifying DNA methylation through the methionine cycle, improving DNA methyltransferase activity and expression, and thus changing the expression of atherosclerosis-related genes. PMID:28475147

  15. Isolation and characterization of fatty acid methyl ester (FAME)-producing Streptomyces sp. S161 from sheep (Ovis aries) faeces.

    Science.gov (United States)

    Lu, Y; Wang, J; Deng, Z; Wu, H; Deng, Q; Tan, H; Cao, L

    2013-09-01

    An actinomycete producing oil-like mixtures was isolated and characterized. The strain was isolated from sheep faeces and identified as Streptomyces sp. S161 based on 16S rRNA gene sequence analysis. The strain showed cellulase and xylanase activities. The (1) H nuclear magnetic resonance (NMR) spectra of the mixtures showed that the mixtures were composed of fatty acid methyl esters (52·5), triglycerides (13·7) and monoglycerides (9·1) (mol.%). Based on the gas chromatography-mass spectrometry (GC-MS) analysis, the fatty acid methyl esters were mainly composed of C14-C16 long-chain fatty acids. The results indicated that Streptomyces sp. S161 could produce fatty acid methyl esters (FAME) directly from starch. To our knowledge, this is the first isolated strain that can produce biodiesel (FAME) directly from starch. © 2013 The Society for Applied Microbiology.

  16. Antioxidant activity of gallic acid and methyl gallate in triacylglycerols of Kilka fish oil and its oil-in-water emulsion.

    Science.gov (United States)

    Asnaashari, Maryam; Farhoosh, Reza; Sharif, Ali

    2014-09-15

    The anti-DPPH radical effect as well as anti-peroxide activity of gallic acid, methyl gallate, and α-tocopherol in a bulk Kilka fish oil and its oil-in-water emulsion stabilized by soy protein isolate at 55°C were investigated. Gallic acid with the lowest hydrophobicity (log P=-0.28) was found to be the most active antiradical agent (IC50=29.5 μM), followed by methyl gallate (IC50=38.0 μM, log P=-0.23) and α-tocopherol (IC50=105.3 μM, log P=0.70). The anti-peroxide activity in the bulk oil system decreased in the order of methyl gallate>gallic acid>α-tocopherol. In the emulsion system, methyl gallate still behaved better than gallic acid, but the highest activity belonged to α-tocopherol. Based on the calculation of a number of kinetic parameters, the antioxidants, in general, showed better performances in the bulk oil system than in the emulsion system. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. 75 FR 78243 - Propionic Acid and Salts, Urea Sulfate, Methidathion, and Methyl Parathion; Registration Review...

    Science.gov (United States)

    2010-12-15

    ... ENVIRONMENTAL PROTECTION AGENCY [EPA-HQ-OPP-2010-0650; FRL-8855-5] Propionic Acid and Salts, Urea.... 4078, urea sulfate, case no. 7213, methidathion, case no. 0034, and methyl parathion, case no. 0153... pesticides in the table below--propionic acid and salts, case 4078, urea sulfate, case no. 7213, methidathion...

  18. Misconceptions about the ether

    International Nuclear Information System (INIS)

    Duffy, M.C.

    1980-01-01

    Several misconceptions concerning the ether concept and ether models are reviewed and clarified so that the relationship between modern ether theory and orthodox relativity may be better understood. The question of the ether's supposed superfluidity as a concept, and its status in modern physics remains to be answered. (author)

  19. Glycerol tertiary butyl ethers via etherification of glycerol with isobutene

    Energy Technology Data Exchange (ETDEWEB)

    Behr, A. [Dortmund Univ. (Germany). Chair of Chemical Process Development/Technical Chemistry A

    2007-07-01

    Glycerol and isobutene can react to a mixture of glycerol tertiary butyl ethers (GTBE) which can be used as additives for gasoline, diesel or biodiesel. This reaction was investigated in lab scale yielding a proposal for a process flow diagram containing reaction, extraction, flash and rectification units. This process has the advantages that only the suitable higher ethers are formed and that both glycerol and isobutene are fully converted. The homogeneous acid catalyst is low-priced and can be completely recycled. (orig.)

  20. Conversion of beet molasses and cheese whey into fatty acid methyl esters by the yeast Cryptococcus curvatus.

    Science.gov (United States)

    Takakuwa, Naoya; Saito, Katsuichi

    2010-01-01

    Eighty-one yeast isolates from raw milk were surveyed for the production of fatty acid methyl esters (FAME). Only one species, identified as Cryptococcus curvatus, produced FAME at a detectable level. Cr. curvatus TYC-19 produced more FAME from beet molasses and cheese whey medium than other strains of the same species. In both media, the major FAME produced were linoleic and oleic acid methyl esters. Sequence analysis of the internal transcribed spacer region of ribosomal DNA indicated that TYC-19 diverged from the same species.